Nonadiabatic effects in electronic and nuclear dynamics
Martin P. Bircher
2017-11-01
Full Text Available Due to their very nature, ultrafast phenomena are often accompanied by the occurrence of nonadiabatic effects. From a theoretical perspective, the treatment of nonadiabatic processes makes it necessary to go beyond the (quasi static picture provided by the time-independent Schrödinger equation within the Born-Oppenheimer approximation and to find ways to tackle instead the full time-dependent electronic and nuclear quantum problem. In this review, we give an overview of different nonadiabatic processes that manifest themselves in electronic and nuclear dynamics ranging from the nonadiabatic phenomena taking place during tunnel ionization of atoms in strong laser fields to the radiationless relaxation through conical intersections and the nonadiabatic coupling of vibrational modes and discuss the computational approaches that have been developed to describe such phenomena. These methods range from the full solution of the combined nuclear-electronic quantum problem to a hierarchy of semiclassical approaches and even purely classical frameworks. The power of these simulation tools is illustrated by representative applications and the direct confrontation with experimental measurements performed in the National Centre of Competence for Molecular Ultrafast Science and Technology.
Nonadiabatic electron wavepacket dynamics behind molecular autoionization
Matsuoka, Takahide; Takatsuka, Kazuo
2018-01-01
A theoretical method for real-time dynamics of nonadiabatic reorganization of electronic configurations in molecules is developed, with dual aim that the intramolecular electron dynamics can be probed by means of direct and/or indirect photoionizations and that the physical origins behind photoionization signals attained in the time domain can be identified in terms of the language of time-dependent quantum chemistry. In doing so, we first formulate and implement a new computational scheme for nonadiabatic electron dynamics associated with molecular ionization, which well fits in the general theory of nonadiabatic electron dynamics. In this method, the total nonadiabatic electron wavepackets are propagated in time directly with complex natural orbitals without referring to Hartree-Fock molecular orbitals, and the amount of electron flux from a molecular region leading to ionization is evaluated in terms of the relevant complex natural orbitals. In the second half of this paper, we apply the method to electron dynamics in the elementary processes consisting of the Auger decay to demonstrate the methodological significance. An illustrative example is taken from an Auger decay starting from the 2a1 orbital hole-state of H2O+. The roles of nuclear momentum (kinetic) couplings in electronic-state mixing during the decay process are analyzed in terms of complex natural orbitals, which are schematically represented in the conventional language of molecular symmetry of the Hartree-Fock orbitals.
Modeling non-adiabatic photoexcited reaction dynamics in condensed phases
Coker, D.F.
2003-01-01
Reactions of photoexcited molecules, ions, and radicals in condensed phase environments involve non-adiabatic dynamics over coupled electronic surfaces. We focus on how local environmental symmetries can effect non-adiabatic coupling between excited electronic states and thus influence, in a possibly controllable way, the outcome of photo-excited reactions. Semi-classical and mixed quantum-classical non-adiabatic molecular dynamics methods, together with semi-empirical excited state potentials are used to probe the dynamical mixing of electronic states in different environments from molecular clusters, to simple liquids and solids, and photo-excited reactions in complex reaction environments such as zeolites
Non-Adiabatic Molecular Dynamics Methods for Materials Discovery
Furche, Filipp [Univ. of California, Irvine, CA (United States); Parker, Shane M. [Univ. of California, Irvine, CA (United States); Muuronen, Mikko J. [Univ. of California, Irvine, CA (United States); Roy, Saswata [Univ. of California, Irvine, CA (United States)
2017-04-04
The flow of radiative energy in light-driven materials such as photosensitizer dyes or photocatalysts is governed by non-adiabatic transitions between electronic states and cannot be described within the Born-Oppenheimer approximation commonly used in electronic structure theory. The non-adiabatic molecular dynamics (NAMD) methods based on Tully surface hopping and time-dependent density functional theory developed in this project have greatly extended the range of molecular materials that can be tackled by NAMD simulations. New algorithms to compute molecular excited state and response properties efficiently were developed. Fundamental limitations of common non-linear response methods were discovered and characterized. Methods for accurate computations of vibronic spectra of materials such as black absorbers were developed and applied. It was shown that open-shell TDDFT methods capture bond breaking in NAMD simulations, a longstanding challenge for single-reference molecular dynamics simulations. The methods developed in this project were applied to study the photodissociation of acetaldehyde and revealed that non-adiabatic effects are experimentally observable in fragment kinetic energy distributions. Finally, the project enabled the first detailed NAMD simulations of photocatalytic water oxidation by titania nanoclusters, uncovering the mechanism of this fundamentally important reaction for fuel generation and storage.
Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics
Makhov, Dmitry V.; Shalashilin, Dmitrii V. [Department of Chemistry, University of Leeds, Leeds LS2 9JT (United Kingdom); Glover, William J.; Martinez, Todd J. [Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA and SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States)
2014-08-07
We present a new algorithm for ab initio quantum nonadiabatic molecular dynamics that combines the best features of ab initio Multiple Spawning (AIMS) and Multiconfigurational Ehrenfest (MCE) methods. In this new method, ab initio multiple cloning (AIMC), the individual trajectory basis functions (TBFs) follow Ehrenfest equations of motion (as in MCE). However, the basis set is expanded (as in AIMS) when these TBFs become sufficiently mixed, preventing prolonged evolution on an averaged potential energy surface. We refer to the expansion of the basis set as “cloning,” in analogy to the “spawning” procedure in AIMS. This synthesis of AIMS and MCE allows us to leverage the benefits of mean-field evolution during periods of strong nonadiabatic coupling while simultaneously avoiding mean-field artifacts in Ehrenfest dynamics. We explore the use of time-displaced basis sets, “trains,” as a means of expanding the basis set for little cost. We also introduce a new bra-ket averaged Taylor expansion (BAT) to approximate the necessary potential energy and nonadiabatic coupling matrix elements. The BAT approximation avoids the necessity of computing electronic structure information at intermediate points between TBFs, as is usually done in saddle-point approximations used in AIMS. The efficiency of AIMC is demonstrated on the nonradiative decay of the first excited state of ethylene. The AIMC method has been implemented within the AIMS-MOLPRO package, which was extended to include Ehrenfest basis functions.
Photodynamics of oxybenzone sunscreen: Nonadiabatic dynamics simulations
Li, Chun-Xiang; Guo, Wei-Wei; Xie, Bin-Bin; Cui, Ganglong, E-mail: ganglong.cui@bnu.edu.cn [Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China)
2016-08-21
Herein we have used combined static electronic structure calculations and “on-the-fly” global-switching trajectory surface-hopping dynamics simulations to explore the photochemical mechanism of oxybenzone sunscreen. We have first employed the multi-configurational CASSCF method to optimize minima, conical intersections, and minimum-energy reaction paths related to excited-state intramolecular proton transfer (ESIPT) and excited-state decays in the {sup 1}ππ{sup ∗}, {sup 1}nπ{sup ∗}, and S{sub 0} states (energies are refined at the higher MS-CASPT2 level). According to the mapped potential energy profiles, we have identified two ultrafast excited-state deactivation pathways for the initially populated {sup 1}ππ{sup ∗} system. The first is the diabatic ESIPT process along the {sup 1}ππ{sup ∗} potential energy profile. The generated {sup 1}ππ{sup ∗} keto species then decays to the S{sub 0} state via the keto {sup 1}ππ{sup ∗}/gs conical intersection. The second is internal conversion to the dark {sup 1}nπ{sup ∗} state near the {sup 1}ππ{sup ∗} /{sup 1}nπ{sup ∗} crossing point in the course of the diabatic {sup 1}ππ{sup ∗} ESIPT process. Our following dynamics simulations have shown that the ESIPT and {sup 1}ππ{sup ∗} → S{sub 0} internal conversion times are 104 and 286 fs, respectively. Finally, our present work demonstrates that in addition to the ESIPT process and the {sup 1}ππ{sup ∗} → S{sub 0} internal conversion in the keto region, the {sup 1}ππ{sup ∗} → {sup 1}nπ{sup ∗} internal conversion in the enol region plays as well an important role for the excited-state relaxation dynamics of oxybenzone.
Nonadiabatic exchange dynamics during adiabatic frequency sweeps.
Barbara, Thomas M
2016-04-01
A Bloch equation analysis that includes relaxation and exchange effects during an adiabatic frequency swept pulse is presented. For a large class of sweeps, relaxation can be incorporated using simple first order perturbation theory. For anisochronous exchange, new expressions are derived for exchange augmented rotating frame relaxation. For isochronous exchange between sites with distinct relaxation rate constants outside the extreme narrowing limit, simple criteria for adiabatic exchange are derived and demonstrate that frequency sweeps commonly in use may not be adiabatic with regard to exchange unless the exchange rates are much larger than the relaxation rates. Otherwise, accurate assessment of the sensitivity to exchange dynamics will require numerical integration of the rate equations. Examples of this situation are given for experimentally relevant parameters believed to hold for in-vivo tissue. These results are of significance in the study of exchange induced contrast in magnetic resonance imaging. Copyright © 2016 Elsevier Inc. All rights reserved.
Memory effects in nonadiabatic molecular dynamics at metal surfaces
Olsen, Thomas; Schiøtz, Jakob
2010-01-01
We study the effect of temporal correlation in a Langevin equation describing nonadiabatic dynamics at metal surfaces. For a harmonic oscillator, the Langevin equation preserves the quantum dynamics exactly and it is demonstrated that memory effects are needed in order to conserve the ground state...... energy of the oscillator. We then compare the result of Langevin dynamics in a harmonic potential with a perturbative master equation approach and show that the Langevin equation gives a better description in the nonperturbative range of high temperatures and large friction. Unlike the master equation......, this approach is readily extended to anharmonic potentials. Using density functional theory, we calculate representative Langevin trajectories for associative desorption of N-2 from Ru(0001) and find that memory effects lower the dissipation of energy. Finally, we propose an ab initio scheme to calculate...
Miyagi, Haruhide; Madsen, Lars Bojer
2013-01-01
We present the time-dependent restricted-active-space self-consistent-field (TD-RASSCF) theory as a framework for the time-dependent many-electron problem. The theory generalizes the multiconfigurational time-dependent Hartree-Fock (MCTDHF) theory by incorporating the restricted-active-space scheme...... well known in time-independent quantum chemistry. Optimization of the orbitals as well as the expansion coefficients at each time step makes it possible to construct the wave function accurately while using only a relatively small number of electronic configurations. In numerical calculations of high...
Nonadiabatic dynamics of electron injection into organic molecules
Zhu Li-Ping; Qiu Yu; Tong Guo-Ping
2012-01-01
We numerically investigate the injection process of electrons from metal electrodes to one-dimensional organic molecules by combining the extended Su—Schrieffer—Heeger (SSH) model with a nonadiabatic dynamics method. It is found that a match between the Fermi level of electrodes and the highest occupied molecular orbital (HOMO) or the lowest unoccupied molecular orbital (LUMO) of organic molecules can be greatly affected by the length of the organic chains, which has a great impact on electron injection. The correlation between oligomers and electrodes is found to open more efficient channels for electron injection as compared with that in polymer/electrode structures. For oligomer/electrode structures, we show that the Schottky barrier essentially does not affect the electron injection as the electrode work function is smaller than a critical value. This means that the Schottky barrier is pinned for a small work-function electrode. For polymer/electrode structures, we find that it is possible for the Fermi level of electrodes to be pinned to the polaronic level. The condition under which the Fermi level of electrodes exceeds the polaronic level of polymers is shown to not always lead to spontaneous electron transfer from electrodes to polymers. (condensed matter: electronic structure, electrical, magnetic, and optical properties)
Classical molecular dynamics simulation of electronically non-adiabatic processes.
Miller, William H; Cotton, Stephen J
2016-12-22
Both classical and quantum mechanics (as well as hybrids thereof, i.e., semiclassical approaches) find widespread use in simulating dynamical processes in molecular systems. For large chemical systems, however, which involve potential energy surfaces (PES) of general/arbitrary form, it is usually the case that only classical molecular dynamics (MD) approaches are feasible, and their use is thus ubiquitous nowadays, at least for chemical processes involving dynamics on a single PES (i.e., within a single Born-Oppenheimer electronic state). This paper reviews recent developments in an approach which extends standard classical MD methods to the treatment of electronically non-adiabatic processes, i.e., those that involve transitions between different electronic states. The approach treats nuclear and electronic degrees of freedom (DOF) equivalently (i.e., by classical mechanics, thereby retaining the simplicity of standard MD), and provides "quantization" of the electronic states through a symmetrical quasi-classical (SQC) windowing model. The approach is seen to be capable of treating extreme regimes of strong and weak coupling between the electronic states, as well as accurately describing coherence effects in the electronic DOF (including the de-coherence of such effects caused by coupling to the nuclear DOF). A survey of recent applications is presented to illustrate the performance of the approach. Also described is a newly developed variation on the original SQC model (found universally superior to the original) and a general extension of the SQC model to obtain the full electronic density matrix (at no additional cost/complexity).
The quantum dynamics of electronically nonadiabatic chemical reactions
Truhlar, Donald G.
1993-01-01
Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally
Matching-pursuit/split-operator Fourier-transform simulations of nonadiabatic quantum dynamics
Wu, Yinghua; Herman, Michael F.; Batista, Victor S.
2005-03-01
A rigorous and practical approach for simulations of nonadiabatic quantum dynamics is introduced. The algorithm involves a natural extension of the matching-pursuit/split-operator Fourier-transform (MP/SOFT) method [Y. Wu and V. S. Batista, J. Chem. Phys. 121, 1676 (2004)] recently developed for simulations of adiabatic quantum dynamics in multidimensional systems. The MP/SOFT propagation scheme, extended to nonadiabatic dynamics, recursively applies the time-evolution operator as defined by the standard perturbation expansion to first-, or second-order, accuracy. The expansion is implemented in dynamically adaptive coherent-state representations, generated by an approach that combines the matching-pursuit algorithm with a gradient-based optimization method. The accuracy and efficiency of the resulting propagation method are demonstrated as applied to the canonical model systems introduced by Tully for testing simulations of dual curve-crossing nonadiabatic dynamics.
Quantum chaos induced by nonadiabatic coupling in wave-packet dynamics
Higuchi, Hisashi; Takatsuka, Kazuo
2002-01-01
The effect of nonadiabatic coupling due to breakdown of the Born-Oppenheimer approximation on chaos is investigated. A couple of measures (indicators) that detect the extent of chaos in wave-packet dynamics on coupled potential functions are devised. Using them, we show that chaos is indeed induced by a nonadiabatic coupling in individual time-dependent wave-packet dynamics. This chaos is genuinely of quantum nature, since it arises from bifurcation and merging of a wave packet at the quasicrossing region of two coupled potential functions
Between ethylene and polyenes--the non-adiabatic dynamics of cis-dienes
Kuhlman, Thomas Scheby; Glover, William J; Mori, Toshifumi
2012-01-01
Using Ab Initio Multiple Spawning (AIMS) with a Multi-State Multi-Reference Perturbation theory (MS-MR-CASPT2) treatment of the electronic structure, we have simulated the non-adiabatic excited state dynamics of cyclopentadiene (CPD) and 1,2,3,4-tetramethyl-cyclopentadiene (Me4-CPD) following exc...
Non-adiabatic molecular dynamic simulations of opening reaction of molecular junctions
Zobač, Vladimír; Lewis, J.P.; Jelínek, Pavel
2016-01-01
Roč. 27, č. 28 (2016), 1-8, č. článku 285202. ISSN 0957-4484 R&D Projects: GA ČR(CZ) GA14-02079S Institutional support: RVO:68378271 Keywords : non-adiabatic molecular dynamics * molecular junctions * molecular switches * DFT Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.440, year: 2016
TREATMENT OF NONADIABATIC TRANSITIONS BY DENSITY-MATRIX EVOLUTION AND MOLECULAR-DYNAMICS SIMULATIONS
MAVRI, J; BERENDSEN, HJC
1994-01-01
A density matrix evolution (DME) method (H.J.C. Berendsen and J. Mavri, J. Phys. Chem., 97 (1993) 13469) to simulate the dynamics of quantum systems embedded in a classical environment is presented. The DME method allows treatment of nonadiabatic transitions. As numerical examples the collinear
Kondorskiy, A.; Nakamura, H.
2004-01-01
The title theory is developed by combining the Herman-Kluk semiclassical theory for adiabatic propagation on single potential-energy surface and the semiclassical Zhu-Nakamura theory for nonadiabatic transition. The formulation with use of natural mathematical principles leads to a quite simple expression for the propagator based on classical trajectories and simple formulas are derived for overall adiabatic and nonadiabatic processes. The theory is applied to electronically nonadiabatic photodissociation processes: a one-dimensional problem of H 2 + in a cw (continuous wave) laser field and a two-dimensional model problem of H 2 O in a cw laser field. The theory is found to work well for the propagation duration of several molecular vibrational periods and wide energy range. Although the formulation is made for the case of laser induced nonadiabatic processes, it is straightforwardly applicable to ordinary electronically nonadiabatic chemical dynamics
Franco de Carvalho, F. [Centre Européen de Calcul Atomique et Moléculaire, Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Tavernelli, I. [IBM Research GmbH, Zurich Research Laboratory, 8803 Ruschlikon (Switzerland)
2015-12-14
In this work, we derive a method to perform trajectory-based nonadiabatic dynamics that is able to describe both nonadiabatic transitions and intersystem crossing events (transitions between states of different spin-multiplicity) at the same level of theory, namely, time-dependent density functional theory (TDDFT). To this end, we combined our previously developed TDDFT-based trajectory surface hopping scheme with an accurate and efficient algorithm for the calculation of the spin-orbit coupling (SOC) matrix elements. More specifically, we designed two algorithms for the calculation of intersystem crossing transitions, one based on an extended Tully’s surface hopping scheme including SOC and the second based on a Landau-Zener approximation applied to the spin sector of the electronic Hilbert space. This development allows for the design of an efficient on-the-fly nonadiabatic approach that can handle, on an equal footing, nonadiabatic and intersystem crossing transitions. The method is applied to the study of the photophysics of sulfur dioxide (SO{sub 2}) in gas and liquid phases.
Semiclassical Monte Carlo: A first principles approach to non-adiabatic molecular dynamics
White, Alexander J.; Gorshkov, Vyacheslav N.; Wang, Ruixi; Tretiak, Sergei; Mozyrsky, Dmitry
2014-01-01
Modeling the dynamics of photophysical and (photo)chemical reactions in extended molecular systems is a new frontier for quantum chemistry. Many dynamical phenomena, such as intersystem crossing, non-radiative relaxation, and charge and energy transfer, require a non-adiabatic description which incorporate transitions between electronic states. Additionally, these dynamics are often highly sensitive to quantum coherences and interference effects. Several methods exist to simulate non-adiabatic dynamics; however, they are typically either too expensive to be applied to large molecular systems (10's-100's of atoms), or they are based on ad hoc schemes which may include severe approximations due to inconsistencies in classical and quantum mechanics. We present, in detail, an algorithm based on Monte Carlo sampling of the semiclassical time-dependent wavefunction that involves running simple surface hopping dynamics, followed by a post-processing step which adds little cost. The method requires only a few quantities from quantum chemistry calculations, can systematically be improved, and provides excellent agreement with exact quantum mechanical results. Here we show excellent agreement with exact solutions for scattering results of standard test problems. Additionally, we find that convergence of the wavefunction is controlled by complex valued phase factors, the size of the non-adiabatic coupling region, and the choice of sampling function. These results help in determining the range of applicability of the method, and provide a starting point for further improvement
Recent Advances and Perspectives on Nonadiabatic Mixed Quantum-Classical Dynamics.
Crespo-Otero, Rachel; Barbatti, Mario
2018-05-16
Nonadiabatic mixed quantum-classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry tailored to investigate the time evolution of nonadiabatic phenomena in molecules and supramolecular assemblies. NA-MQC is characterized by a partition of the molecular system into two subsystems: one to be treated quantum mechanically (usually but not restricted to electrons) and another to be dealt with classically (nuclei). The two subsystems are connected through nonadiabatic couplings terms to enforce self-consistency. A local approximation underlies the classical subsystem, implying that direct dynamics can be simulated, without needing precomputed potential energy surfaces. The NA-MQC split allows reducing computational costs, enabling the treatment of realistic molecular systems in diverse fields. Starting from the three most well-established methods-mean-field Ehrenfest, trajectory surface hopping, and multiple spawning-this review focuses on the NA-MQC dynamics methods and programs developed in the last 10 years. It stresses the relations between approaches and their domains of application. The electronic structure methods most commonly used together with NA-MQC dynamics are reviewed as well. The accuracy and precision of NA-MQC simulations are critically discussed, and general guidelines to choose an adequate method for each application are delivered.
Trajectory-based nonadiabatic dynamics with time-dependent density functional theory.
Curchod, Basile F E; Rothlisberger, Ursula; Tavernelli, Ivano
2013-05-10
Understanding the fate of an electronically excited molecule constitutes an important task for theoretical chemistry, and practical implications range from the interpretation of atto- and femtosecond spectroscopy to the development of light-driven molecular machines, the control of photochemical reactions, and the possibility of capturing sunlight energy. However, many challenging conceptual and technical problems are involved in the description of these phenomena such as 1) the failure of the well-known Born-Oppenheimer approximation; 2) the need for accurate electronic properties such as potential energy surfaces, excited nuclear forces, or nonadiabatic coupling terms; and 3) the necessity of describing the dynamics of the photoexcited nuclear wavepacket. This review provides an overview of the current methods to address points 1) and 3) and shows how time-dependent density functional theory (TDDFT) and its linear-response extension can be used for point 2). First, the derivation of Ehrenfest dynamics and nonadiabatic Bohmian dynamics is discussed and linked to Tully's trajectory surface hopping. Second, the coupling of these trajectory-based nonadiabatic schemes with TDDFT is described in detail with special emphasis on the derivation of the required electronic structure properties. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Nonadiabatic excited-state molecular dynamics: On-the-fly limiting of essential excited states
Nelson, Tammie [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Naumov, Artem [Skolkovo Institute of Science and Technology, Moscow 143026 (Russian Federation); Fernandez-Alberti, Sebastian [Universidad Nacional de Quilmes, Roque Saenz Pea 352, B1876BXD Bernal (Argentina); Tretiak, Sergei, E-mail: serg@lanl.gov [Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)
2016-12-20
The simulation of nonadiabatic dynamics in extended molecular systems involving hundreds of atoms and large densities of states is particularly challenging. Nonadiabatic coupling terms (NACTs) represent a significant numerical bottleneck in surface hopping approaches. Rather than using unreliable NACT cutting schemes, here we develop “on-the-fly” state limiting methods to eliminate states that are no longer essential for the non-radiative relaxation dynamics as a trajectory proceeds. We propose a state number criteria and an energy-based state limit. The latter is more physically relevant by requiring a user-imposed energy threshold. For this purpose, we introduce a local kinetic energy gauge by summing contributions from atoms within the spatial localization of the electronic wavefunction to define the energy available for upward hops. The proposed state limiting schemes are implemented within the nonadiabatic excited-state molecular dynamics framework to simulate photoinduced relaxation in poly-phenylene vinylene (PPV) and branched poly-phenylene ethynylene (PPE) oligomers for benchmark evaluation.
Non-adiabatic molecular dynamics with complex quantum trajectories. I. The diabatic representation.
Zamstein, Noa; Tannor, David J
2012-12-14
We extend a recently developed quantum trajectory method [Y. Goldfarb, I. Degani, and D. J. Tannor, J. Chem. Phys. 125, 231103 (2006)] to treat non-adiabatic transitions. Each trajectory evolves on a single surface according to Newton's laws with complex positions and momenta. The transfer of amplitude between surfaces stems naturally from the equations of motion, without the need for surface hopping. In this paper we derive the equations of motion and show results in the diabatic representation, which is rarely used in trajectory methods for calculating non-adiabatic dynamics. We apply our method to the first two benchmark models introduced by Tully [J. Chem. Phys. 93, 1061 (1990)]. Besides giving the probability branching ratios between the surfaces, the method also allows the reconstruction of the time-dependent wavepacket. Our results are in quantitative agreement with converged quantum mechanical calculations.
Multiple coupled landscapes and non-adiabatic dynamics with applications to self-activating genes.
Chen, Cong; Zhang, Kun; Feng, Haidong; Sasai, Masaki; Wang, Jin
2015-11-21
Many physical, chemical and biochemical systems (e.g. electronic dynamics and gene regulatory networks) are governed by continuous stochastic processes (e.g. electron dynamics on a particular electronic energy surface and protein (gene product) synthesis) coupled with discrete processes (e.g. hopping among different electronic energy surfaces and on and off switching of genes). One can also think of the underlying dynamics as the continuous motion on a particular landscape and discrete hoppings among different landscapes. The main difference of such systems from the intra-landscape dynamics alone is the emergence of the timescale involved in transitions among different landscapes in addition to the timescale involved in a particular landscape. The adiabatic limit when inter-landscape hoppings are fast compared to continuous intra-landscape dynamics has been studied both analytically and numerically, but the analytical treatment of the non-adiabatic regime where the inter-landscape hoppings are slow or comparable to continuous intra-landscape dynamics remains challenging. In this study, we show that there exists mathematical mapping of the dynamics on 2(N) discretely coupled N continuous dimensional landscapes onto one single landscape in 2N dimensional extended continuous space. On this 2N dimensional landscape, eddy current emerges as a sign of non-equilibrium non-adiabatic dynamics and plays an important role in system evolution. Many interesting physical effects such as the enhancement of fluctuations, irreversibility, dissipation and optimal kinetics emerge due to non-adiabaticity manifested by the eddy current illustrated for an N = 1 self-activator. We further generalize our theory to the N-gene network with multiple binding sites and multiple synthesis rates for discretely coupled non-equilibrium stochastic physical and biological systems.
Beyond Ehrenfest: correlated non-adiabatic molecular dynamics
Horsfield, Andrew P; Bowler, D R; Fisher, A J; Todorov, Tchavdar N; Sanchez, Cristian G
2004-01-01
A method for introducing correlations between electrons and ions that is computationally affordable is described. The central assumption is that the ionic wavefunctions are narrow, which makes possible a moment expansion for the full density matrix. To make the problem tractable we reduce the remaining many-electron problem to a single-electron problem by performing a trace over all electronic degrees of freedom except one. This introduces both one- and two-electron quantities into the equations of motion. Quantities depending on more than one electron are removed by making a Hartree-Fock approximation. Using the first-moment approximation, we perform a number of tight binding simulations of the effect of an electric current on a mobile atom. The classical contribution to the ionic kinetic energy exhibits cooling and is independent of the bias. The quantum contribution exhibits strong heating, with the heating rate proportional to the bias. However, increased scattering of electrons with increasing ionic kinetic energy is not observed. This effect requires the introduction of the second moment
Du, Likai; Lan, Zhenggang
2015-04-14
Nonadiabatic dynamics simulations have rapidly become an indispensable tool for understanding ultrafast photochemical processes in complex systems. Here, we present our recently developed on-the-fly nonadiabatic dynamics package, JADE, which allows researchers to perform nonadiabatic excited-state dynamics simulations of polyatomic systems at an all-atomic level. The nonadiabatic dynamics is based on Tully's surface-hopping approach. Currently, several electronic structure methods (CIS, TDHF, TDDFT(RPA/TDA), and ADC(2)) are supported, especially TDDFT, aiming at performing nonadiabatic dynamics on medium- to large-sized molecules. The JADE package has been interfaced with several quantum chemistry codes, including Turbomole, Gaussian, and Gamess (US). To consider environmental effects, the Langevin dynamics was introduced as an easy-to-use scheme into the standard surface-hopping dynamics. The JADE package is mainly written in Fortran for greater numerical performance and Python for flexible interface construction, with the intent of providing open-source, easy-to-use, well-modularized, and intuitive software in the field of simulations of photochemical and photophysical processes. To illustrate the possible applications of the JADE package, we present a few applications of excited-state dynamics for various polyatomic systems, such as the methaniminium cation, fullerene (C20), p-dimethylaminobenzonitrile (DMABN) and its primary amino derivative aminobenzonitrile (ABN), and 10-hydroxybenzo[h]quinoline (10-HBQ).
Miyagi, Haruhide; Madsen, Lars Bojer
We have developed a new theoretical framework for time-dependent many-electron problems named time-dependent restricted-active-space self-consistent field (TD-RASSCF) theory. The theory generalizes the multicongurational time-dependent Hartree-Fock (MCTDHF) theory by truncating the expansion...
Path-integral isomorphic Hamiltonian for including nuclear quantum effects in non-adiabatic dynamics
Tao, Xuecheng; Shushkov, Philip; Miller, Thomas F.
2018-03-01
We describe a path-integral approach for including nuclear quantum effects in non-adiabatic chemical dynamics simulations. For a general physical system with multiple electronic energy levels, a corresponding isomorphic Hamiltonian is introduced such that Boltzmann sampling of the isomorphic Hamiltonian with classical nuclear degrees of freedom yields the exact quantum Boltzmann distribution for the original physical system. In the limit of a single electronic energy level, the isomorphic Hamiltonian reduces to the familiar cases of either ring polymer molecular dynamics (RPMD) or centroid molecular dynamics Hamiltonians, depending on the implementation. An advantage of the isomorphic Hamiltonian is that it can easily be combined with existing mixed quantum-classical dynamics methods, such as surface hopping or Ehrenfest dynamics, to enable the simulation of electronically non-adiabatic processes with nuclear quantum effects. We present numerical applications of the isomorphic Hamiltonian to model two- and three-level systems, with encouraging results that include improvement upon a previously reported combination of RPMD with surface hopping in the deep-tunneling regime.
Peters, William K.; Tiwari, Vivek; Jonas, David M.
2017-11-01
The nonadiabatic states and dynamics are investigated for a linear vibronic coupling Hamiltonian with a static electronic splitting and weak off-diagonal Jahn-Teller coupling through a single vibration with a vibrational-electronic resonance. With a transformation of the electronic basis, this Hamiltonian is also applicable to the anti-correlated vibration in a symmetric homodimer with marginally strong constant off-diagonal coupling, where the non-adiabatic states and dynamics model electronic excitation energy transfer or self-exchange electron transfer. For parameters modeling a free-base naphthalocyanine, the nonadiabatic couplings are deeply quantum mechanical and depend on wavepacket width; scalar couplings are as important as the derivative couplings that are usually interpreted to depend on vibrational velocity in semiclassical curve crossing or surface hopping theories. A colored visualization scheme that fully characterizes the non-adiabatic states using the exact factorization is developed. The nonadiabatic states in this nested funnel have nodeless vibrational factors with strongly avoided zeroes in their vibrational probability densities. Vibronic dynamics are visualized through the vibrational coordinate dependent density of the time-dependent dipole moment in free induction decay. Vibrational motion is amplified by the nonadiabatic couplings, with asymmetric and anisotropic motions that depend upon the excitation polarization in the molecular frame and can be reversed by a change in polarization. This generates a vibrational quantum beat anisotropy in excess of 2/5. The amplitude of vibrational motion can be larger than that on the uncoupled potentials, and the electronic population transfer is maximized within one vibrational period. Most of these dynamics are missed by the adiabatic approximation, and some electronic and vibrational motions are completely suppressed by the Condon approximation of a coordinate-independent transition dipole between
Profiling the overdamped dynamics of a nonadiabatic system
Sarkar, Prasun [Department of Chemistry, Bose Institute, 93/1 A P C Road, Kolkata 700009 (India); Shit, Anindita [Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur, Howrah 711103 (India); Chattopadhyay, Sudip, E-mail: sudip_chattopadhyay@rediffmail.com [Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur, Howrah 711103 (India); Banik, Suman K., E-mail: skbanik@jcbose.ac.in [Department of Chemistry, Bose Institute, 93/1 A P C Road, Kolkata 700009 (India)
2015-09-08
Graphical abstract: The theoretical analysis that is addressed here can be used to illustrate both a qualitative and a quantitative understanding of the dynamics of a particle in the presence of an external probe. - Highlights: • Interaction of systems with strong fields results in many interesting observations. • The relevant systems are characterized by an extremely high degree of control. • The theory that is addressed here is useful to investigate the transport process. • Effective to understand the trapping mechanism in a rapidly oscillating potential. • Useful to study the dynamics of particles in the presence of an external probe. - Abstract: Rapidly oscillating time-periodic potentials with a vanishing time average have been exploited to investigate the dynamics of an overdamped particle. Using the multiple scale perturbation theory, it has been shown that the dynamics can be adequately characterized by an explicitly time-independent effective potential. The resulting “effective equation of motion” can offer various avenues to handle the dynamics of the system driven by a high-frequency field. We study the effects of the field parameters on the mobility of the overdamped particle moving in the effective potential. The variation of the mobility with the field parameters is associated with the interplay of spatially periodic gradients, time periodic modulation and thermal noise in the overdamped region. Good agreement between the simulations and theoretical estimates validates our methodology that captures the constitutional features ruling the dynamics in the overdamped limit. The results observed here can also be extended to the quantum system.
Joubert-Doriol, Loïc; Izmaylov, Artur F.
2018-03-01
A new methodology of simulating nonadiabatic dynamics using frozen-width Gaussian wavepackets within the moving crude adiabatic representation with the on-the-fly evaluation of electronic structure is presented. The main feature of the new approach is the elimination of any global or local model representation of electronic potential energy surfaces; instead, the electron-nuclear interaction is treated explicitly using the Gaussian integration. As a result, the new scheme does not introduce any uncontrolled approximations. The employed variational principle ensures the energy conservation and leaves the number of electronic and nuclear basis functions as the only parameter determining the accuracy. To assess performance of the approach, a model with two electronic and two nuclear spacial degrees of freedom containing conical intersections between potential energy surfaces has been considered. Dynamical features associated with nonadiabatic transitions and nontrivial geometric (or Berry) phases were successfully reproduced within a limited basis expansion.
Nonadiabatic quantum dynamics and laser control of Br2 in solid argon.
Accardi, A; Borowski, A; Kühn, O
2009-07-02
A five-dimensional reaction surface-vibronic coupling model is introduced to describe the B- to C-state predissociation dynamics of Br(2) occupying a double substitutional lattice site in a face-centered cubic argon crystal at low temperatures. The quantum dynamics driven by a Franck-Condon vertical excitation is investigated, revealing the role of matrix cage compression for efficient nonadiabatic transitions. Vibrational preexcitation of the Br(2) bond in the electronic ground state can be used to access a different regime of predissociation which does not require substantial matrix compression because the Franck-Condon window shifts into the energetic range of the B-C level crossing. Using optimal control theory, it is shown how vibrational preexcitation can be achieved via a pump-dump-type mechanism involving the repulsive C state.
Bochenkova, Anastasia; Andersen, Lars Henrik
2013-01-01
The anionic wild-type Green Fluorescent Protein (GFP) chromophore defines the entire class of naturally occurring chromophores, which are based on the oxydized tyrosine side chain. The GFP chromophore exhibits an enriched photoinduced non-adiabatic dynamics in the multiple excited-state decay cha...
Nelson, Tammie Renee [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Tretiak, Sergei [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
2017-01-06
Understanding and controlling excited state dynamics lies at the heart of all our efforts to design photoactive materials with desired functionality. This tailor-design approach has become the standard for many technological applications (e.g., solar energy harvesting) including the design of organic conjugated electronic materials with applications in photovoltaic and light-emitting devices. Over the years, our team has developed efficient LANL-based codes to model the relevant photophysical processes following photoexcitation (spatial energy transfer, excitation localization/delocalization, and/or charge separation). The developed approach allows the non-radiative relaxation to be followed on up to ~10 ps timescales for large realistic molecules (hundreds of atoms in size) in the realistic solvent dielectric environment. The Collective Electronic Oscillator (CEO) code is used to compute electronic excited states, and the Non-adiabatic Excited State Molecular Dynamics (NA-ESMD) code is used to follow the non-adiabatic dynamics on multiple coupled Born-Oppenheimer potential energy surfaces. Our preliminary NA-ESMD simulations have revealed key photoinduced mechanisms controlling competing interactions and relaxation pathways in complex materials, including organic conjugated polymer materials, and have provided a detailed understanding of photochemical products and intermediates and the internal conversion process during the initiation of energetic materials. This project will be using LANL-based CEO and NA-ESMD codes to model nonradiative relaxation in organic and energetic materials. The NA-ESMD and CEO codes belong to a class of electronic structure/quantum chemistry codes that require large memory, “long-queue-few-core” distribution of resources in order to make useful progress. The NA-ESMD simulations are trivially parallelizable requiring ~300 processors for up to one week runtime to reach a meaningful restart point.
Efficient and Flexible Computation of Many-Electron Wave Function Overlaps.
Plasser, Felix; Ruckenbauer, Matthias; Mai, Sebastian; Oppel, Markus; Marquetand, Philipp; González, Leticia
2016-03-08
A new algorithm for the computation of the overlap between many-electron wave functions is described. This algorithm allows for the extensive use of recurring intermediates and thus provides high computational efficiency. Because of the general formalism employed, overlaps can be computed for varying wave function types, molecular orbitals, basis sets, and molecular geometries. This paves the way for efficiently computing nonadiabatic interaction terms for dynamics simulations. In addition, other application areas can be envisaged, such as the comparison of wave functions constructed at different levels of theory. Aside from explaining the algorithm and evaluating the performance, a detailed analysis of the numerical stability of wave function overlaps is carried out, and strategies for overcoming potential severe pitfalls due to displaced atoms and truncated wave functions are presented.
Nonadiabatic Ponderomotive Potentials
Dodin IY, Fisch NJ
2005-01-01
An approximate integral of the Manley-Rowe type is found for a particle moving in a high-frequency field, which may interact resonantly with natural particle oscillations. An effective ponderomotive potential is introduced accordingly and can capture nonadiabatic particle dynamics. We show that nonadiabatic ponderomotive barriers can trap classical particles, produce cooling effect, and generate one-way walls for resonant species. Possible atomic applications are also envisioned
Martens, Craig C., E-mail: cmartens@uci.edu
2016-12-20
In this paper, we revisit the semiclassical Liouville approach to describing molecular dynamics with electronic transitions using classical trajectories. Key features of the formalism are highlighted. The locality in phase space and presence of nonclassical terms in the generalized Liouville equations are emphasized and discussed in light of trajectory surface hopping methodology. The representation dependence of the coupled semiclassical Liouville equations in the diabatic and adiabatic bases are discussed and new results for the transformation theory of the Wigner functions representing the corresponding density matrix elements given. We show that the diagonal energies of the state populations are not conserved during electronic transitions, as energy is stored in the electronic coherence. We discuss the implications of this observation for the validity of imposing strict energy conservation in trajectory based methods for simulating nonadiabatic processes.
Hatcher, Elizabeth; Soudackov, Alexander; Hammes-Schiffer, Sharon
2005-01-01
The dynamical aspects of a model proton-coupled electron transfer (PCET) reaction in solution are analyzed with molecular dynamics simulations. The rate for nonadiabatic PCET is expressed in terms of a time-dependent probability flux correlation function. The impact of the proton donor-acceptor and solvent dynamics on the probability flux is examined. The dynamical behavior of the probability flux correlation function is dominated by a solvent damping term that depends on the energy gap correlation function. The proton donor-acceptor motion does not impact the dynamical behavior of the probability flux correlation function but does influence the magnitude of the rate. The approximations previously invoked for the calculation of PCET rates are tested. The effects of solvent damping on the proton donor-acceptor vibrational motion are found to be negligible, and the short-time solvent approximation, in which only equilibrium fluctuations of the solvent are considered, is determined to be valid for these types of reactions. The analysis of PCET reactions is compared to previous analyses of single electron and proton transfer reactions. The dynamical behavior is qualitatively similar for all three types of reactions, but the time scale of the decay of the probability flux correlation function is significantly longer for single proton transfer than for PCET and single electron transfer due to a smaller solvent reorganization energy for proton transfer
Greene, Samuel M; Batista, Victor S
2017-09-12
We introduce the "tensor-train split-operator Fourier transform" (TT-SOFT) method for simulations of multidimensional nonadiabatic quantum dynamics. TT-SOFT is essentially the grid-based SOFT method implemented in dynamically adaptive tensor-train representations. In the same spirit of all matrix product states, the tensor-train format enables the representation, propagation, and computation of observables of multidimensional wave functions in terms of the grid-based wavepacket tensor components, bypassing the need of actually computing the wave function in its full-rank tensor product grid space. We demonstrate the accuracy and efficiency of the TT-SOFT method as applied to propagation of 24-dimensional wave packets, describing the S 1 /S 2 interconversion dynamics of pyrazine after UV photoexcitation to the S 2 state. Our results show that the TT-SOFT method is a powerful computational approach for simulations of quantum dynamics of polyatomic systems since it avoids the exponential scaling problem of full-rank grid-based representations.
Humeniuk, Alexander; Mitrić, Roland
2017-12-01
A software package, called DFTBaby, is published, which provides the electronic structure needed for running non-adiabatic molecular dynamics simulations at the level of tight-binding DFT. A long-range correction is incorporated to avoid spurious charge transfer states. Excited state energies, their analytic gradients and scalar non-adiabatic couplings are computed using tight-binding TD-DFT. These quantities are fed into a molecular dynamics code, which integrates Newton's equations of motion for the nuclei together with the electronic Schrödinger equation. Non-adiabatic effects are included by surface hopping. As an example, the program is applied to the optimization of excited states and non-adiabatic dynamics of polyfluorene. The python and Fortran source code is available at http://www.dftbaby.chemie.uni-wuerzburg.de.
Nonadiabatic Dynamics for Electrons at Second-Order: Real-Time TDDFT and OSCF2.
Nguyen, Triet S; Parkhill, John
2015-07-14
We develop a new model to simulate nonradiative relaxation and dephasing by combining real-time Hartree-Fock and density functional theory (DFT) with our recent open-systems theory of electronic dynamics. The approach has some key advantages: it has been systematically derived and properly relaxes noninteracting electrons to a Fermi-Dirac distribution. This paper combines the new dissipation theory with an atomistic, all-electron quantum chemistry code and an atom-centered model of the thermal environment. The environment is represented nonempirically and is dependent on molecular structure in a nonlocal way. A production quality, O(N(3)) closed-shell implementation of our theory applicable to realistic molecular systems is presented, including timing information. This scaling implies that the added cost of our nonadiabatic relaxation model, time-dependent open self-consistent field at second order (OSCF2), is computationally inexpensive, relative to adiabatic propagation of real-time time-dependent Hartree-Fock (TDHF) or time-dependent density functional theory (TDDFT). Details of the implementation and numerical algorithm, including factorization and efficiency, are discussed. We demonstrate that OSCF2 approaches the stationary self-consistent field (SCF) ground state when the gap is large relative to k(b)T. The code is used to calculate linear-response spectra including the effects of bath dynamics. Finally, we show how our theory of finite-temperature relaxation can be used to correct ground-state DFT calculations.
Matsuoka, Takahide; Takatsuka, Kazuo
2017-04-07
A theory for dynamics of molecular photoionization from nonadiabatic electron wavepackets driven by intense pulse lasers is proposed. Time evolution of photoelectron distribution is evaluated in terms of out-going electron flux (current of the probability density of electrons) that has kinetic energy high enough to recede from the molecular system. The relevant electron flux is in turn evaluated with the complex-valued electronic wavefunctions that are time evolved in nonadiabatic electron wavepacket dynamics in laser fields. To uniquely rebuild such wavefunctions with its electronic population being lost by ionization, we adopt the complex-valued natural orbitals emerging from the electron density as building blocks of the total wavefunction. The method has been implemented into a quantum chemistry code, which is based on configuration state mixing for polyatomic molecules. Some of the practical aspects needed for its application will be presented. As a first illustrative example, we show the results of hydrogen molecule and its isotope substitutes (HD and DD), which are photoionized by a two-cycle pulse laser. Photon emission spectrum associated with above threshold ionization is also shown. Another example is taken from photoionization dynamics from an excited state of a water molecule. Qualitatively significant effects of nonadiabatic interaction on the photoelectron spectrum are demonstrated.
Nonadiabatic semiclassical dynamics in the mixed quantum-classical initial value representation
Church, Matthew S.; Hele, Timothy J. H.; Ezra, Gregory S.; Ananth, Nandini
2018-03-01
We extend the Mixed Quantum-Classical Initial Value Representation (MQC-IVR), a semiclassical method for computing real-time correlation functions, to electronically nonadiabatic systems using the Meyer-Miller-Stock-Thoss (MMST) Hamiltonian in order to treat electronic and nuclear degrees of freedom (dofs) within a consistent dynamic framework. We introduce an efficient symplectic integration scheme, the MInt algorithm, for numerical time evolution of the phase space variables and monodromy matrix under the non-separable MMST Hamiltonian. We then calculate the probability of transmission through a curve crossing in model two-level systems and show that MQC-IVR reproduces quantum-limit semiclassical results in good agreement with exact quantum methods in one limit, and in the other limit yields results that are in keeping with classical limit semiclassical methods like linearized IVR. Finally, exploiting the ability of the MQC-IVR to quantize different dofs to different extents, we present a detailed study of the extents to which quantizing the nuclear and electronic dofs improves numerical convergence properties without significant loss of accuracy.
Two-level system in spin baths: Non-adiabatic dynamics and heat transport
Segal, Dvira
2014-04-01
We study the non-adiabatic dynamics of a two-state subsystem in a bath of independent spins using the non-interacting blip approximation, and derive an exact analytic expression for the relevant memory kernel. We show that in the thermodynamic limit, when the subsystem-bath coupling is diluted (uniformly) over many (infinite) degrees of freedom, our expression reduces to known results, corresponding to the harmonic bath with an effective, temperature-dependent, spectral density function. We then proceed and study the heat current characteristics in the out-of-equilibrium spin-spin-bath model, with a two-state subsystem bridging two thermal spin-baths of different temperatures. We compare the behavior of this model to the case of a spin connecting boson baths, and demonstrate pronounced qualitative differences between the two models. Specifically, we focus on the development of the thermal diode effect, and show that the spin-spin-bath model cannot support it at weak (subsystem-bath) coupling, while in the intermediate-strong coupling regime its rectifying performance outplays the spin-boson model.
Two-level system in spin baths: Non-adiabatic dynamics and heat transport
Segal, Dvira [Chemical Physics Theory Group, Department of Chemistry, University of Toronto, 80 Saint George St., Toronto, Ontario M5S 3H6 (Canada)
2014-04-28
We study the non-adiabatic dynamics of a two-state subsystem in a bath of independent spins using the non-interacting blip approximation, and derive an exact analytic expression for the relevant memory kernel. We show that in the thermodynamic limit, when the subsystem-bath coupling is diluted (uniformly) over many (infinite) degrees of freedom, our expression reduces to known results, corresponding to the harmonic bath with an effective, temperature-dependent, spectral density function. We then proceed and study the heat current characteristics in the out-of-equilibrium spin-spin-bath model, with a two-state subsystem bridging two thermal spin-baths of different temperatures. We compare the behavior of this model to the case of a spin connecting boson baths, and demonstrate pronounced qualitative differences between the two models. Specifically, we focus on the development of the thermal diode effect, and show that the spin-spin-bath model cannot support it at weak (subsystem-bath) coupling, while in the intermediate-strong coupling regime its rectifying performance outplays the spin-boson model.
Kelly, Aaron; Brackbill, Nora; Markland, Thomas E
2015-03-07
In this article, we show how Ehrenfest mean field theory can be made both a more accurate and efficient method to treat nonadiabatic quantum dynamics by combining it with the generalized quantum master equation framework. The resulting mean field generalized quantum master equation (MF-GQME) approach is a non-perturbative and non-Markovian theory to treat open quantum systems without any restrictions on the form of the Hamiltonian that it can be applied to. By studying relaxation dynamics in a wide range of dynamical regimes, typical of charge and energy transfer, we show that MF-GQME provides a much higher accuracy than a direct application of mean field theory. In addition, these increases in accuracy are accompanied by computational speed-ups of between one and two orders of magnitude that become larger as the system becomes more nonadiabatic. This combination of quantum-classical theory and master equation techniques thus makes it possible to obtain the accuracy of much more computationally expensive approaches at a cost lower than even mean field dynamics, providing the ability to treat the quantum dynamics of atomistic condensed phase systems for long times.
Kelly, Aaron; Markland, Thomas E., E-mail: tmarkland@stanford.edu [Department of Chemistry, Stanford University, Stanford, California 94305 (United States); Brackbill, Nora [Department of Physics, Stanford University, Stanford, California 94305 (United States)
2015-03-07
In this article, we show how Ehrenfest mean field theory can be made both a more accurate and efficient method to treat nonadiabatic quantum dynamics by combining it with the generalized quantum master equation framework. The resulting mean field generalized quantum master equation (MF-GQME) approach is a non-perturbative and non-Markovian theory to treat open quantum systems without any restrictions on the form of the Hamiltonian that it can be applied to. By studying relaxation dynamics in a wide range of dynamical regimes, typical of charge and energy transfer, we show that MF-GQME provides a much higher accuracy than a direct application of mean field theory. In addition, these increases in accuracy are accompanied by computational speed-ups of between one and two orders of magnitude that become larger as the system becomes more nonadiabatic. This combination of quantum-classical theory and master equation techniques thus makes it possible to obtain the accuracy of much more computationally expensive approaches at a cost lower than even mean field dynamics, providing the ability to treat the quantum dynamics of atomistic condensed phase systems for long times.
Xie, Changjian; Guo, Hua
2018-01-01
The choice of the active degrees of freedom (DOFs) is a pivotal issue in a reduced-dimensional model of quantum dynamics when a full-dimensional one is not feasible. Here, several five-dimensional (5D) models are used to investigate the nonadiabatic photodissociation dynamics of the hydroxymethyl (CH2OH) radical, which possesses nine internal DOFs, in its lowest absorption band. A normal-mode based scheme is used to identify the active and spectator modes, and its predictions are confirmed by 5D quantum dynamical calculations. Our results underscore the important role of the CO stretching mode in the photodissociation dynamics of CH2OH, originating from the photo-induced promotion of an electron from the half-occupied π*CO antibonding orbital to a carbon Rydberg orbital.
Nonadiabatic Spin Torque Investigated Using Thermally Activated Magnetic Domain Wall Dynamics
Eltschka, M.; Woetzel, Mathias; Rhensius, J.
2010-01-01
of the DW as a quasiparticle in a one-dimensional potential landscape. By injecting small currents, the potential is modified, allowing for the determination of the nonadiabatic spin torque: βt=0.010±0.004 for a transverse DW and βv=0.073±0.026 for a vortex DW. The larger value is attributed to the higher...
Photodissociation dynamics of CH3C(O)SH in argon matrix: A QM/MM nonadiabatic dynamics simulation
Xia, Shu-Hua; Liu, Xiang-Yang; Fang, Qiu; Cui, Ganglong
2015-11-01
In this work, we have first employed the combined quantum mechanics/molecular mechanics (QM/MM) method to study the photodissociation mechanism of thioacetic acid CH3C(O)SH in the S1, T1, and S0 states in argon matrix. CH3C(O)SH is treated quantum mechanically using the complete active space self-consistent field and complete active space second-order perturbation theory methods; argon matrix is described classically using Lennard-Jones potentials. We find that the C-S bond fission is predominant due to its small barriers of ca. 3.0 and 1.0 kcal/mol in the S1 and T1 states. It completely suppresses the nearby C—C bond fission. After the bond fission, the S1 radical pair of CH3CO and SH can decay to the S0 and T1 states via internal conversion and intersystem crossing, respectively. In the S0 state, the radical pair can either recombine to form CH3C(O)SH or proceed to form molecular products of CH2CO and H2S. We have further employed our recently developed QM/MM generalized trajectory-based surface-hopping method to simulate the photodissociation dynamics of CH3C(O)SH. In 1 ps dynamics simulation, 56% trajectories stay at the Franck-Condon region; the S1 C—S bond fission takes place in the remaining 44% trajectories. Among all nonadiabatic transitions, the S1 → S0 internal conversion is major (55%) but the S1 → T1 intersystem crossing is still comparable and cannot be ignored, which accounts for 28%. Finally, we have found a radical channel generating the molecular products of CH2CO and H2S, which is complementary to the concerted molecular channel. The present work sets the stage for simulating photodissociation dynamics of similar thio-carbonyl systems in matrix.
Taioli, Simone [Interdisciplinary Laboratory for Computational Science, FBK-Center for Materials and Microsystems and University of Trento, Trento (Italy); Department of Physics, University of Trento, Trento (Italy); Istituto Nazionale di Fisica Nucleare, Sezione di Perugia (Italy); Department of Chemistry, University of Bologna, Bologna (Italy); Garberoglio, Giovanni [Interdisciplinary Laboratory for Computational Science, FBK-Center for Materials and Microsystems and University of Trento, Trento (Italy); Simonucci, Stefano [Interdisciplinary Laboratory for Computational Science, FBK-Center for Materials and Microsystems and University of Trento, Trento (Italy); Istituto Nazionale di Fisica Nucleare, Sezione di Perugia (Italy); Department of Physics, University of Camerino, Camerino (Italy); Beccara, Silvio a [Interdisciplinary Laboratory for Computational Science, FBK-Center for Materials and Microsystems and University of Trento, Trento (Italy); Department of Physics, University of Trento, Trento (Italy); Aversa, Lucrezia [Institute of Materials for Electronics and Magnetism, IMEM-CNR, Trento (Italy); Nardi, Marco [Institute of Materials for Electronics and Magnetism, IMEM-CNR, Trento (Italy); Institut fuer Physik, Humboldt-Universitaet zu Berlin, Berlin (Germany); Verucchi, Roberto [Institute of Materials for Electronics and Magnetism, FBK-CNR, Trento (Italy); Iannotta, Salvatore [Institute of Materials for Electronics and Magnetism, IMEM-CNR, Parma (Italy); Dapor, Maurizio [Interdisciplinary Laboratory for Computational Science, FBK-Center for Materials and Microsystems and University of Trento, Trento (Italy); Department of Materials Engineering and Industrial Technologies, University of Trento, Trento (Italy); Istituto Nazionale di Fisica Nucleare, Sezione di Padova (Italy); and others
2013-01-28
In this work, we investigate the processes leading to the room-temperature growth of silicon carbide thin films by supersonic molecular beam epitaxy technique. We present experimental data showing that the collision of fullerene on a silicon surface induces strong chemical-physical perturbations and, for sufficient velocity, disruption of molecular bonds, and cage breaking with formation of nanostructures with different stoichiometric character. We show that in these out-of-equilibrium conditions, it is necessary to go beyond the standard implementations of density functional theory, as ab initio methods based on the Born-Oppenheimer approximation fail to capture the excited-state dynamics. In particular, we analyse the Si-C{sub 60} collision within the non-adiabatic nuclear dynamics framework, where stochastic hops occur between adiabatic surfaces calculated with time-dependent density functional theory. This theoretical description of the C{sub 60} impact on the Si surface is in good agreement with our experimental findings.
Wang, Yu; Chou, Chia-Chun
2018-05-01
The coupled complex quantum Hamilton-Jacobi equations for electronic nonadiabatic transitions are approximately solved by propagating individual quantum trajectories in real space. Equations of motion are derived through use of the derivative propagation method for the complex actions and their spatial derivatives for wave packets moving on each of the coupled electronic potential surfaces. These equations for two surfaces are converted into the moving frame with the same grid point velocities. Excellent wave functions can be obtained by making use of the superposition principle even when nodes develop in wave packet scattering.
Franck--Condon factors in studies of dynamics of chemical reactions. IV. Nonadiabatic collisions
Zvijac, D.J.; Ross, J.
1978-01-01
We investigate the application of the Franck--Condon approach to nonadiabatic molecular scattering processes. Computationally simple, analytic formulas are developed to describe the energy dependence of quenching of electronically excited atoms by atoms and molecules. These formulas include the dependence of the Franck--Condon factors on the translational wavefunctions as well as the wavefunctions for the internal degrees of freedom. We use these formulas to evaluate the translational energy dependence of the fine structure transition cross sections for F( 2 P/sub 3/2/)+X→F( 2 P/sub 1/2/)+X, where X= Xe, H + , and H 2 . The cross sections generally increase as the initial translational energy increases. Our results agree semiquantiatively (or better) with those obtained from other theoretical techniques. In the case of F+H + we find that the absolute cross section is sensitive to the analytic form used for the nonadiabatic coupling but our model gives the correct energy dependence. At the energies of our calculations we find only a small amount of vibrational excitation of H 2 . Finally, we use our expressions to interpret some trends of available experimental results on the quenching of Hg ( 3 P 2 → 3 P 1 ) by several molecules. We find that collisional excitation of the internal modes of the molecule becomes more important as the initial translational energy increases. However, these modes do not contribute to the quenching cross section in a statistical fashion
Quantum-classical correspondence in steady states of nonadiabatic systems
Fujii, Mikiya; Yamashita, Koichi
2015-01-01
We first present nonadiabatic path integral which is exact formulation of quantum dynamics in nonadiabatic systems. Then, by applying the stationary phase approximations to the nonadiabatic path integral, a semiclassical quantization condition, i.e., quantum-classical correspondence, for steady states of nonadiabatic systems is presented as a nonadiabatic trace formula. The present quantum-classical correspondence indicates that a set of primitive hopping periodic orbits, which are invariant under time evolution in the phase space of the slow degree of freedom, should be quantized. The semiclassical quantization is then applied to a simple nonadiabatic model and accurately reproduces exact quantum energy levels
Xie, Changjian [Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing 210093 (China); Zhu, Xiaolei; Yarkony, David R., E-mail: jianyi.m@gmail.com, E-mail: yarkony@jhu.edu, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States); Ma, Jianyi, E-mail: jianyi.m@gmail.com, E-mail: yarkony@jhu.edu, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, Sichuan 610065 (China); Xie, Daiqian, E-mail: jianyi.m@gmail.com, E-mail: yarkony@jhu.edu, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing 210093 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Guo, Hua, E-mail: jianyi.m@gmail.com, E-mail: yarkony@jhu.edu, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)
2015-03-07
Non-adiabatic processes play an important role in photochemistry, but the mechanism for conversion of electronic energy to chemical energy is still poorly understood. To explore the possibility of vibrational control of non-adiabatic dynamics in a prototypical photoreaction, namely, the A-band photodissociation of NH{sub 3}(X{sup ~1}A{sub 1}), full-dimensional state-to-state quantum dynamics of symmetric or antisymmetric stretch excited NH{sub 3}(X{sup ~1}A{sub 1}) is investigated on recently developed coupled diabatic potential energy surfaces. The experimentally observed H atom kinetic energy distributions are reproduced. However, contrary to previous inferences, the NH{sub 2}(A{sup ~2}A{sub 1})/NH{sub 2}(X{sup ~2}B{sub 1}) branching ratio is found to be small regardless of the initial preparation of NH{sub 3}(X{sup ~1}A{sub 1}), while the internal state distribution of the preeminent fragment, NH{sub 2}(X{sup ~2}B{sub 1}), is found to depend strongly on the initial vibrational excitation of NH{sub 3}(X{sup ~1}A{sub 1}). The slow H atoms in photodissociation mediated by the antisymmetric stretch fundamental state are due to energy sequestered in the internally excited NH{sub 2}(X{sup ~2}B{sub 1}) fragment, rather than in NH{sub 2}(A{sup ~2}A{sub 1}) as previously proposed. The high internal excitation of the NH{sub 2}(X{sup ~2}B{sub 1}) fragment is attributed to the torques exerted on the molecule as it passes through the conical intersection seam to the ground electronic state of NH{sub 3}. Thus in this system, contrary to previous assertions, the control of electronic state branching by selective excitation of ground state vibrational modes is concluded to be ineffective. The juxtaposition of precise quantum mechanical results with complementary results based on quasi-classical surface hopping trajectories provides significant insights into the non-adiabatic process.
Castro, A., E-mail: acastro@bifi.es [Institute for Biocomputation and Physics of Complex Systems (BIFI) and Zaragoza Scientific Center for Advanced Modelling (ZCAM), University of Zaragoza, 50018 Zaragoza (Spain); Isla, M. [Departamento de Fisica Teorica, Atomica y Optica, Universidad de Valladolid, 47005 Valladolid (Spain); Martinez, Jose I. [Departamento de Fisica Teorica de la Materia Condensada, Universidad Autonoma de Madrid, ES-28049 Madrid (Spain); Alonso, J.A. [Departamento de Fisica Teorica, Atomica y Optica, Universidad de Valladolid, 47005 Valladolid (Spain)
2012-05-03
Graphical abstract: Two trajectories for the collision of a proton with the Lithium tetramer. On the left, the proton is scattered away, and a Li{sub 2} molecule plus two isolated Lithium atoms result. On the right, the proton is captured and a LiH molecule is created. Highlights: Black-Right-Pointing-Pointer Scattering of a proton with Lithium clusters described from first principles. Black-Right-Pointing-Pointer Description based on non-adiabatic molecular dynamics. Black-Right-Pointing-Pointer The electronic structure is described with time-dependent density-functional theory. Black-Right-Pointing-Pointer The method allows to discern reaction channels depending on initial parameters. - Abstract: We have employed non-adiabatic molecular dynamics based on time-dependent density-functional theory to characterize the scattering behavior of a proton with the Li{sub 4} cluster. This technique assumes a classical approximation for the nuclei, effectively coupled to the quantum electronic system. This time-dependent theoretical framework accounts, by construction, for possible charge transfer and ionization processes, as well as electronic excitations, which may play a role in the non-adiabatic regime. We have varied the incidence angles in order to analyze the possible reaction patterns. The initial proton kinetic energy of 10 eV is sufficiently high to induce non-adiabatic effects. For all the incidence angles considered the proton is scattered away, except in one interesting case in which one of the Lithium atoms captures it, forming a LiH molecule. This theoretical formalism proves to be a powerful, effective and predictive tool for the analysis of non-adiabatic processes at the nanoscale.
Shit, Anindita [Department of Chemistry, Bengal Engineering and Science University, Shibpur, Howrah 711103 (India); Chattopadhyay, Sudip, E-mail: sudip_chattopadhyay@rediffmail.com [Department of Chemistry, Bengal Engineering and Science University, Shibpur, Howrah 711103 (India); Ray Chaudhuri, Jyotipratim, E-mail: jprc_8@yahoo.com [Department of Physics, Katwa College, Katwa, Burdwan 713130 (India)
2014-03-18
Highlights: • Nonadiabatic dynamics of quantum particle under the impact of high-frequency force. • Formulation of time-independent dynamics via Floquet and Kapitza schemes. • Manipulation of external force parameters allows us to control the escape rate. • Increase of (amplitudes/frequency) causes the system to decay faster, in general. • Crossover temperature increases in the presence of the field. - Abstract: Escape under the action of the external modulation constitutes a nontrivial generalization of an conventional Kramers rate because the system is away from thermal equilibrium. A derivation of this result from the point of view of Langevin dynamics in the frame of Floquet theorem in conjunction with the Kapitza–Landau time window (that leads to an attractive description of the time-dependent quantum dynamics in terms of time-independent one) has been provided. The quantum escape rate in the intermediate-to-high and very-high damping regime so obtained analytically using the phase space formalism associated with the Wigner distribution and path-integral formalism bears a quantum correction that depends strongly on the barrier height. It is shown that an increase of (amplitude/frequency) ratio causes the system to decay faster, in general. The crossover temperature between tunneling and thermal activation increases in the presence of field so that quantum effects in the escape are relevant at higher temperatures.
Bera, Anupam; Ghosh, Jayanta; Bhattacharya, Atanu
2017-07-28
Conical intersections are now firmly established to be the key features in the excited electronic state processes of polyatomic energetic molecules. In the present work, we have explored conical intersection-mediated nonadiabatic chemical dynamics of a simple analogue nitramine molecule, dimethylnitramine (DMNA, containing one N-NO 2 energetic group), and its complex with an iron atom (DMNA-Fe). For this task, we have used the ab initio multiple spawning (AIMS) dynamics simulation at the state averaged-complete active space self-consistent field(8,5)/6-31G(d) level of theory. We have found that DMNA relaxes back to the ground (S 0 ) state following electronic excitation to the S 1 excited state [which is an (n,π*) excited state] with a time constant of approximately 40 fs. This AIMS result is in very good agreement with the previous surface hopping-result and femtosecond laser spectroscopy result. DMNA does not dissociate during this fast internal conversion from the S 1 to the S 0 state. DMNA-Fe also undergoes extremely fast relaxation from the upper S 1 state to the S 0 state; however, this relaxation pathway is dissociative in nature. DMNA-Fe undergoes initial Fe-O, N-O, and N-N bond dissociations during relaxation from the upper S 1 state to the ground S 0 state through the respective conical intersection. The AIMS simulation reveals the branching ratio of these three channels as N-N:Fe-O:N-O = 6:3:1 (based on 100 independent simulations). Furthermore, the AIMS simulation reveals that the Fe-O bond dissociation channel exhibits the fastest (time constant 24 fs) relaxation, while the N-N bond dissociation pathway features the slowest (time constant 128 fs) relaxation. An intermediate time constant (30 fs) is found for the N-O bond dissociation channel. This is the first nonadiabatic chemical dynamics study of metal-contained energetic molecules through conical intersections.
Bera, Anupam; Ghosh, Jayanta; Bhattacharya, Atanu
2017-07-01
Conical intersections are now firmly established to be the key features in the excited electronic state processes of polyatomic energetic molecules. In the present work, we have explored conical intersection-mediated nonadiabatic chemical dynamics of a simple analogue nitramine molecule, dimethylnitramine (DMNA, containing one N-NO2 energetic group), and its complex with an iron atom (DMNA-Fe). For this task, we have used the ab initio multiple spawning (AIMS) dynamics simulation at the state averaged-complete active space self-consistent field(8,5)/6-31G(d) level of theory. We have found that DMNA relaxes back to the ground (S0) state following electronic excitation to the S1 excited state [which is an (n,π*) excited state] with a time constant of approximately 40 fs. This AIMS result is in very good agreement with the previous surface hopping-result and femtosecond laser spectroscopy result. DMNA does not dissociate during this fast internal conversion from the S1 to the S0 state. DMNA-Fe also undergoes extremely fast relaxation from the upper S1 state to the S0 state; however, this relaxation pathway is dissociative in nature. DMNA-Fe undergoes initial Fe-O, N-O, and N-N bond dissociations during relaxation from the upper S1 state to the ground S0 state through the respective conical intersection. The AIMS simulation reveals the branching ratio of these three channels as N-N:Fe-O:N-O = 6:3:1 (based on 100 independent simulations). Furthermore, the AIMS simulation reveals that the Fe-O bond dissociation channel exhibits the fastest (time constant 24 fs) relaxation, while the N-N bond dissociation pathway features the slowest (time constant 128 fs) relaxation. An intermediate time constant (30 fs) is found for the N-O bond dissociation channel. This is the first nonadiabatic chemical dynamics study of metal-contained energetic molecules through conical intersections.
Mizuno, Yuta; Arasaki, Yasuki; Takatsuka, Kazuo
2016-11-14
We propose a theoretical principle to directly monitor the bifurcation of quantum wavepackets passing through nonadiabatic regions of a molecule that is placed in intense continuous wave (CW) laser fields. This idea makes use of the phenomenon of laser-driven photon emission from molecules that can undergo nonadiabatic transitions between ionic and covalent potential energy surfaces like Li + F - and LiF. The resultant photon emission spectra are of anomalous yet characteristic frequency and intensity, if pumped to an energy level in which the nonadiabatic region is accessible and placed in a CW laser field. The proposed method is designed to take the time-frequency spectrogram with an appropriate time-window from this photon emission to detect the time evolution of the frequency and intensity, which depends on the dynamics and location of the relevant nuclear wavepackets. This method is specifically designed for the study of dynamics in intense CW laser fields and is rather limited in scope than other techniques for femtosecond chemical dynamics in vacuum. The following characteristic features of dynamics can be mapped onto the spectrogram: (1) the period of driven vibrational motion (temporally confined vibrational states in otherwise dissociative channels, the period and other states of which dramatically vary depending on the CW driving lasers applied), (2) the existence of multiple nuclear wavepackets running individually on the field-dressed potential energy surfaces, (3) the time scale of coherent interaction between the nuclear wavepackets running on ionic and covalent electronic states after their branching (the so-called coherence time in the terminology of the theory of nonadiabatic interaction), and so on.
Schwerdtfeger, Christine A.; Soudackov, Alexander V.; Hammes-Schiffer, Sharon
2014-01-01
The development of efficient theoretical methods for describing electron transfer (ET) reactions in condensed phases is important for a variety of chemical and biological applications. Previously, dynamical dielectric continuum theory was used to derive Langevin equations for a single collective solvent coordinate describing ET in a polar solvent. In this theory, the parameters are directly related to the physical properties of the system and can be determined from experimental data or explicit molecular dynamics simulations. Herein, we combine these Langevin equations with surface hopping nonadiabatic dynamics methods to calculate the rate constants for thermal ET reactions in polar solvents for a wide range of electronic couplings and reaction free energies. Comparison of explicit and implicit solvent calculations illustrates that the mapping from explicit to implicit solvent models is valid even for solvents exhibiting complex relaxation behavior with multiple relaxation time scales and a short-time inertial response. The rate constants calculated for implicit solvent models with a single solvent relaxation time scale corresponding to water, acetonitrile, and methanol agree well with analytical theories in the Golden rule and solvent-controlled regimes, as well as in the intermediate regime. The implicit solvent models with two relaxation time scales are in qualitative agreement with the analytical theories but quantitatively overestimate the rate constants compared to these theories. Analysis of these simulations elucidates the importance of multiple relaxation time scales and the inertial component of the solvent response, as well as potential shortcomings of the analytical theories based on single time scale solvent relaxation models. This implicit solvent approach will enable the simulation of a wide range of ET reactions via the stochastic dynamics of a single collective solvent coordinate with parameters that are relevant to experimentally accessible
Ohta, Ayumi; Kobayashi, Osamu; Danielache, Sebastian O.; Nanbu, Shinkoh
2015-01-01
Highlights: • The photoisomerization between cyclohexadiene and hexatriene was simulated. • Nonadiabatic ab initio MD simulations were employed to elucidate the mechanism. • Each excitations to S_1 and S_2 were simulated using full-dimensional model. • Specific molecular motions at CoIns and molecular vibrations on S_1 PES were found. • The one-sided product branching ratio was obtained at the photoexcitation to S_2. - Abstract: The photoisomerization process between 1,3-cyclohexadiene (CHD) and 1,3,5-cis-hexatriene (HT) has been studied by nonadiabatic ab initio molecular dynamics based on trajectory surface-hopping approach with a full-dimensional reaction model. The quantum chemical calculations were treated at MS-MR-CASPT2 level for 8 electrons in 8 orbitals with the cc-pVDZ basis set. The Zhu–Nakamura formula was employed to evaluate nonadiabatic transition probabilities. S_1 and S_2 states were included in the photoisomerization dynamics. Lifetimes and CHD:HT branching ratios were computationally estimated on the basis of statistical analysis of multiple executed trajectories. The analysis of trajectories suggested that the nonadiabatic transitions at the S_0/S_1 and S_1/S_2 conical intersections (CoIn) are correlated to the Kekulé-type vibration and the C3–C4–C5 bending motion, respectively. The one-sided branching ratio was obtained by excitations to the S_2 state; 70:30. The critical branching process was found to be dominated by the location of CoIn in potential energy hypersurface of the excited state.
Induced photoemission from driven nonadiabatic dynamics in an avoided crossing system
Arasaki, Yasuki; Mizuno, Yuta; Takatsuka, Kazuo, E-mail: kaztak@mns2.c.u-tokyo.ac.jp [Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, Komaba, 153-8902 Tokyo (Japan); Scheit, Simona [Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, Komaba, 153-8902 Tokyo (Japan); Theoretische Chemie, Universität Heidelberg, Im Neuneheimer Feld 229, 69120 Heidelberg (Germany)
2014-12-21
When vibrational dynamics on an ionic state (large dipole moment) is coupled to that on a neutral state (small dipole moment) such as at an avoided crossing in the alkali halide system, the population transfer between the states cause oscillation of the molecular dipole, leading to dipole emission. Such dynamics may be driven by an external field. We study how the coupled wavepacket dynamics is affected by the parameters (intensity, frequency) of the driving field with the aim of making use of the photoemission as an alternative detection scheme of femtosecond and subfemtosecond vibrational and electronic dynamics or as a characteristic optical source.
Dittmann, Niklas; Splettstoesser, Janine; Helbig, Nicole
2018-04-01
We simulate the dynamics of a single-electron source, modeled as a quantum dot with on-site Coulomb interaction and tunnel coupling to an adjacent lead in time-dependent density-functional theory. Based on this system, we develop a time-nonlocal exchange-correlation potential by exploiting analogies with quantum-transport theory. The time nonlocality manifests itself in a dynamical potential step. We explicitly link the time evolution of the dynamical step to physical relaxation timescales of the electron dynamics. Finally, we discuss prospects for simulations of larger mesoscopic systems.
Henriet, Loïc; Sclocchi, Antonio; Orth, Peter P.; Le Hur, Karyn
2017-02-01
We analyze the topological deformations of the ground state manifold of a quantum spin-1/2 in a magnetic field H =H (sinθ cosϕ ,sinθ sinϕ ,cosθ ) induced by a coupling to an ohmic quantum dissipative environment at zero temperature. From Bethe ansatz results and a variational approach, we confirm that the Chern number associated with the geometry of the reduced spin ground state manifold is preserved in the delocalized phase for α <1 . We report a divergence of the Berry curvature at αc=1 for magnetic fields aligned along the equator θ =π /2 . This divergence is caused by the complete quenching of the transverse magnetic field by the bath associated with a gap closing that occurs at the localization Kosterlitz-Thouless quantum phase transition in this model. Recent experiments in quantum circuits have engineered nonequilibrium protocols to access topological properties from a measurement of a dynamical Chern number defined via the out-of-equilibrium spin expectation values. Applying a numerically exact stochastic Schrödinger approach we find that, for a fixed field sweep velocity θ (t )=v t , the bath induces a crossover from (quasi)adiabatic to nonadiabatic dynamical behavior when the spin bath coupling α increases. We also investigate the particular regime H /ωc≪v /H ≪1 with large bath cutoff frequency ωc, where the dynamical Chern number vanishes already at α =1 /2 . In this regime, the mapping to an interacting resonance level model enables us to analytically describe the behavior of the dynamical Chern number in the vicinity of α =1 /2 . We further provide an intuitive physical explanation of the bath-induced breakdown of adiabaticity in analogy to the Faraday effect in electromagnetism. We demonstrate that the driving of the spin leads to the production of a large number of bosonic excitations in the bath, which strongly affect the spin dynamics. Finally, we quantify the spin-bath entanglement and formulate an analogy with an effective
Glover, William J; Mori, Toshifumi; Schuurman, Michael S; Boguslavskiy, Andrey E; Schalk, Oliver; Stolow, Albert; Martínez, Todd J
2018-04-28
The excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene (BD), has long been the subject of controversy due to its strong coupling, ultrafast time scales and the difficulties that theory faces in describing the relevant electronic states in a balanced fashion. Here we apply Ab Initio Multiple Spawning (AIMS) using state-averaged complete active space multistate second order perturbation theory [SA-3-CAS(4/4)-MSPT2] which describes both static and dynamic electron correlation effects, providing a balanced description of both the initially prepared bright 1 1 B u (ππ*) state and non-adiabatically coupled dark 2 1 A g state of BD. Importantly, AIMS allows for on-the-fly calculations of experimental observables. We validate our approach by directly simulating the time resolved photoelectron-photoion coincidence spectroscopy results presented in Paper I [A. E. Boguslavskiy et al., J. Chem. Phys. 148, 164302 (2018)], demonstrating excellent agreement with experiment. Our simulations reveal that the initial excitation to the 1 1 B u state rapidly evolves via wavepacket dynamics that follow both bright- and dark-state pathways as well as mixtures of these. In order to test the sensitivity of the AIMS results to the relative ordering of states, we considered two hypothetical scenarios biased toward either the bright 1 B u or the dark 2 1 A g state. In contrast with AIMS/SA-3-CAS(4/4)-MSPT2 simulations, neither of these scenarios yields favorable agreement with experiment. Thus, we conclude that the excited state non-adiabatic dynamics in BD involves both of these ultrafast pathways.
Glover, William J.; Mori, Toshifumi; Schuurman, Michael S.; Boguslavskiy, Andrey E.; Schalk, Oliver; Stolow, Albert; Martínez, Todd J.
2018-04-01
The excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene (BD), has long been the subject of controversy due to its strong coupling, ultrafast time scales and the difficulties that theory faces in describing the relevant electronic states in a balanced fashion. Here we apply Ab Initio Multiple Spawning (AIMS) using state-averaged complete active space multistate second order perturbation theory [SA-3-CAS(4/4)-MSPT2] which describes both static and dynamic electron correlation effects, providing a balanced description of both the initially prepared bright 11Bu (ππ*) state and non-adiabatically coupled dark 21Ag state of BD. Importantly, AIMS allows for on-the-fly calculations of experimental observables. We validate our approach by directly simulating the time resolved photoelectron-photoion coincidence spectroscopy results presented in Paper I [A. E. Boguslavskiy et al., J. Chem. Phys. 148, 164302 (2018)], demonstrating excellent agreement with experiment. Our simulations reveal that the initial excitation to the 11Bu state rapidly evolves via wavepacket dynamics that follow both bright- and dark-state pathways as well as mixtures of these. In order to test the sensitivity of the AIMS results to the relative ordering of states, we considered two hypothetical scenarios biased toward either the bright 1Bu or the dark 21Ag state. In contrast with AIMS/SA-3-CAS(4/4)-MSPT2 simulations, neither of these scenarios yields favorable agreement with experiment. Thus, we conclude that the excited state non-adiabatic dynamics in BD involves both of these ultrafast pathways.
Wang, Jun; Huang, Jing; Du, Likai; Lan, Zhenggang
2015-07-09
The photoinduced intramolecular excited-state energy-transfer (EET) process in conjugated polymers has received a great deal of research interest because of its important role in the light harvesting and energy transport of organic photovoltaic materials in photoelectric devices. In this work, the silylene-bridged biphenyl and stilbene (SBS) system was chosen as a simplified model system to obtain physical insight into the photoinduced intramolecular energy transfer between the different building units of the SBS copolymer. In the SBS system, the vinylbiphenyl and vinylstilbene moieties serve as the donor (D) unit and the acceptor (A) unit, respectively. The ultrafast excited-state dynamics of the SBS system was investigated from the point of view of nonadiabatic dynamics with the surface-hopping method at the TDDFT level. The first two excited states (S1 and S2) are characterized by local excitations at the acceptor (vinylstilbene) and donor (vinylbiphenyl) units, respectively. Ultrafast S2-S1 decay is responsible for the intramolecular D-A excitonic energy transfer. The geometric distortion of the D moiety play an essential role in this EET process, whereas the A moiety remains unchanged during the nonadiabatic dynamics simulation. The present work provides a direct dynamical approach to understand the ultrafast intramolecular energy-transfer dynamics in SBS copolymers and other similar organic photovoltaic copolymers.
Ultrafast non-adiabatic dynamics of methyl substituted ethylenes: The π3s Rydberg state
Wu, Guorong; Boguslavskiy, Andrey E.; Schalk, Oliver; Schuurman, Michael S.; Stolow, Albert
2011-10-01
Excited state unimolecular reactions of some polyenes exhibit localization of their dynamics at a single ethylenic double bond. Here we present studies of the fundamental photophysical processes in the ethylene unit itself. Combined femtosecond time-resolved photoelectron spectroscopy (TRPES) and ab initio quantum chemical calculations was applied to the study of excited state dynamics in cis-butene, trans-butene, trimethylethylene, and tetramethylethylene, following initial excitation to their respective π3s Rydberg states. The wavelength dependence of the π3s Rydberg state dynamics of tetramethylethylene was investigated in more detail. The π3s Rydberg to ππ* valence state decay rate varies greatly with substituent: the 1,2-di- and tri-methyl substituted ethylenes (cis-butene, trans-butene, and trimethylethylene) show an ultrafast decay (˜20 fs), whereas the fully methylated tetramethylethylene shows a decay rate of 2 to 4 orders of magnitude slower. These observations are rationalized in terms of topographical trends in the relevant potential energy surfaces, as found from ab initio calculations: (1) the barrier between the π3s state and the ππ* state increases with increasing methylation, and (2) the π3s/ππ* minimum energy conical intersection displaces monotonically away from the π3s Franck-Condon region with increasing methylation. The use of systematic methylation in combination with TRPES and ab initio computation is emerging as an important tool in discerning the excited state dynamics of unsaturated hydrocarbons.
Yamamoto, Kentaro, E-mail: kyamamoto@fukui.kyoto-u.ac.jp; Takatsuka, Kazuo, E-mail: kaztak@fukui.kyoto-u.ac.jp
2016-08-22
Graphical abstract: Asymptotic biradical state produced by the excited-state coupled proton–electron transfer (CPET), resulting in charge separation (proton–electron pair creation) on a proton–electron acceptor A, in a series of photochemical systems generally denoted as X–Mn–OH{sub 2}⋯A, where X = (OH, Ca(OH){sub 3}) and A = (N-methylformamidine, guanidine, imidazole, or ammonia clusters). - Abstract: In this perspective article, we review, along with presenting new results, a series of our theoretical analyses on the excited-state mechanism of charge separation (proton–electron pair creation) relevant to the photoinduced water-splitting reaction (2H{sub 2}O → 4H{sup +} + 4e{sup −} + O{sub 2}) in organic and biological systems, which quite often includes Mn clusters in various molecular configurations. The present mechanism is conceived to be universal in the triggering process of the photoexcited water splitting dynamics. In other words, any Mn-based catalytic charge separation is quite likely to be initiated according to this mechanism. As computationally tractable yet realistic models, we examine a series of systems generally expressed as X–Mn–OH{sub 2}⋯A, where X = (OH, Ca(OH){sub 3}) and A = (N-methylformamidine, guanidine, imidazole or ammonia cluster) in terms of the theory of nonadiabatic electron wavepacket dynamics. We first find both an electron and a proton are simultaneously transferred to the acceptors through conical intersections upon photoexcitation. In this mechanism, the electron takes different pathways from that of the proton and reaches the densely lying Rydberg-like states of the acceptors in the end, thereby inducing charge separation. Therefore the presence of the Rydberg-like diffused unoccupied states as an electron acceptor is critical for this reaction to proceed. We also have found another crucial nonadiabatic process that deteriorates the efficiency of charge separation by rendering the created pair of proton
Semiclassical quantization of nonadiabatic systems with hopping periodic orbits
Fujii, Mikiya; Yamashita, Koichi
2015-01-01
We present a semiclassical quantization condition, i.e., quantum–classical correspondence, for steady states of nonadiabatic systems consisting of fast and slow degrees of freedom (DOFs) by extending Gutzwiller’s trace formula to a nonadiabatic form. The quantum–classical correspondence indicates that a set of primitive hopping periodic orbits, which are invariant under time evolution in the phase space of the slow DOF, should be quantized. The semiclassical quantization is then applied to a simple nonadiabatic model and accurately reproduces exact quantum energy levels. In addition to the semiclassical quantization condition, we also discuss chaotic dynamics involved in the classical limit of nonadiabatic dynamics
Wave Packet Simulation of Nonadiabatic Dynamics in Highly Excited 1,3-Dibromopropane
Brogaard, Rasmus Y.; Møller, Klaus Braagaard; Sølling, Theis Ivan
2008-01-01
]. In the experiment. DBP is excited to a Rydberg state 8 eV above the ground state. The interpretation of the results is that a torsional motion of the bromomethylene groups with a vibrational period of 680 is is activated upon excitation. The Rydberg state decays to a valence state, causing a dissociation of one...... of the carbon bromine bonds oil a time scale of 2.5 ps. Building the theoretical framework for the wave packet propagation around this model of the reaction dynamics, the Simulations reproduce, to a good extent, the time scales observed in the experiment. Furthermore. the Simulations provide insight into how...... the torsion motion influences the bond breakage, and C we can conclude that the mechanism that delays the dissociation is solely the electronic transition from the Rydberg state to the valence state and does not involve, for example, intramolecular vibrational energy redistribution (IVR)....
Bennett, Kochise; Kowalewski, Markus; Mukamel, Shaul
2016-02-09
We present a hierarchy of Fermi golden rules (FGRs) that incorporate strongly coupled electronic/nuclear dynamics in time-resolved photoelectron spectroscopy (TRPES) signals at different levels of theory. Expansion in the joint electronic and nuclear eigenbasis yields the numerically most challenging exact FGR (eFGR). The quasistatic Fermi Golden Rule (qsFGR) neglects nuclear motion during the photoionization process but takes into account electronic coherences as well as populations initially present in the pumped matter as well as those generated internally by coupling between electronic surfaces. The standard semiclassical Fermi Golden Rule (scFGR) neglects the electronic coherences and the nuclear kinetic energy during the ionizing pulse altogether, yielding the classical Condon approximation. The coherence contributions depend on the phase-profile of the ionizing field, allowing coherent control of TRPES signals. The photoelectron spectrum from model systems is simulated using these three levels of theory. The eFGR and the qsFGR show temporal oscillations originating from the electronic or vibrational coherences generated as the nuclear wave packet traverses a conical intersection. These oscillations, which are missed by the scFGR, directly reveal the time-evolving splitting between electronic states of the neutral molecule in the curve-crossing regime.
Fischer, Sean A; Lingerfelt, David B; May, Joseph W; Li, Xiaosong
2014-09-07
The unique electronic structure of Mn(2+)-doped ZnO quantum dots gives rise to photoionization states that can be used to manipulate the magnetic state of the material and to generate zero-reabsorption luminescence. Fast formation and long non-radiative decay of this photoionization state is a necessary requirement for these important applications. In this work, surface hopping based non-adiabatic molecular dynamics are used to demonstrate the fast formation of a metal-to-ligand charge transfer state in a Mn(2+)-doped ZnO quantum dot. The formation occurs on an ultrafast timescale and is aided by the large density of states and significant mixing of the dopant Mn(2+) 3dt2 levels with the valence-band levels of the ZnO lattice. The non-radiative lifetime of the photoionization states is also investigated.
Boguslavskiy, Andrey E.; Schalk, Oliver; Gador, Niklas; Glover, William J.; Mori, Toshifumi; Schultz, Thomas; Schuurman, Michael S.; Martínez, Todd J.; Stolow, Albert
2018-04-01
The ultrafast excited state dynamics of the smallest polyene, trans-1,3-butadiene, were studied by femtosecond time-resolved photoelectron-photoion coincidence (TRPEPICO) spectroscopy. The evolution of the excited state wavepacket, created by pumping the bright 1Bu (ππ*) electronic state at its origin of 216 nm, is projected via one- and two-photon ionization at 267 nm onto several ionization continua. The results are interpreted in terms of Koopmans' correlations and Franck-Condon factors for the excited and cationic states involved. The known predissociative character of the cation excited states is utilized to assign photoelectron bands to specific continua using TRPEPICO spectroscopy. This permits us to report the direct observation of the famously elusive S1(21Ag) dark electronic state during the internal conversion of trans 1,3-butadiene. Our phenomenological analysis permits the spectroscopic determination of several important time constants. We report the overall decay lifetimes of the 11Bu and 21Ag states and observe the re-appearance of the hot ground state molecule. We argue that the apparent dephasing time of the S2(11Bu) state, which leads to the extreme breadth of the absorption spectrum, is principally due to large amplitude torsional motion on the 1Bu surface in conjunction with strong non-adiabatic couplings via conical intersections, whereupon nuclear wavepacket revivals to the initial Franck-Condon region become effectively impossible. In Paper II [W. J. Glover et al., J. Chem. Phys. 148, 164303 (2018)], ab initio multiple spawning is used for on-the-fly computations of the excited state non-adiabatic wavepacket dynamics and their associated TRPEPICO observables, allowing for direct comparisons of experiment with theory.
Wu, Guorong; Neville, Simon P.; Schalk, Oliver; Sekikawa, Taro; Ashfold, Michael N. R.; Worth, Graham A.; Stolow, Albert
2016-01-01
The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A 2 (πσ ∗ ) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B 1 (π3p y ) Rydberg state, followed by prompt internal conversion to the A 2 (πσ ∗ ) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A 2 (πσ ∗ ) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A 2 (πσ ∗ ) state, facilitating wavepacket motion around the potential barrier in the N–CH 3 dissociation coordinate
Wu, Guorong [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Synergetic Innovation Center of Quantum Information & Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Neville, Simon P. [Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Schalk, Oliver [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Physics, AlbaNova University Center, Stockholm University, Roslagstullsbacken 21, 106 91 Stockholm (Sweden); Sekikawa, Taro [Department of Applied Physics, Hokkaido University, Kita-13 Nishi-8, Kita-ku, Sapporo 060-8628 (Japan); Ashfold, Michael N. R. [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Worth, Graham A. [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Stolow, Albert, E-mail: astolow@uottawa.ca [National Research Council Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada); Department of Physics, University of Ottawa, 150 Louis Pasteur, Ottawa, Ontario K1N 6N5 (Canada)
2016-01-07
The dynamics of N-methylpyrrole following excitation at wavelengths in the range 241.5-217.0 nm were studied using a combination of time-resolved photoelectron spectroscopy (TRPES), ab initio quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree method, as well as high-level photoionization cross section calculations. Excitation at 241.5 and 236.2 nm results in population of the A{sub 2}(πσ{sup ∗}) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B{sub 1}(π3p{sub y}) Rydberg state, followed by prompt internal conversion to the A{sub 2}(πσ{sup ∗}) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A{sub 2}(πσ{sup ∗}) state was found to vary with excitation wavelength, decreasing by one order of magnitude upon tuning from 241.5 nm to 236.2 nm and by more than three orders of magnitude when excited at 217.0 nm. The order of magnitude difference in lifetimes measured at the longer excitation wavelengths is attributed to vibrational excitation in the A{sub 2}(πσ{sup ∗}) state, facilitating wavepacket motion around the potential barrier in the N–CH{sub 3} dissociation coordinate.
Glowacki, David
Recently, we outlined an efficient multi-tiered parallel excitonic framework that utilizes time dependent density functional theory (TDDFT) to calculate ground/excited state energies and gradients of large supramolecular complexes in atomistic detail. In this paper, we apply our ab initioexciton framework to the 27 coupled bacteriocholorophyll-a chromophores which make up the LH2 complex, using it to compute linear absorption spectra and short-time, on-the-fly nonadiabatic surface-hopping (SH) dynamics of electronically excited LH2. Our ab initio exciton model includes two key parameters whose values are determined by fitting to experiment: d, which is added to the diagonal elements, corrects for the error in TDDFT vertical excitation energies on a single chromophore; and e, which occurs on the off-diagonal matrix elements, describes the average dielectric screening of the inter-chromophore transition-dipole coupling. Using snapshots obtained from equilibrium molecular dynamics simulations (MD) of LH2, best-fit values of both d and e were obtained by fitting to the thermally broadened experimental absorption spectrum within the Frank-Condon approximation, providing a linear absorption spectrum that agrees reasonably well with the experimental observations. We follow the nonadiabatic dynamics using surface hopping to construct time-resolved visualizations of the EET dynamics in the sub-picosecond regime following photoexcitation. This provides some qualitative insight into the excitonic energy transfer (EET) that results from atomically resolved vibrational fluctuations of the chromophores. The dynamical picture that emerges is one of rapidly fluctuating eigenstates that are delocalized over multiple chromophores and undergo frequent crossing on a femtosecond timescale as a result of the underlying chromophore vibrational dynamics. The eigenstate fluctuations arise from disorder in both the diagonal chromophore site energies and the off-diagonal inter
Nonadiabatic holonomic quantum computation using Rydberg blockade
Kang, Yi-Hao; Chen, Ye-Hong; Shi, Zhi-Cheng; Huang, Bi-Hua; Song, Jie; Xia, Yan
2018-04-01
In this paper, we propose a scheme for realizing nonadiabatic holonomic computation assisted by two atoms and the shortcuts to adiabaticity (STA). The blockade effect induced by strong Rydberg-mediated interaction between two Rydberg atoms provides us the possibility to simplify the dynamics of the system, and the STA helps us design pulses for implementing the holonomic computation with high fidelity. Numerical simulations show the scheme is noise immune and decoherence resistant. Therefore, the current scheme may provide some useful perspectives for realizing nonadiabatic holonomic computation.
Xia, Shu-Hua; Liu, Xiang-Yang; Fang, Qiu; Cui, Ganglong, E-mail: ganglong.cui@bnu.edu.cn [Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China)
2015-11-21
In this work, we have first employed the combined quantum mechanics/molecular mechanics (QM/MM) method to study the photodissociation mechanism of thioacetic acid CH{sub 3}C(O)SH in the S{sub 1}, T{sub 1}, and S{sub 0} states in argon matrix. CH{sub 3}C(O)SH is treated quantum mechanically using the complete active space self-consistent field and complete active space second-order perturbation theory methods; argon matrix is described classically using Lennard-Jones potentials. We find that the C-S bond fission is predominant due to its small barriers of ca. 3.0 and 1.0 kcal/mol in the S{sub 1} and T{sub 1} states. It completely suppresses the nearby C—C bond fission. After the bond fission, the S{sub 1} radical pair of CH{sub 3}CO and SH can decay to the S{sub 0} and T{sub 1} states via internal conversion and intersystem crossing, respectively. In the S{sub 0} state, the radical pair can either recombine to form CH{sub 3}C(O)SH or proceed to form molecular products of CH{sub 2}CO and H{sub 2}S. We have further employed our recently developed QM/MM generalized trajectory-based surface-hopping method to simulate the photodissociation dynamics of CH{sub 3}C(O)SH. In 1 ps dynamics simulation, 56% trajectories stay at the Franck-Condon region; the S{sub 1} C—S bond fission takes place in the remaining 44% trajectories. Among all nonadiabatic transitions, the S{sub 1} → S{sub 0} internal conversion is major (55%) but the S{sub 1} → T{sub 1} intersystem crossing is still comparable and cannot be ignored, which accounts for 28%. Finally, we have found a radical channel generating the molecular products of CH{sub 2}CO and H{sub 2}S, which is complementary to the concerted molecular channel. The present work sets the stage for simulating photodissociation dynamics of similar thio-carbonyl systems in matrix.
Many-electron model for multiple ionization in atomic collisions
Archubi, C D; Montanari, C C; Miraglia, J E
2007-01-01
We have developed a many-electron model for multiple ionization of heavy atoms bombarded by bare ions. It is based on the transport equation for an ion in an inhomogeneous electronic density. Ionization probabilities are obtained by employing the shell-to-shell local plasma approximation with the Levine and Louie dielectric function to take into account the binding energy of each shell. Post-collisional contributions due to Auger-like processes are taken into account by employing recent photoemission data. Results for single-to-quadruple ionization of Ne, Ar, Kr and Xe by protons are presented showing a very good agreement with experimental data
Many-electron model for multiple ionization in atomic collisions
Archubi, C D [Instituto de AstronomIa y Fisica del Espacio, Casilla de Correo 67, Sucursal 28 (C1428EGA) Buenos Aires (Argentina); Montanari, C C [Instituto de AstronomIa y Fisica del Espacio, Casilla de Correo 67, Sucursal 28 (C1428EGA) Buenos Aires (Argentina); Miraglia, J E [Instituto de AstronomIa y Fisica del Espacio, Casilla de Correo 67, Sucursal 28 (C1428EGA) Buenos Aires (Argentina)
2007-03-14
We have developed a many-electron model for multiple ionization of heavy atoms bombarded by bare ions. It is based on the transport equation for an ion in an inhomogeneous electronic density. Ionization probabilities are obtained by employing the shell-to-shell local plasma approximation with the Levine and Louie dielectric function to take into account the binding energy of each shell. Post-collisional contributions due to Auger-like processes are taken into account by employing recent photoemission data. Results for single-to-quadruple ionization of Ne, Ar, Kr and Xe by protons are presented showing a very good agreement with experimental data.
Theory of many-electron atoms. Selected papers
Jucys, A.P.
1978-01-01
Selected papers of the founder of contemporary theoretical physics in Lithuania Adolfas Jucys on the theory of many-electron atoms and their spectra are presented, as well as a complete bibliography of his scientific works, a brief biographical essay and description of his scientific and social activities, reminiscences of other scientists about him. In these papers such questions are considered: Fock's self-consistent field in different approximations, various problems of the many-configurational approximation, incomplete separation of variables, expanded calculation method, application of nonorthogonal radial orbitals, method of irreducible tensor operators, graphical representation of the matrix elements and a number of other problems
Nonadiabatic transition path sampling
Sherman, M. C.; Corcelli, S. A.
2016-01-01
Fewest-switches surface hopping (FSSH) is combined with transition path sampling (TPS) to produce a new method called nonadiabatic path sampling (NAPS). The NAPS method is validated on a model electron transfer system coupled to a Langevin bath. Numerically exact rate constants are computed using the reactive flux (RF) method over a broad range of solvent frictions that span from the energy diffusion (low friction) regime to the spatial diffusion (high friction) regime. The NAPS method is shown to quantitatively reproduce the RF benchmark rate constants over the full range of solvent friction. Integrating FSSH within the TPS framework expands the applicability of both approaches and creates a new method that will be helpful in determining detailed mechanisms for nonadiabatic reactions in the condensed-phase.
Andriiko, Aleksandr A. [National Technical Univ. Ukraine, Kyiv (Ukraine). Kyiv Polytechnic Inst.; Andriyko, Yuriy O. [CEST Centre of Electrochemical Surface Technology, Wiener Neustadt (Austria); Nauer, Gerhard E. [Vienna Univ. (Austria). Inst. of Physical Chemistry
2013-02-01
The authors provide a unified concept for understanding multi-electron processes in electrochemical systems such as molten salts, ionic liquids, or ionic solutions. A major advantage of this concept is its independence of assumptions like one-step many-electron transfers or 'discrete' discharge of complex species. This book contains the following main topics: 1. Many-electron electrochemical systems: Concepts and definitions. 2. Many-electron systems at equilibrium. 3. Phenomenology of electrochemical kinetics. 4. Electrode film systems: experimental evidences. 5. Dynamics of a non-equilibrium electrochemical system. 6. Electrochemistry of Ti(IV) in ionic liquids.
Gan, Yanzhen; Yue, Ling; Guo, Xugeng; Zhu, Chaoyuan; Cao, Zexing
2017-05-17
An on-the-fly trajectory surface hopping dynamic simulation has been performed for revealing the multi-state nonadiabatic deactivation mechanism of coumarin. The mechanism involves three adiabatic excited states, S 3 (ππ*L b ), S 2 (nπ*, ππ*L a ) and S 1 (ππ*L a , nπ*), and the ground state S 0 at the four state-averaged complete active space self-consistent field, SA4-CASSCF(12,10)/6-31G* level of theory. Upon photoexcitation to the third excited state S 3 (ππ*L b ) in the Franck-Condon region, 80% sampling trajectories decay to the dark S 2 (nπ*) state within an average of 5 fs via the conical intersection S 3 (ππ*L b )/S 2 (nπ*), while 20% decay to the S 2 (ππ*L a ) state within an average of 11 fs via the conical intersection S 3 (ππ*L b )/S 2 (ππ*L a ). Then, sampling trajectories via S 2 (nπ*)/S 1 (ππ*L a ) continue with ultrafast decay processes to give a final distribution of quantum yields as follows: 42% stay on the dark S 1 (nπ*) state, 43.3% go back to the ground S 0 state, 12% undergo a ring-opening reaction to the Z-form S 0 (Z) state, and 2.7% go to the E-form S 0 (E) state. The lifetimes of the excited states are estimated as follows: the S 3 state is about 12 fs on average, the S 2 state is about 80 fs, and the S 1 state has a fast component of about 160 fs and a slow component of 15 ps. The simulated ultrafast radiationless deactivation pathways of photoexcited coumarin immediately interpret the experimentally observed weak fluorescence emission.
Many-electron phenomena in the ionization of ions
Mueller, A.
2004-01-01
Full text: Single and multiple ionization in ion-atom collisions involve a multitude of complex interactions between the electrons and nuclei of projectile and target. Some of the complexity is avoided in studies of fast collisions when the impulse approximation can be applied and the electrons can be described as independent quasi-free particles with a known momentum distribution. For the detailed investigation of ionization mechanisms that can occur in fast ion-atom collisions, it is illuminating to consider collisions of ions (or atoms) and really free electrons with a narrow energy spread. High energy resolution in electron-ion collision studies provides access to individual, possibly even state-selective, reaction pathways. Even in the simple electron-ion collision system (simple compared with the initial ion-atom problem) single and multiple ionization still involve a multitude of complex mechanisms. Besides the direct removal of one or several electrons from the target by electron impact, resonant and non-resonant formation of intermediate multiply excited states which subsequently decay by electron emission is important in single and multiple ionization of ions and atoms. Direct ionization proceeds via one-step or multi-step knock-off mechanisms which can partly be disentangled by studying effects of different projectile species. The role of multiply excited states in the ionization can be experimentally studied in great detail by a further reduction of the initial ion-atom problem. Multiply excited states of atoms and ions can be selectively populated by photon-ion interactions making use of the potential for extreme energy resolution made available at modern synchrotron radiation sources. In the review talk, examples of studies on single and multiple ionization in electron-ion collisions will be discussed in some detail. Electron-ion collision experiments will also be compared with photon-ion interaction studies. Many-electron phenomena have been observed
Enhanced Nonadiabaticity in Vortex Cores due to the Emergent Hall Effect
Bisig, André
2017-01-04
We present a combined theoretical and experimental study, investigating the origin of the enhanced nonadiabaticity of magnetic vortex cores. Scanning transmission x-ray microscopy is used to image the vortex core gyration dynamically to measure the nonadiabaticity with high precision, including a high confidence upper bound. We show theoretically, that the large nonadiabaticity parameter observed experimentally can be explained by the presence of local spin currents arising from a texture induced emergent Hall effect. This study demonstrates that the magnetic damping α and nonadiabaticity parameter β are very sensitive to the topology of the magnetic textures, resulting in an enhanced ratio (β/α>1) in magnetic vortex cores or Skyrmions.
Enhanced Nonadiabaticity in Vortex Cores due to the Emergent Hall Effect
Bisig, André
2017-01-01
We present a combined theoretical and experimental study, investigating the origin of the enhanced nonadiabaticity of magnetic vortex cores. Scanning transmission x-ray microscopy is used to image the vortex core gyration dynamically to measure the nonadiabaticity with high precision, including a high confidence upper bound. We show theoretically, that the large nonadiabaticity parameter observed experimentally can be explained by the presence of local spin currents arising from a texture induced emergent Hall effect. This study demonstrates that the magnetic damping α and nonadiabaticity parameter β are very sensitive to the topology of the magnetic textures, resulting in an enhanced ratio (β/α>1) in magnetic vortex cores or Skyrmions.
Zhou, Linsen [Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing 210093 (China); Xie, Daiqian, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Institute of Theoretical and Computational Chemistry, Nanjing University, Nanjing 210093 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Guo, Hua, E-mail: dqxie@nju.edu.cn, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)
2015-03-28
A detailed quantum mechanical characterization of the photodissociation dynamics of H{sub 2}O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH(X{sup ~}/A{sup ~}) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH(X{sup ~}, v = 0) exhibit very different characteristics. The A′ states, produced mostly via the B{sup ~}→X{sup ~} conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B{sup ~}→A{sup ~} Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH(X{sup ~}) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B{sup ~}→X{sup ~} non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH(A{sup ~}) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces.
Zhou, Linsen; Xie, Daiqian; Guo, Hua
2015-01-01
A detailed quantum mechanical characterization of the photodissociation dynamics of H 2 O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH(X ~ /A ~ ) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH(X ~ , v = 0) exhibit very different characteristics. The A′ states, produced mostly via the B ~ →X ~ conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B ~ →A ~ Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH(X ~ ) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B ~ →X ~ non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH(A ~ ) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces
Zhou, Linsen; Xie, Daiqian; Guo, Hua
2015-03-01
A detailed quantum mechanical characterization of the photodissociation dynamics of H2O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH( X ˜ / A ˜ ) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH( X ˜ , v = 0) exhibit very different characteristics. The A' states, produced mostly via the B ˜ → X ˜ conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B ˜ → A ˜ Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH( X ˜ ) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B ˜ → X ˜ non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH( A ˜ ) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces.
Zhou, Linsen; Xie, Daiqian; Guo, Hua
2015-03-28
A detailed quantum mechanical characterization of the photodissociation dynamics of H2O at 121.6 nm is presented. The calculations were performed using a full-dimensional wave packet method on coupled potential energy surfaces of all relevant electronic states. Our state-to-state model permits a detailed analysis of the OH(X̃/Ã) product fine-structure populations as a probe of the non-adiabatic dissociation dynamics. The calculated rotational state distributions of the two Λ-doublet levels of OH(X̃, v = 0) exhibit very different characteristics. The A' states, produced mostly via the B̃→X̃ conical intersection pathway, have significantly higher populations than the A″ counterparts, which are primarily from the B̃→Ã Renner-Teller pathway. The former features a highly inverted and oscillatory rotational state distribution, while the latter has a smooth distribution with much less rotational excitation. In good agreement with experiment, the calculated total OH(X̃) rotational state distribution and anisotropy parameters show clear even-odd oscillations, which can be attributed to a quantum mechanical interference between waves emanating from the HOH and HHO conical intersections in the B̃→X̃ non-adiabatic pathway. On the other hand, the experiment-theory agreement for the OH(Ã) fragment is also satisfactory, although some small quantitative differences suggest remaining imperfections of the ab initio based potential energy surfaces.
Nonadiabatic anharmonic electron transfer
Schmidt, P. P. [Molecular Physics Research, 6547 Kristina Ursula Court, Falls Church, Virginia 22044 (United States)
2013-03-28
The effect of an inner sphere, local mode vibration on an electron transfer is modeled using the nonadiabatic transition probability (rate) expression together with both the anharmonic Morse and the harmonic oscillator potential. For an anharmonic inner sphere mode, a variational analysis uses harmonic oscillator basis functions to overcome the difficulties evaluating Morse-model Franck-Condon overlap factors. Individual matrix elements are computed with the use of new, fast, robust, and flexible recurrence relations. The analysis therefore readily addresses changes in frequency and/or displacement of oscillator minimums in the different electron transfer states. Direct summation of the individual Boltzmann weighted Franck-Condon contributions avoids the limitations inherent in the use of the familiar high-temperature, Gaussian form of the rate constant. The effect of harmonic versus anharmonic inner sphere modes on the electron transfer is readily seen, especially in the exoergic, inverted region. The behavior of the transition probability can also be displayed as a surface for all temperatures and values of the driving force/exoergicity {Delta}=-{Delta}G. The temperature insensitivity of the transfer rate is clearly seen when the exoergicity equals the collective reorganization energy ({Delta}={Lambda}{sub s}) along a maximum ln (w) vs. {Delta} ridge of the surface. The surface also reveals additional regions for {Delta} where ln (w) appears to be insensitive to temperature, or effectively activationless, for some kinds of inner sphere contributions.
Vibrational nonadiabaticity and tunneling effects in transition state theory
Marcus, R.A.
1979-01-01
The usual quantum mechanical derivation of transition state theory is a statistical one (a quasi-equilibrium is assumed) or dynamical. The typical dynamical one defines a set of internal states and assumes vibrational adiabaticity. Effects of nonadiabaticity before and after the transition state are included in the present derivation, assuming a classical treatment of the reaction coordinate. The relation to a dynamical derivation of classical mechanical transition state theory is described, and tunneling effects are considered
Du Luchun; Mei Dongcheng
2011-01-01
The non-adiabatic regime of stochastic resonance (SR) in a bistable system with time delay, an additive white noise and a periodic signal was investigated. The signal power amplification η was employed to characterize the SR of the system. The simulation results indicate that (i) in the case of intermediate frequency Ω of the periodic signal, the typical behavior of SR is lowered monotonically by increasing the delay time τ; in the case of large Ω, τ weakens the SR behavior and then enhances it, with a non-monotonic behavior as a function of time delay; (ii) time delay induces SR when A is above the threshold, whereas no such resonance exists in the absence of time delay; (iii) time delay induces a transition from bimodal to unimodal configuration of η; (iv) varying the particular form of time delay results in different phenomena.
Nonadiabatic transitions in electrostatically trapped ammonia molecules
Kirste, Moritz; Schnell, Melanie; Meijer, Gerard; Sartakov, Boris G.
2009-01-01
Nonadiabatic transitions are known to be major loss channels for atoms in magnetic traps but have thus far not been experimentally reported upon for trapped molecules. We have observed and quantified losses due to nonadiabatic transitions for three isotopologues of ammonia in electrostatic traps by comparing the trapping times in traps with a zero and a nonzero electric field at the center. Nonadiabatic transitions are seen to dominate the overall loss rate even for the present samples that are at relatively high temperatures of 30 mK. It is anticipated that losses due to nonadiabatic transitions in electric fields are omnipresent in ongoing experiments on cold molecules.
Habershon, Scott
2013-01-01
We introduce a new approach for calculating quantum time-correlation functions and time-dependent expectation values in many-body thermal systems; both electronically adiabatic and non-adiabatic cases can be treated. Our approach uses a path integral simulation to sample an initial thermal density matrix; subsequent evolution of this density matrix is equivalent to solution of the time-dependent Schrödinger equation, which we perform using a linear expansion of Gaussian wavepacket basis functions which evolve according to simple classical-like trajectories. Overall, this methodology represents a formally exact approach for calculating time-dependent quantum properties; by introducing approximations into both the imaginary-time and real-time propagations, this approach can be adapted for complex many-particle systems interacting through arbitrary potentials. We demonstrate this method for the spin Boson model, where we find good agreement with numerically exact calculations. We also discuss future directions of improvement for our approach with a view to improving accuracy and efficiency
Habershon, Scott
2013-09-14
We introduce a new approach for calculating quantum time-correlation functions and time-dependent expectation values in many-body thermal systems; both electronically adiabatic and non-adiabatic cases can be treated. Our approach uses a path integral simulation to sample an initial thermal density matrix; subsequent evolution of this density matrix is equivalent to solution of the time-dependent Schrödinger equation, which we perform using a linear expansion of Gaussian wavepacket basis functions which evolve according to simple classical-like trajectories. Overall, this methodology represents a formally exact approach for calculating time-dependent quantum properties; by introducing approximations into both the imaginary-time and real-time propagations, this approach can be adapted for complex many-particle systems interacting through arbitrary potentials. We demonstrate this method for the spin Boson model, where we find good agreement with numerically exact calculations. We also discuss future directions of improvement for our approach with a view to improving accuracy and efficiency.
Thomas, Aaron M; Dangi, Beni B; Yang, Tao; Kaiser, Ralf I; Lin, Lin; Chou, Tzu-Jung; Chang, Agnes H H
2018-06-06
The bimolecular gas phase reaction of ground-state silicon (Si; 3 P) with dimethylacetylene (C 4 H 6 ; X 1 A 1g ) was investigated under single collision conditions in a crossed molecular beams machine. Merged with electronic structure calculations, the data propose nonadiabatic reaction dynamics leading to the formation of singlet SiC 4 H 4 isomer(s) and molecular hydrogen (H 2 ) via indirect scattering dynamics along with intersystem crossing (ISC) from the triplet to the singlet surface. The reaction may lead to distinct energetically accessible singlet SiC 4 H 4 isomers ( 1 p8- 1 p24) in overall exoergic reaction(s) (-107 -20 +12 kJ mol -1 ). All feasible reaction products are either cyclic, carry carbene analogous silylene moieties, or carry C-Si-H or C-Si-C bonds that would require extensive isomerization from the initial collision complex(es) to the fragmenting singlet intermediate(s). The present study demonstrates the first successful crossed beams study of an exoergic reaction channel arising from bimolecular collisions of silicon, Si( 3 P), with a hydrocarbon molecule.
Many-electron approaches in physics, chemistry and mathematics a multidisciplinary view
Site, Luigi
2014-01-01
This book provides a broad description of the development and (computational) application of many-electron approaches from a multidisciplinary perspective. In the context of studying many-electron systems Computer Science, Chemistry, Mathematics and Physics are all intimately interconnected. However, beyond a handful of communities working at the interface between these disciplines, there is still a marked separation of subjects. This book seeks to offer a common platform for possible exchanges between the various fields and to introduce the reader to perspectives for potential further developments across the disciplines. The rapid advances of modern technology will inevitably require substantial improvements in the approaches currently used, which will in turn make exchanges between disciplines indispensable. In essence this book is one of the very first attempts at an interdisciplinary approach to the many-electron problem.
Evidence for a new class of many-electron Auger transitions in atoms
Lee, I.; Wehlitz, R.; Becker, U.; Amusia, M.Ya.; Academy of Sciences, Saint Petersburg
1993-01-01
The possibility of the joint decay of two holes and one excited electron is discussed as one way many-electron Auger transitions can take place. It is shown that existing experimental decay spectra of resonantly excited states in krypton and xenon exhibit weak lines which may be associated with this new type of Auger process. (Author)
Nonadiabatic effect on the quantum heat flux control.
Uchiyama, Chikako
2014-05-01
We provide a general formula of quantum transfer that includes the nonadiabatic effect under periodic environmental modulation by using full counting statistics in Hilbert-Schmidt space. Applying the formula to an anharmonic junction model that interacts with two bosonic environments within the Markovian approximation, we find that the quantum transfer is divided into the adiabatic (dynamical and geometrical phases) and nonadiabatic contributions. This extension shows the dependence of quantum transfer on the initial condition of the anharmonic junction just before the modulation, as well as the characteristic environmental parameters such as interaction strength and cut-off frequency of spectral density. We show that the nonadiabatic contribution represents the reminiscent effect of past modulation including the transition from the initial condition of the anharmonic junction to a steady state determined by the very beginning of the modulation. This enables us to tune the frequency range of modulation, whereby we can obtain the quantum flux corresponding to the geometrical phase by setting the initial condition of the anharmonic junction.
Pederzoli, Marek; Pittner, Jiří
2017-01-01
Roč. 146, č. 11 (2017), č. článku 114101. ISSN 0021-9606 R&D Projects: GA ČR(CZ) GAP208/12/0559 Institutional support: RVO:61388955 Keywords : configuration-interaction method * potential-energy surfaces * excited-state dynamics * photodissociation dynamics * electronic states * quantum dynamics Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 2.965, year: 2016
Nonlinear ionization of many-electron systems over a broad photon-energy range
Karamatskou, Antonia
2015-11-01
Rapid developments in laser technology and, in particular, the advances in the realm of free-electron lasers have initiated tremendous progress in both theoretical and experimental atomic, molecular and optical physics. Owing to high intensities in combination with short pulse durations we can enter the utterly nonlinear regime of light-matter interaction and study the dynamics and features of matter under extreme conditions. The capabilities of X-ray free-electron laser sources have promoted the importance of nonlinear optics also in the X-ray regime. I show in my thesis how we can exploit the nonlinear response regime to reveal hidden information about resonance structures that are not resolved in the weak-field regime. This prospect points to many applications for future investigations of various complex systems with free-electron lasers. In the present thesis the interaction of atomic closed-shell systems with ultrashort and strong laser pulses is investigated. Over a broad photon-energy range the characteristics of the atomic shell are studied with a particular focus on the nonlinear response regime and on electron correlation effects. Several computational extensions of the XCID package for multi-electron dynamics are presented and their applications in various studies are demonstrated; a completely new capability of the numerical method is realized by implementing the calculation of photoelectron spectra and by calculating eigenstates of the many-electron Hamiltonian. The field of study within the present work encompasses (1) the strong-field regime, where the question of the adiabatic character in tunneling ionization is discussed and analyzed, especially for the case of few-cycle pulses; (2) the XUV regime, in which we show for the first time that the collectivity in resonant excitation reveals new information; and (3) the (hard) x-ray regime, which is highly relevant for x-ray free-electron laser experiments, and where we show how important two
Communication: Unambiguous comparison of many-electron wavefunctions through their overlaps
Plasser, Felix, E-mail: felix.plasser@univie.ac.at; González, Leticia, E-mail: leticia.gonzalez@univie.ac.at [Institute for Theoretical Chemistry, Faculty of Chemistry, University of Vienna, Währingerstr. 17, 1090 Vienna (Austria)
2016-07-14
A simple and powerful method for comparing many-electron wavefunctions constructed at different levels of theory is presented. By using wavefunction overlaps, it is possible to analyze the effects of varying wavefunction models, molecular orbitals, and one-electron basis sets. The computation of wavefunction overlaps eliminates the inherent ambiguity connected to more rudimentary wavefunction analysis protocols, such as visualization of orbitals or comparing selected physical observables. Instead, wavefunction overlaps allow processing the many-electron wavefunctions in their full inherent complexity. The presented method is particularly effective for excited state calculations as it allows for automatic monitoring of changes in the ordering of the excited states. A numerical demonstration based on multireference computations of two test systems, the selenoacrolein molecule and an iridium complex, is presented.
Many electron variational ground state of the two dimensional Anderson lattice
Zhou, Y.; Bowen, S.P.; Mancini, J.D.
1991-02-01
A variational upper bound of the ground state energy of two dimensional finite Anderson lattices is determined as a function of lattice size (up to 16 x 16). Two different sets of many-electron basis vectors are used to determine the ground state for all values of the coulomb integral U. This variational scheme has been successfully tested for one dimensional models and should give good estimates in two dimensions
Theory of many-electron atoms. Selected papers. Teoriya mnogoehlektronnykh atomov. Izbrannye trudy
Jucys, A P
1978-01-01
Selected papers of the founder of contemporary theoretical physics in Lithuania Adolfas Jucys on the theory of many-electron atoms and their spectra are presented, as well as a complete bibliography of his scientific works, a brief biographical essay and description of his scientific and social activities, reminiscences of other scientists about him. In these papers such questions are considered: Fock's self-consistent field in different approximations, various problems of the many-configurational approximation, incomplete separation of variables, expanded calculation method, application of nonorthogonal radial orbitals, method of irreducible tensor operators, graphical representation of the matrix elements and a number of other problems.
Nonadiabatic production of spinor condensates with a quadrupole-Ioffe-configuration trap
Zhang, P.; Xu, Z.; You, L.
2006-01-01
Motivated by the recent experimental observation of multicomponent spinor condensates via a time-dependent quadrupole-Ioffe-configuration trap, we provide a general framework for the investigation of nonadiabatic Landau-Zener dynamics of a hyperfine spin, e.g., from an atomic magnetic dipole moment coupled to a weak time-dependent magnetic (B-) field. The spin flipped population distribution, or the so-called Majorona formula, is expressed in terms of system parameters and experimental observables; thus, the distribution provides much needed insight into the underlying mechanism for the production of spinor condensates due to nonadiabatic level crossings
Cao, Jun
2015-01-01
In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π * transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π * excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S 1 ( 1 ππ * ) and S 2 ( 1 n N π * ) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles
Cao, Jun, E-mail: caojunbnu@mail.bnu.edu.cn [Guizhou Provincial Key Laboratory of Computational Nano-Material Sciences, Guizhou Normal College, Guiyang, Guizhou 550018, China and Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China)
2015-06-28
In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π{sup *} transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π{sup *} excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S{sub 1}({sup 1}ππ{sup *}) and S{sub 2}({sup 1}n{sub N}π{sup *}) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.
Cao, Jun
2015-06-01
In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π* transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π* excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S1(1ππ*) and S2(1nNπ*) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.
Mueller, C.; Gruen, N.; Voitkiv, A.B.
2002-01-01
We study single- and double-electron loss from heavy heliumlike projectiles in ultrarelativistic collisions with neutral many-electron target atoms. The simultaneous interaction of the target with two projectile electrons is found to be the dominant process in the double-electron loss provided the atomic number of the projectile, Z p , that of the target, Z t , and the collision velocity, v, satisfy the condition Z p Z t /v>0.4. It is shown that for a wide range of projectile and target atomic numbers the asymptotic double-to-single loss ratio strongly depends on the target atomic number but is nearly independent of the nuclear charge of the projectile. It is also demonstrated that many-photon exchange between the target and each of the projectile electrons considerably influences the double loss in collisions with very heavy targets
Time-dependent density functional theory for many-electron systems interacting with cavity photons.
Tokatly, I V
2013-06-07
Time-dependent (current) density functional theory for many-electron systems strongly coupled to quantized electromagnetic modes of a microcavity is proposed. It is shown that the electron-photon wave function is a unique functional of the electronic (current) density and the expectation values of photonic coordinates. The Kohn-Sham system is constructed, which allows us to calculate the above basic variables by solving self-consistent equations for noninteracting particles. We suggest possible approximations for the exchange-correlation potentials and discuss implications of this approach for the theory of open quantum systems. In particular we show that it naturally leads to time-dependent density functional theory for systems coupled to the Caldeira-Leggett bath.
On the secondly quantized theory of the many-electron atom
Gaigalas, Gediminas; Rudzikas, Zenonas
1996-01-01
The traditional theory of many-electron atoms and ions is based on the coefficients of fractional parentage and matrix elements of tensorial operators, composed of unit tensors. The calculation of spin-angular coefficients of radial integrals appearing in the expressions of matrix elements of arbitrary physical operators of atomic quantities has two main disadvantages: (i) the numerical codes for the calculation of spin-angular coefficients are usually very time consuming; (ii) f-shells are often omitted from programs for matrix element calculations since the tables for their coefficients of fractional parentage are very extensive. The authors assume that a series of difficulties persisting in the traditional approach to the calculation of spin-angular parts of matrix elements can be avoided by using this secondly quantized methodology, based on angular momentum theory, on the concept of the irreducible tensorial sets, on a generalized graphical method, on quasispin and on the reduced coefficients of fractional parentage. (author)
Mandal, Sudhansu S.; Mukherjee, Sutirtha; Ray, Koushik
2018-03-01
A method for determining the ground state of a planar interacting many-electron system in a magnetic field perpendicular to the plane is described. The ground state wave-function is expressed as a linear combination of a set of basis functions. Given only the flux and the number of electrons describing an incompressible state, we use the combinatorics of partitioning the flux among the electrons to derive the basis wave-functions as linear combinations of Schur polynomials. The procedure ensures that the basis wave-functions form representations of the angular momentum algebra. We exemplify the method by deriving the basis functions for the 5/2 quantum Hall state with a few particles. We find that one of the basis functions is precisely the Moore-Read Pfaffian wave function.
Quantum electrodynamics and the relativistic theory of many-electron atoms
Sucher, J.
1981-01-01
The development of relativistic theories of many-electron atoms is reviewed, with emphasis on the fact that the Dirac-Coulomb Hamiltonian H/sub DC/ has no bound states. This fact implies that neither the Dirac-Hartree-Fock (DHF) equations nor the DHF wavefunction chi have a simple theoretical interpretation. A no-pair hamiltonian H/sub +/ is defined which does not have the fatal flaw of H/sub DC/ and hence can serve as a starting point for a systematic study of relativistic effects in many-electron atoms which can go beyond central-field approximations. H/sub +/ differs from H/sub DC/ by the presence of external-field positive-energy projection operators in the electron-electron interaction terms. Unlike H/sub DC/, H/sub +/ and its eigenfunctions psi have a clear-cut field-theoretic meaning, which is described. Similar remarks hold for a simpler no-pair Hamiltonian h/sub +/, which involves free positive-energy projection operators and for related Hamiltonians H/sub +/' and h/sup +/' which include the Breit operator. Relativistic Hartree-Fock equations are obtained from H/sub +/ and the relation between their solutions psi and the DHF solutions chi is discussed. The DHF equations may be reinterpreted as approximations to the new HF-type equations; this provides a rationale for their success in applications. It is argued that the Breit operator ought to be included even in the original DHF equations
Castro, A; Gross, E K U
2014-01-01
We derive the fundamental equations of an optimal control theory for systems containing both quantum electrons and classical ions. The system is modeled with Ehrenfest dynamics, a non-adiabatic variant of molecular dynamics. The general formulation, that needs the fully correlated many-electron wavefunction, can be simplified by making use of time-dependent density-functional theory. In this case, the optimal control equations require some modifications that we will provide. The abstract general formulation is complemented with the simple example of the H 2 + molecule in the presence of a laser field. (paper)
Non-adiabatic perturbations in multi-component perfect fluids
Koshelev, N.A., E-mail: koshna71@inbox.ru [Ulyanovsk State University, Leo Tolstoy str 42, 432970 (Russian Federation)
2011-04-01
The evolution of non-adiabatic perturbations in models with multiple coupled perfect fluids with non-adiabatic sound speed is considered. Instead of splitting the entropy perturbation into relative and intrinsic parts, we introduce a set of symmetric quantities, which also govern the non-adiabatic pressure perturbation in models with energy transfer. We write the gauge invariant equations for the variables that determine on a large scale the non-adiabatic pressure perturbation and the rate of changes of the comoving curvature perturbation. The analysis of evolution of the non-adiabatic pressure perturbation has been made for several particular models.
Non-adiabatic perturbations in multi-component perfect fluids
Koshelev, N.A.
2011-01-01
The evolution of non-adiabatic perturbations in models with multiple coupled perfect fluids with non-adiabatic sound speed is considered. Instead of splitting the entropy perturbation into relative and intrinsic parts, we introduce a set of symmetric quantities, which also govern the non-adiabatic pressure perturbation in models with energy transfer. We write the gauge invariant equations for the variables that determine on a large scale the non-adiabatic pressure perturbation and the rate of changes of the comoving curvature perturbation. The analysis of evolution of the non-adiabatic pressure perturbation has been made for several particular models
Nonadiabatic three-neutrino oscillations in matter
DOlivo, J.C.; Oteo, J.A.
1996-01-01
Oscillations of three neutrinos in matter are analyzed by using the Magnus expansion for the time-evolution operator. We derive a simple expression for the electron-neutrino survival probability which is applied to the examination of the effect of a third neutrino on the nonadiabatic flavor transformations. copyright 1996 The American Physical Society
Nonadiabatic particle motion in magnetic mirror traps
Irie, H.; Otsuka, S.; Varma, R.K.; Watanabe, T.; Nishikawa, Kyoji.
1982-01-01
By numerical integration of the equation of single particle motion, the basic features of the actual nonadiabatic escape of particles are studied. The results are compared with the predictions of two existing theoretical models: ''diffusion'' model derived by B. V. Chirikov and ''tunneling'' model introduced by R. K. Varma. (author)
Time dependence, complex scaling, and the calculation of resonances in many-electron systems
Nicolaides, C.A.; Beck, D.R.
1978-01-01
The theory deals with certain aspects of the formal properties of atomic and molecular highly excited nonstationary states and the problem of calculating their wave functions, energies, and widths. The conceptual framework is a decay theory based on the consistent definition and calculation of the t = 0 localized state, vertical bar psi 0 >. Given this framework, the following topics are treated: The variational calculation of psi 0 and E 0 using a previously published theory that generalized the projection operator approach to many-electron systems. The exact definition of the resonance energy. The possibility of bound states in the continuum. The relation of psi 0 to the resonance (Gamow) function psi and of the Hamiltonian to the rotated Hamiltonian H(theta) based on the notion of perturbation of boundary conditions in the asymptotic region. The variational calculation of real and complex energies employing matrix elements of H and H 2 with square-integrable and resonance functions. The mathematical structure of the time evolution of vertical bar psi 0 > and the possibility of observing nonexponential decays in certain autoionizing states that are very close to the ionization threshold. A many-body theory of atomic and molecular resonances that employs the coordinate rotation method. 107 references
Electrons, pseudoparticles, and quasiparticles in the one-dimensional many-electron problem
Carmelo, J.M.; Castro Neto, A.H.
1996-01-01
We generalize the concept of quasiparticle for one-dimensional (1D) interacting electronic systems. The ↑ and ↓ quasiparticles recombine the pseudoparticle colors c and s (charge and spin at zero-magnetic field) and are constituted by one many-pseudoparticle topological-momentum shift and one or two pseudoparticles. These excitations cannot be separated. We consider the case of the Hubbard chain. We show that the low-energy electron-quasiparticle transformation has a singular character which justifies the perturbative and nonperturbative nature of the quantum problem in the pseudoparticle and electronic basis, respectively. This follows from the absence of zero-energy electron-quasiparticle overlap in 1D. The existence of Fermi-surface quasiparticles both in 1D and three dimensional (3D) many-electron systems suggests their existence in quantum liquids in dimensions 1 1 or whether it becomes finite as soon as we leave 1D remains an unsolved question. copyright 1996 The American Physical Society
Universal scaling relations for the energies of many-electron Hooke atoms
Odriazola, A.; Solanpää, J.; Kylänpää, I.; González, A.; Räsänen, E.
2017-04-01
A three-dimensional harmonic oscillator consisting of N ≥2 Coulomb-interacting charged particles, often called a (many-electron) Hooke atom, is a popular model in computational physics for, e.g., semiconductor quantum dots and ultracold ions. Starting from Thomas-Fermi theory, we show that the ground-state energy of such a system satisfies a nontrivial relation: Eg s=ω N4 /3fg s(β N1 /2) , where ω is the oscillator strength, β is the ratio between Coulomb and oscillator characteristic energies, and fg s is a universal function. We perform extensive numerical calculations to verify the applicability of the relation. In addition, we show that the chemical potentials and addition energies also satisfy approximate scaling relations. In all cases, analytic expressions for the universal functions are provided. The results have predictive power in estimating the key ground-state properties of the system in the large-N limit, and can be used in the development of approximative methods in electronic structure theory.
Exact many-electron ground states on diamond and triangle Hubbard chains
Gulacsi, Zsolt; Kampf, Arno; Vollhardt, Dieter
2009-01-01
We construct exact ground states of interacting electrons on triangle and diamond Hubbard chains. The construction requires (1) a rewriting of the Hamiltonian into positive semidefinite form, (2) the construction of a many-electron ground state of this Hamiltonian, and (3) the proof of the uniqueness of the ground state. This approach works in any dimension, requires no integrability of the model, and only demands sufficiently many microscopic parameters in the Hamiltonian which have to fulfill certain relations. The scheme is first employed to construct exact ground state for the diamond Hubbard chain in a magnetic field. These ground states are found to exhibit a wide range of properties such as flat-band ferromagnetism and correlation induced metallic, half-metallic or insulating behavior, which can be tuned by changing the magnetic flux, local potentials, or electron density. Detailed proofs of the uniqueness of the ground states are presented. By the same technique exact ground states are constructed for triangle Hubbard chains and a one-dimensional periodic Anderson model with nearest-neighbor hybridization. They permit direct comparison with results obtained by variational techniques for f-electron ferromagnetism due to a flat band in CeRh 3 B 2 . (author)
Quantum dynamics in nanoscale magnets in dissipative environments
Miyashita, S; Saito, K; Kobayashi, H.; de Raedt, H.A.
2000-01-01
In discrete energy structure of nanoscale magnets, nonadiabatic transitions at avoided level crossings lead to fundamental processes of dynamics of magnetizations. The thermal environment causes dissipative effects on these processes. In this paper we review the features of the nonadiabatic
Plasma Jet Braking: Energy Dissipation and Nonadiabatic Electrons
Khotyaintsev, Yu. V.; Cully, C. M.; Vaivads, A.; Andre, M.; Owen, C. J.
2011-01-01
We report in situ observations by the Cluster spacecraft of wave-particle interactions in a magnetic flux pileup region created by a magnetic reconnection outflow jet in Earth's magnetotail. Two distinct regions of wave activity are identified: lower-hybrid drift waves at the front edge and whistler-mode waves inside the pileup region. The whistler-mode waves are locally generated by the electron temperature anisotropy, and provide evidence for ongoing betatron energization caused by magnetic flux pileup. The whistler-mode waves cause fast pitch-angle scattering of electrons and isotropization of the electron distribution, thus making the flow braking process nonadiabatic. The waves strongly affect the electron dynamics and thus play an important role in the energy conversion chain during plasma jet braking.
Time-dependent quantum chemistry of laser driven many-electron molecules
Nguyen-Dang, Thanh-Tung; Couture-Bienvenue, Étienne; Viau-Trudel, Jérémy; Sainjon, Amaury
2014-01-01
A Time-Dependent Configuration Interaction approach using multiple Feshbach partitionings, corresponding to multiple ionization stages of a laser-driven molecule, has recently been proposed [T.-T. Nguyen-Dang and J. Viau-Trudel, J. Chem. Phys. 139, 244102 (2013)]. To complete this development toward a fully ab-initio method for the calculation of time-dependent electronic wavefunctions of an N-electron molecule, we describe how tools of multiconfiguration quantum chemistry such as the management of the configuration expansion space using Graphical Unitary Group Approach concepts can be profitably adapted to the new context, that of time-resolved electronic dynamics, as opposed to stationary electronic structure. The method is applied to calculate the detailed, sub-cycle electronic dynamics of BeH 2 , treated in a 3–21G bound-orbital basis augmented by a set of orthogonalized plane-waves representing continuum-type orbitals, including its ionization under an intense λ = 800 nm or λ = 80 nm continuous-wave laser field. The dynamics is strongly non-linear at the field-intensity considered (I ≃ 10 15 W/cm 2 ), featuring important ionization of an inner-shell electron and strong post-ionization bound-electron dynamics
Kanno, Manabu; Kono, Hirohiko; Fujimura, Yuichi; Lin, Sheng H.
2010-01-01
We theoretically investigated the nonadiabatic couplings between optically induced π-electron rotations and molecular vibrations in a chiral aromatic molecule irradiated by a nonhelical, linearly polarized laser pulse. The results of wave packet dynamics simulation show that the vibrational amplitudes strongly depend on the initial rotation direction, clockwise or counterclockwise, which is controlled by the polarization direction of the incident pulse. This suggests that attosecond π-electron rotations can be observed by spectroscopic detection of femtosecond molecular vibrations.
Levitation of Bose-Einstein condensates induced by macroscopic non-adiabatic quantum tunneling
Nakamura, Katsuhiro; Kohi, Akihisa; Yamasaki, Hisatsugu; Perez-Garcia, Victor M.
2006-01-01
We study the dynamics of two-component Bose-Einstein condensates trapped in different vertical positions in the presence of an oscillating magnetic field. It is shown here how tuning appropriately the oscillation frequency of the magnetic field leads to the levitation of the system against gravity. This phenomenon is a manifestation of a macroscopic non-adiabatic tunneling in a system with internal degrees of freedom.
Turi, László
2016-04-01
We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.
Turi, László, E-mail: turi@chem.elte.hu [Department of Physical Chemistry, Eötvös Loránd University, P.O. Box 32, H-1518 Budapest 112 (Hungary)
2016-04-21
We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.
Tiwari, Vivek; Peters, William K.; Jonas, David M.
2017-10-01
Non-adiabatic vibrational-electronic resonance in the excited electronic states of natural photosynthetic antennas drastically alters the adiabatic framework, in which electronic energy transfer has been conventionally studied, and suggests the possibility of exploiting non-adiabatic dynamics for directed energy transfer. Here, a generalized dimer model incorporates asymmetries between pigments, coupling to the environment, and the doubly excited state relevant for nonlinear spectroscopy. For this generalized dimer model, the vibrational tuning vector that drives energy transfer is derived and connected to decoherence between singly excited states. A correlation vector is connected to decoherence between the ground state and the doubly excited state. Optical decoherence between the ground and singly excited states involves linear combinations of the correlation and tuning vectors. Excitonic coupling modifies the tuning vector. The correlation and tuning vectors are not always orthogonal, and both can be asymmetric under pigment exchange, which affects energy transfer. For equal pigment vibrational frequencies, the nonadiabatic tuning vector becomes an anti-correlated delocalized linear combination of intramolecular vibrations of the two pigments, and the nonadiabatic energy transfer dynamics become separable. With exchange symmetry, the correlation and tuning vectors become delocalized intramolecular vibrations that are symmetric and antisymmetric under pigment exchange. Diabatic criteria for vibrational-excitonic resonance demonstrate that anti-correlated vibrations increase the range and speed of vibronically resonant energy transfer (the Golden Rule rate is a factor of 2 faster). A partial trace analysis shows that vibronic decoherence for a vibrational-excitonic resonance between two excitons is slower than their purely excitonic decoherence.
The nonadiabatic deactivation paths of pyrrole
Barbatti, Mario; Vazdar, Mario; Aquino, Adelia J. A.; Eckert-Maksic, Mirjana; Lischka, Hans
2006-01-01
Multireference configuration interaction (MRCI) calculations have been performed for pyrrole with the aim of providing an explanation for the experimentally observed photochemical deactivation processes. Potential energy curves and minima on the crossing seam were determined using the analytic MRCI gradient and nonadiabatic coupling features of the COLUMBUS program system. A new deactivation mechanism based on an out-of-plane ring deformation is presented. This mechanism directly couples the charge transfer 1 ππ* and ground states. It may be responsible for more than 50% of the observed photofragments of ππ*-excited pyrrole. The ring deformation mechanism should act complementary to the previously proposed NH-stretching mechanism, thus offering a more complete interpretation of the pyrrole photodynamics
Theory of fast (nonadiabatic) nuclear rotation
Nosov, V.G.; Kamchatnov, A.M.
1977-01-01
The theory of backbending is developed taking into accout the increasing role of nonadiabatic effects, which are concerned with quantum number K violation. Above the transition point, rotation quantum number j (>=) jsub(c) (second-kind transition point), all possible values of the quantity K in the interval -J ( Jsub(c) are obtained. The radius of global nucleon mass distribution in the nucleus is defined from the analysis of the experimental moments of inertia in n-phase. It is in agreement with the radius of distribution of protons alone obtained from electron scattering on nuclei. Assuming the simplest singularity of parametric derivative of the Hamiltonian of the system the general theory of non-temperature (ground state)second-kind phase transitions is developed
Sequential nonadiabatic excitation of large molecules and ions driven by strong laser fields
Markevitch, Alexei N.; Levis, Robert J.; Romanov, Dmitri A.; Smith, Stanley M.; Schlegel, H. Bernhard; Ivanov, Misha Yu.
2004-01-01
Electronic processes leading to dissociative ionization of polyatomic molecules in strong laser fields are investigated experimentally, theoretically, and numerically. Using time-of-flight ion mass spectroscopy, we study the dependence of fragmentation on laser intensity for a series of related molecules and report regular trends in this dependence on the size, symmetry, and electronic structure of a molecule. Based on these data, we develop a model of dissociative ionization of polyatomic molecules in intense laser fields. The model is built on three elements: (i) nonadiabatic population transfer from the ground electronic state to the excited-state manifold via a doorway (charge-transfer) transition; (ii) exponential enhancement of this transition by collective dynamic polarization of all electrons, and (iii) sequential energy deposition in both neutral molecules and resulting molecular ions. The sequential nonadiabatic excitation is accelerated by a counterintuitive increase of a large molecule's polarizability following its ionization. The generic theory of sequential nonadiabatic excitation forms a basis for quantitative description of various nonlinear processes in polyatomic molecules and ions in strong laser fields
Nuclear quantum effects on the nonadiabatic decay mechanism of an excited hydrated electron
Borgis, Daniel; Rossky, Peter J.; Turi, László
2007-11-01
We present a kinetic analysis of the nonadiabatic decay mechanism of an excited state hydrated electron to the ground state. The theoretical treatment is based on a quantized, gap dependent golden rule rate constant formula which describes the nonadiabatic transition rate between two quantum states. The rate formula is expressed in terms of quantum time correlation functions of the energy gap and of the nonadiabatic coupling. These gap dependent quantities are evaluated from three different sets of mixed quantum-classical molecular dynamics simulations of a hydrated electron equilibrated (a) in its ground state, (b) in its first excited state, and (c) on a hypothetical mixed potential energy surface which is the average of the ground and the first excited electronic states. The quantized, gap dependent rate results are applied in a phenomenological kinetic equation which provides the survival probability function of the excited state electron. Although the lifetime of the equilibrated excited state electron is computed to be very short (well under 100fs), the survival probability function for the nonequilibrium process in pump-probe experiments yields an effective excited state lifetime of around 300fs, a value that is consistent with the findings of several experimental groups and previous theoretical estimates.
Zhu, Chaoyuan; Lin, Sheng Hsien
2006-07-28
Unified semiclasical solution for general nonadiabatic tunneling between two adiabatic potential energy surfaces is established by employing unified semiclassical solution for pure nonadiabatic transition [C. Zhu, J. Chem. Phys. 105, 4159 (1996)] with the certain symmetry transformation. This symmetry comes from a detailed analysis of the reduced scattering matrix for Landau-Zener type of crossing as a special case of nonadiabatic transition and nonadiabatic tunneling. Traditional classification of crossing and noncrossing types of nonadiabatic transition can be quantitatively defined by the rotation angle of adiabatic-to-diabatic transformation, and this rotational angle enters the analytical solution for general nonadiabatic tunneling. The certain two-state exponential potential models are employed for numerical tests, and the calculations from the present general nonadiabatic tunneling formula are demonstrated in very good agreement with the results from exact quantum mechanical calculations. The present general nonadiabatic tunneling formula can be incorporated with various mixed quantum-classical methods for modeling electronically nonadiabatic processes in photochemistry.
Nonadiabatic effects in C-Br bond scission in the photodissociation of bromoacetyl chloride
Valero, Rosendo; Truhlar, Donald G.
2006-01-01
Bromoacetyl chloride photodissociation has been interpreted as a paradigmatic example of a process in which nonadiabatic effects play a major role. In molecular beam experiments by Butler and co-workers [J. Chem. Phys. 95, 3848 (1991); J. Chem. Phys. 97, 355 (1992)], BrCH 2 C(O)Cl was prepared in its ground electronic state (S 0 ) and excited with a laser at 248 nm to its first excited singlet state (S 1 ). The two main ensuing photoreactions are the ruptures of the C-Cl bond and of the C-Br bond. A nonadiabatic model was proposed in which the C-Br scission is strongly suppressed due to nonadiabatic recrossing at the barrier formed by the avoided crossing between the S 1 and S 2 states. Recent reduced-dimensional dynamical studies lend support to this model. However, another interpretation that has been given for the experimental results is that the reduced probability of C-Br scission is a consequence of incomplete intramolecular energy redistribution. To provide further insight into this problem, we have studied the energetically lowest six singlet electronic states of bromoacetyl chloride by using an ab initio multiconfigurational perturbative electronic structure method. Stationary points (minima and saddle points) and minimum energy paths have been characterized on the S 0 and S 1 potential energy surfaces. The fourfold way diabatization method has been applied to transform five adiabatic excited electronic states to a diabatic representation. The diabatic potential energy matrix of the first five excited singlet states has been constructed along several cuts of the potential energy hypersurfaces. The thermochemistry of the photodissociation reactions and a comparison with experimental translational energy distributions strongly suggest that nonadiabatic effects dominate the C-Br scission, but that the reaction proceeds along the energetically allowed diabatic pathway to excited-state products instead of being nonadiabatically suppressed. This conclusion is
Mendieta-Moreno, Jesús I; Trabada, Daniel G; Mendieta, Jesús; Lewis, James P; Gómez-Puertas, Paulino; Ortega, José
2016-11-03
The absorption of ultraviolet radiation by DNA may result in harmful genetic lesions that affect DNA replication and transcription, ultimately causing mutations, cancer, and/or cell death. We analyze the most abundant photochemical reaction in DNA, the cyclobutane thymine dimer, using hybrid quantum mechanics/molecular mechanics (QM/MM) techniques and QM/MM nonadiabatic molecular dynamics. We find that, due to its double helix structure, DNA presents a free energy barrier between nonreactive and reactive conformations leading to the photolesion. Moreover, our nonadiabatic simulations show that most of the photoexcited reactive conformations return to standard B-DNA conformations after an ultrafast nonradiative decay to the ground state. This work highlights the importance of dynamical effects (free energy, excited-state dynamics) for the study of photochemical reactions in biological systems.
Generation of helical electron beams by a nonadiabatic gun
Barroso, J.J.; Stellati, C.
1996-01-01
The design of a non-adiabatic gun to produce a 10A, 50kV hollow laminar electron beam for gyrotron applications is reported. The beam is extracted from the emitting ring in a direction parallel to the axial guide magnetic field and then propagates across the radial electric field in the anode gap. The electrons are thereby given a transverse velocity upon passing through the modulation anode region where an electrostatic pumping mechanism takes place, so that a considerable amount of the electron energy is converted to transverse kinetic energy. Such a beam extraction method gives rise to favourable features that are examined throughout the work. The dynamics of hollow electron beams with gyromotion propagating down a cylindrical drift tube are also analysed. Due to the action of the beam's self-space charge field, the transverse velocity spread has an oscillatory behaviour along the drift tube wherein the spatial automodulation period shortens with increasing current. Numerical simulation results indicate that even at a 10A beam current, the resulting transverse velocity spread is still less than the spread for a zero beam current. (UK)
Denisov, S.; Flach, S.; Ovchinnikov, A. A.
2002-01-01
We consider low-dimensional dynamical systems exposed to a heat bath and to additional ac fields. The presence of these ac fields may lead to a breaking of certain spatial or temporal symmetries, which in turn cause nonzero averages of relevant observables. Nonlinear (non)adiabatic response is em...... is employed to explain the effect. We consider a case of a particle in a periodic potential as an example and discuss the relevant symmetry breakings and the mechanisms of rectification of the current in such a system.......We consider low-dimensional dynamical systems exposed to a heat bath and to additional ac fields. The presence of these ac fields may lead to a breaking of certain spatial or temporal symmetries, which in turn cause nonzero averages of relevant observables. Nonlinear (non)adiabatic response...
Non-adiabatic perturbations in Ricci dark energy model
Karwan, Khamphee; Thitapura, Thiti
2012-01-01
We show that the non-adiabatic perturbations between Ricci dark energy and matter can grow both on superhorizon and subhorizon scales, and these non-adiabatic perturbations on subhorizon scales can lead to instability in this dark energy model. The rapidly growing non-adiabatic modes on subhorizon scales always occur when the equation of state parameter of dark energy starts to drop towards -1 near the end of matter era, except that the parameter α of Ricci dark energy equals to 1/2. In the case where α = 1/2, the rapidly growing non-adiabatic modes disappear when the perturbations in dark energy and matter are adiabatic initially. However, an adiabaticity between dark energy and matter perturbations at early time implies a non-adiabaticity between matter and radiation, this can influence the ordinary Sachs-Wolfe (OSW) effect. Since the amount of Ricci dark energy is not small during matter domination, the integrated Sachs-Wolfe (ISW) effect is greatly modified by density perturbations of dark energy, leading to a wrong shape of CMB power spectrum. The instability in Ricci dark energy is difficult to be alleviated if the effects of coupling between baryon and photon on dark energy perturbations are included
Nonadiabatic effects in the Quantum Hall regime
Page, D.A.; Brown, E.
1993-01-01
The authors consider the effect of a finite electric field on the states of a Bloch electron in two dimensions, with a uniform magnetic field present. They make use of the concept of electric time translation symmetry and treat the electric and magnetic fields symmetrically in a time dependent formalism. In addition to a wave vector k, the states are characterized by a frequency specifying the behavior under electric time translations. An effective Hamiltonian is employed to obtain the splitting of an isolated Bloch band into open-quotes frequencyclose quotes subbands. The time-averaged velocity and energy of the states are expressed in terms of the frequency dispersion. The relationship to the Stark ladder eigenstates in a scalar potential representation of the electric field is examined. This is seen to justify the use of the averaged energy in determining occupation of the states. In the weak electric field (adiabatic) limit, an expression is recovered for the quantized Hall conductivity of a magnetic subband as a topological invariant. A numerical procedure is outlined and results obtained over a range of electric field strengths. A transition between strong and weak field regimes is seen, with level repulsions between the frequencies playing an important role. The numerical results show how the magnetic subband structure and quantized Hall conductivity emerge as the electric field becomes weaker. In this regime, the behavior can be understood by comparison to the predictions of the adiabatic approximation. The latter predicts crossings in the frequencies at certain locations in wave vector space. Nonadiabatic effects are seen to produce gaps in the frequency spectrum at these locations. 35 refs., 14 figs
A design study of non-adiabatic electron guns
Barroso, J.J.; Stellati, C.
1994-01-01
The design of a non-adiabatic gun capable of producing a 10 A, 50 KeV high-quality laminar electron beam is reported. In contrast to the magnetron injection gun with a conical cathode, where the beam is generated initially with a transverse velocity component, in the non-adiabatic gun electrons are extracted in a direction parallel to the axial guide magnetic field. The beam electrons acquire cyclotron motion as result of non-adiabatic processes in a strong non uniform electric field across the modulation anode. Such an extraction method gives rise to favourable features that are explored throughout the work. An extensive numerical simulation study has also been done to minimize velocity and energy spreads. (author). 3 refs, 5 figs, 1 tab
Intrinsic nonadiabatic topological torque in magnetic skyrmions and vortices
Akosa, Collins Ashu; Ndiaye, Papa Birame; Manchon, Aurelien
2017-01-01
We propose that topological spin currents flowing in topologically nontrivial magnetic textures, such as magnetic skyrmions and vortices, produce an intrinsic nonadiabatic torque of the form Tt∼[(∂xm×∂ym)·m]∂ym. We show that this torque, which is absent in one-dimensional domain walls and/or nontopological textures, is responsible for the enhanced nonadiabaticity parameter observed in magnetic vortices compared to one-dimensional textures. The impact of this torque on the motion of magnetic skyrmions is expected to be crucial, especially to determine their robustness against defects and pinning centers.
Intrinsic nonadiabatic topological torque in magnetic skyrmions and vortices
Akosa, Collins Ashu
2017-03-01
We propose that topological spin currents flowing in topologically nontrivial magnetic textures, such as magnetic skyrmions and vortices, produce an intrinsic nonadiabatic torque of the form Tt∼[(∂xm×∂ym)·m]∂ym. We show that this torque, which is absent in one-dimensional domain walls and/or nontopological textures, is responsible for the enhanced nonadiabaticity parameter observed in magnetic vortices compared to one-dimensional textures. The impact of this torque on the motion of magnetic skyrmions is expected to be crucial, especially to determine their robustness against defects and pinning centers.
Song, Xiaohong; Lin, Cheng; Sheng, Zhihao; Liu, Peng; Chen, Zhangjin; Yang, Weifeng; Hu, Shilin; Lin, C D; Chen, Jing
2016-06-22
Strong field photoelectron holography has been proposed as a means for interrogating the spatial and temporal information of electrons and ions in a dynamic system. After ionization, part of the electron wave packet may directly go to the detector (the reference wave), while another part may be driven back and scatters off the ion(the signal wave). The interference hologram of the two waves may be used to extract target information embedded in the collision process. Unlike conventional optical holography, however, propagation of the electron wave packet is affected by the Coulomb potential as well as by the laser field. In addition, electrons are emitted over the whole laser pulse duration, thus multiple interferences may occur. In this work, we used a generalized quantum-trajectory Monte Carlo method to investigate the effect of Coulomb potential and the nonadiabatic subcycle ionization on the photoelectron hologram. We showed that photoelectron hologram can be well described only when the effect of nonadiabatic ionization is accounted for, and Coulomb potential can be neglected only in the tunnel ionization regime. Our results help paving the way for establishing photoelectron holography for probing spatial and dynamic properties of atoms and molecules.
Naftchi-Ardebili, Kasra; Hau, Nathania W.; Mazziotti, David A.
2011-01-01
Variational minimization of the ground-state energy as a function of the two-electron reduced density matrix (2-RDM), constrained by necessary N-representability conditions, provides a polynomial-scaling approach to studying strongly correlated molecules without computing the many-electron wave function. Here we introduce a route to enhancing necessary conditions for N representability through rank restriction of the 2-RDM. Rather than adding computationally more expensive N-representability conditions, we directly enhance the accuracy of two-particle (2-positivity) conditions through rank restriction, which removes degrees of freedom in the 2-RDM that are not sufficiently constrained. We select the rank of the particle-hole 2-RDM by deriving the ranks associated with model wave functions, including both mean-field and antisymmetrized geminal power (AGP) wave functions. Because the 2-positivity conditions are exact for quantum systems with AGP ground states, the rank of the particle-hole 2-RDM from the AGP ansatz provides a minimum for its value in variational 2-RDM calculations of general quantum systems. To implement the rank-restricted conditions, we extend a first-order algorithm for large-scale semidefinite programming. The rank-restricted conditions significantly improve the accuracy of the energies; for example, the percentages of correlation energies recovered for HF, CO, and N 2 improve from 115.2%, 121.7%, and 121.5% without rank restriction to 97.8%, 101.1%, and 100.0% with rank restriction. Similar results are found at both equilibrium and nonequilibrium geometries. While more accurate, the rank-restricted N-representability conditions are less expensive computationally than the full-rank conditions.
Non-adiabatic rotational excitation of dipolar molecule under the ...
J. Chem. Sci. Vol. 125, No. 5, September 2013, pp. 1213–1221. c Indian Academy of Sciences. ... The rotational wave packets of LiCl molecule excited non-adiabatically by half cycle pulse. (HCP) is .... pared to the intensities required for the ionization of ..... out and with delayed ultrashort HCP at different initial pulse dura-.
Nonadiabatic corrections to a quantum dot quantum computer
Home; Journals; Pramana – Journal of Physics; Volume 83; Issue 1. Nonadiabatic corrections to a quantum dot quantum computer working in adiabatic limit. M Ávila ... The time of operation of an adiabatic quantum computer must be less than the decoherence time, otherwise the computer would be nonoperative. So far, the ...
Nonadiabatic geometrical quantum gates in semiconductor quantum dots
Solinas, Paolo; Zanghi, Nino; Zanardi, Paolo; Rossi, Fausto
2003-01-01
In this paper, we study the implementation of nonadiabatic geometrical quantum gates with in semiconductor quantum dots. Different quantum information enconding (manipulation) schemes exploiting excitonic degrees of freedom are discussed. By means of the Aharanov-Anandan geometrical phase, one can avoid the limitations of adiabatic schemes relying on adiabatic Berry phase; fast geometrical quantum gates can be, in principle, implemented
2017-01-20
AFRL-AFOSR-JP-TR-2017-0012 The Strength of Chaos : accurate simulation of resonant electron scattering by many-electron ions and atoms in the presence...of quantum chaos Igor Bray CURTIN UNIVERSITY OF TECHNOLOGY Final Report 01/20/2017 DISTRIBUTION A: Distribution approved for public release. AF...SUBTITLE The Strength of Chaos : accurate simulation of resonant electron scattering by many- electron ions and atoms in the presence of quantum chaos
Cao Jun; Liu Lihong; Fang Weihai [Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875 (China); Xie Zhizhong [Department of Chemistry, School of Science, Wuhan University of Technology, Wuhan 430070 (China); Zhang Yong [Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, New Jersey 07030 (United States)
2013-04-07
Azobenzene is one of the most widely used photoactive units and recently an ethylene-bridged azobenzene (BAB) was reported to have greatly enhanced conversion efficiency, quantum yield, and other favorable properties. As the first step towards exploring its photo-switchable character in real systems, we report here a systematic study on the photoisomerization dynamics between trans (E) and cis (Z) isomers in the gas phase and the CH{sub 3}OH solution, using ab initio based surface hopping and molecular dynamics, which is the first report of dynamics simulation to reveal the environmental effects on BAB photoreactions. Results show that while the relatively faster S{sub 1} relaxation of the photo-induced E{yields}Z process is only mildly affected by the solvent effect, the relatively slower S{sub 1} relaxation of the reverse reaction becomes even slower in the solution compared to the gas phase. The subsequent S{sub 0} dynamics from the conical intersection between S{sub 1} and S{sub 0} (CI{sub E}) to Z is accelerated in solution compared to the gas phase because of avoided re-crossing to the S{sub 1} state, while the S{sub 0} dynamics from the conical intersection between S{sub 1} and S{sub 0} (CI{sub Z}) to E are basically the same in both phases. Overall, the solvent effect was found to enhance the back-and-forth photo-switch efficiency between the Z and E isomers compared to the gas phase, while the quantum yields are reduced. But the solution yields of both the forward and backward photoreactions are still around 0.4. Therefore, BAB may have good photo-responsive properties if used as a photoactive unit in real systems. These results will facilitate future experimental and theoretical studies in this area to help design new azobenzene derivatives as photoactive units in biological processes, nanoscale devices, and photo-responsive materials.
Spatial non-adiabatic passage using geometric phases
Benseny, Albert; Busch, Thomas [Okinawa Institute of Science and Technology Graduate University, Quantum Systems Unit, Okinawa (Japan); Kiely, Anthony; Ruschhaupt, Andreas [University College Cork, Department of Physics, Cork (Ireland); Zhang, Yongping [Okinawa Institute of Science and Technology Graduate University, Quantum Systems Unit, Okinawa (Japan); Shanghai University, Department of Physics, Shanghai (China)
2017-12-15
Quantum technologies based on adiabatic techniques can be highly effective, but often at the cost of being very slow. Here we introduce a set of experimentally realistic, non-adiabatic protocols for spatial state preparation, which yield the same fidelity as their adiabatic counterparts, but on fast timescales. In particular, we consider a charged particle in a system of three tunnel-coupled quantum wells, where the presence of a magnetic field can induce a geometric phase during the tunnelling processes. We show that this leads to the appearance of complex tunnelling amplitudes and allows for the implementation of spatial non-adiabatic passage. We demonstrate the ability of such a system to transport a particle between two different wells and to generate a delocalised superposition between the three traps with high fidelity in short times. (orig.)
Non-adiabatic generator-coordinate calculation of H2+
Tostes, J.G.R.; Para Univ., Belem; Toledo Piza, A.F.R. de
1982-10-01
A non-adiabatic calculation of the few lowest J=O states in the H 2+ molecule done within the framework of the Generator Coordinate Method is reported. Substantial accuracy is achivied with the diagonalization of matrices of very modest dimensions. The resulting wavefunctions are strongly dominated by just a few basis states. The computational scheme is set up so as to take the best advantage of good analytical approximations to existing adiabatic molecular wavefunctions. (Author) [pt
Nonadiabatic electron response in the Hasegawa-Wakatani equations
Stoltzfus-Dueck, T.; Scott, B. D.; Krommes, J. A.
2013-01-01
Tokamak edge turbulence is strongly influenced by parallel electron physics, which relaxes density and potential fluctuations towards electron adiabatic response. Beginning with the paradigmatic Hasegawa-Wakatani equations (HWEs) for resistive tokamak edge turbulence, a unique decomposition of the electric potential (φ) into adiabatic (a) and nonadiabatic (b) portions is derived, based on the requirement that a neither drive nor respond to the parallel current j ∥ . The form of the decomposition clarifies that, at perpendicular scales large relative to the sound radius, the electron adiabatic response controls the nonzonal φ, not the fluctuating density n. Simple energy balance arguments allow one to rigorously bound the ratio of rms nonzonal nonadiabatic fluctuations (b(tilde sign)) relative to adiabatic ones (ã). The role of the vorticity nonlinearity in transferring energy between adiabatic and nonadiabatic fluctuations aids intuitive understanding of self-sustained turbulence in the HWEs. When the normalized parallel resistivity is weak, b(tilde sign) becomes effectively slaved, allowing the reduction to an approximate one-field model that remains valid for strong turbulence. In addition to guiding physical intuition, the one-field reduction should greatly ease further analytical manipulations. Direct numerical simulation of the 2D HWEs confirms the convergence of the asymptotic formula for b(tilde sign)
Particle pitch angle diffusion due to nonadiabatic effects in the plasma sheet
Gray, P.C.; Lee, L.C.
1982-01-01
In order to understand certain aspects of the plasma sheet dynamics, a numerical study of the nonadiabatic behavior of particles in a model field geometry is performed. The particle's magnetic moment as a function of time is calculated for various initial parameters, corresponding to various particle energies and degrees of field curvature. It is shown that the magnetic moment changes as the particle passes through the plasma sheet and that the magnitude of the change is related to the curvature of the field at the middle of the plasma sheet. The relation of the magnitude of the change in magnetic moment to the particle's pitch and phase angles as it passes through the sheet is numerically resolved. The nature of the change may be considered as a mechanism for pitch angle diffusion, and the diffusion coefficient is calculated. This scattering mechanism is significant for plasma sheet ions (1--10 keV) as well as energetic electrons (>100 keV)
Martínez-Mesa, Aliezer [Departmento de Física Teórica, Universidad de la Habana, San Lázaro y L, La Habana 10400 (Cuba); Institut für Chemie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, D-14476 Potsdam-Golm (Germany); Saalfrank, Peter [Institut für Chemie, Universität Potsdam, Karl-Liebknecht-Strasse 24-25, D-14476 Potsdam-Golm (Germany)
2015-05-21
Femtosecond-laser pulse driven non-adiabatic spectroscopy and dynamics in molecular and condensed phase systems continue to be a challenge for theoretical modelling. One of the main obstacles is the “curse of dimensionality” encountered in non-adiabatic, exact wavepacket propagation. A possible route towards treating complex molecular systems is via semiclassical surface-hopping schemes, in particular if they account not only for non-adiabatic post-excitation dynamics but also for the initial optical excitation. One such approach, based on initial condition filtering, will be put forward in what follows. As a simple test case which can be compared with exact wavepacket dynamics, we investigate the influence of the different parameters determining the shape of a laser pulse (e.g., its finite width and a possible chirp) on the predissociation dynamics of a NaI molecule, upon photoexcitation of the A(0{sup +}) state. The finite-pulse effects are mapped into the initial conditions for semiclassical surface-hopping simulations. The simulated surface-hopping diabatic populations are in qualitative agreement with the quantum mechanical results, especially concerning the subpicosend photoinduced dynamics, the main deviations being the relative delay of the non-adiabatic transitions in the semiclassical picture. Likewise, these differences in the time-dependent electronic populations calculated via the semiclassical and the quantum methods are found to have a mild influence on the overall probability density distribution. As a result, the branching ratios between the bound and the dissociative reaction channels and the time-evolution of the molecular wavepacket predicted by the semiclassical method agree with those computed using quantum wavepacket propagation. Implications for more challenging molecular systems are given.
Watanabe, Shinta, E-mail: s-watanabe@nucl.nagoya-u.ac.jp, E-mail: j-onoe@nucl.nagoya-u.ac.jp; Sawada, Yuki; Nakaya, Masato; Yoshino, Masahito; Nagasaki, Takanori; Onoe, Jun, E-mail: s-watanabe@nucl.nagoya-u.ac.jp, E-mail: j-onoe@nucl.nagoya-u.ac.jp [Department of Materials, Physics and Energy Engineering, Graduated School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan); Kameyama, Tatsuya; Torimoto, Tsukasa [Department of Crystalline Materials Science, Graduated School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8603 (Japan); Inaba, Yusuke; Takahashi, Hideharu; Takeshita, Kenji [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1-N1-16 O-okayama, Meguro-ku, Tokyo 152-8550 (Japan)
2016-06-21
We have investigated the electronic structures and optical properties of Fe, Co, and Ni ferrocyanide nanoparticles using first-principles relativistic many-electron calculations. The overall features of the theoretical absorption spectra for Fe, Ni, and Co ferrocyanides calculated using a first-principles many-electron method well reproduced the experimental one. The origins of the experimental absorption spectra were clarified by performing a configuration analysis based on the many-electron wave functions. For Fe ferrocyanide, the experimental absorption peaks originated from not only the charge-transfer transitions from Fe{sup 2+} to Fe{sup 3+} but also the 3d-3d intra-transitions of Fe{sup 3+} ions. In addition, the spin crossover transition of Fe{sup 3+} predicted by the many-electron calculations was about 0.24 eV. For Co ferrocyanide, the experimental absorption peaks were mainly attributed to the 3d-3d intra-transitions of Fe{sup 2+} ions. In contrast to the Fe and Co ferrocyanides, Ni ferrocyanide showed that the absorption peaks originated from the 3d-3d intra-transitions of Ni{sup 3+} ions in a low-energy region, while from both the 3d-3d intra-transitions of Fe{sup 2+} ions and the charge-transfer transitions from Fe{sup 2+} to Ni{sup 3+} in a high-energy region. These results were quite different from those of density-functional theory (DFT) calculations. The discrepancy between the results of DFT calculations and those of many-electron calculations suggested that the intra- and inter-atomic transitions of transition metal ions are significantly affected by the many-body effects of strongly correlated 3d electrons.
Nonadiabatic quantum Vlasov equation for Schwinger pair production
Kim, Sang Pyo; Schubert, Christian
2011-01-01
Using Lewis-Riesenfeld theory, we derive an exact nonadiabatic master equation describing the time evolution of the QED Schwinger pair-production rate for a general time-varying electric field. This equation can be written equivalently as a first-order matrix equation, as a Vlasov-type integral equation, or as a third-order differential equation. In the last version it relates to the Korteweg-de Vries equation, which allows us to construct an exact solution using the well-known one-soliton solution to that equation. The case of timelike delta function pulse fields is also briefly considered.
Non-adiabatic study of the Kepler subgiant KIC 6442183
Grosjean M.
2015-01-01
Full Text Available Thanks to the precision of Kepler observations, [3] were able to measure the linewidth and amplitude of individual modes (including mixed modes in several subgiant power spectra. We perform a forward modelling of a Kepler subgiant based on surface properties and observed frequencies. Non-adiabatic computations including a time- dependent treatment of convection give the lifetimes of radial and non-radial modes. Next, combining the lifetimes and inertias with a stochastic excitation model gives the amplitudes of the modes. We can now directly compare theoretical and observed linewidths and amplitudes of mixed-modes to obtain new constraints on our theoretical models.
Electron-phonon interactions and intrinsic nonadiabatic state of superconductors
Banacky, Pavol
2007-01-01
Study of band structure of YBa 2 Cu 3 O 7 has shown that electron coupling to A g , B 2g and B 3g modes results in fluctuation of saddle point of one of the CuO plane d-pσ band in Y point of 1st BZ across Fermi level. It represents breakdown of adiabatic Born-Oppenheimer approximation and transition of the system into intrinsic nonadiabatic state, ω > E F . Results show that system is stabilized in this state at distorted nuclear geometry. Stabilization effect is mainly due to strong dependence of the electronic motion on instantaneous nuclear momenta. On the lattice scale, the intrinsic nonadiabatic state is geometrically degenerate at broken translation symmetry - system has fluxional nuclear configuration of O2, O3 atoms in CuO planes. It enables formation of mobile bipolarons that can move in the lattice without dissipation. Described effects are absent in non-superconducting YBa 2 Cu 3 O 6
Electron phonon interactions and intrinsic nonadiabatic state of superconductors
Baňacký, Pavol
2007-09-01
Study of band structure of YBa 2Cu 3O 7 has shown that electron coupling to A g, B 2g and B 3g modes results in fluctuation of saddle point of one of the CuO plane d-pσ band in Y point of 1st BZ across Fermi level. It represents breakdown of adiabatic Born-Oppenheimer approximation and transition of the system into intrinsic nonadiabatic state, ω > EF. Results show that system is stabilized in this state at distorted nuclear geometry. Stabilization effect is mainly due to strong dependence of the electronic motion on instantaneous nuclear momenta. On the lattice scale, the intrinsic nonadiabatic state is geometrically degenerate at broken translation symmetry - system has fluxional nuclear configuration of O2, O3 atoms in CuO planes. It enables formation of mobile bipolarons that can move in the lattice without dissipation. Described effects are absent in non-superconducting YBa 2Cu 3O 6.
Nonadiabatic optical transitions as a turn-on switch for pulse shaping
Hashmi, F. A.; Bouchene, M. A.
2010-01-01
A strong nonresonant, asymmetric ultrashort pulse drives an atomic transition and causes a complete population inversion because of a sudden nonadiabatic jump. This jump is probed in real time by propagating a weak ultrashort pulse in the system which is resonant on an adjacent transition. The probe at the exit of the medium presents an oscillatory structure with the nonadiabatic jump marked in time by the onset of oscillations. The nonadiabatic jump thus acts as a 'turn-on' switch for the shaping of the probe.
Nonadiabatic quantum state control of many bosons in few wells
Tichy, Malte C.; Kock Pedersen, Mads; Mølmer, Klaus
2013-01-01
We present a fast scheme for arbitrary unitary control of interacting bosonic atoms in a double well. Assuming fixed interwell tunneling rate and intrawell interaction strength, we control the many-atom state by a discrete sequence of shifts of the single-well energies. For strong interactions......, resonant tunneling transitions implement beam-splitter U(2) rotations among atom number eigenstates, which can be combined and, thus, permit full controllability. By numerically optimizing such sequences of couplings at avoided level crossings, we extend the realm of full controllability to a wide range...... of realistic interaction parameters, while we remain in the simple control space. We demonstrate the efficiency and the high achievable fidelity of our proposal with nonadiabatic population transfer, NOON-state creation, a cnot gate, and a transistorlike, conditional evolution of several atoms....
Observational tests of non-adiabatic Chaplygin gas
Carneiro, S.; Pigozzo, C., E-mail: saulo.carneiro@pq.cnpq.br, E-mail: cpigozzo@ufba.br [Instituto de Física, Universidade Federal da Bahia, Campus de Ondina, Salvador, BA 40210-340 (Brazil)
2014-10-01
In a previous paper [1] it was shown that any dark sector model can be mapped into a non-adiabatic fluid formed by two interacting components, one with zero pressure and the other with equation-of-state parameter ω = -1. It was also shown that the latter does not cluster and, hence, the former is identified as the observed clustering matter. This guarantees that the dark matter power spectrum does not suffer from oscillations or instabilities. It applies in particular to the generalised Chaplygin gas, which was shown to be equivalent to interacting models at both background and perturbation levels. In the present paper we test the non-adiabatic Chaplygin gas against the Hubble diagram of type Ia supernovae, the position of the first acoustic peak in the anisotropy spectrum of the cosmic microwave background and the linear power spectrum of large scale structures. We consider two different compilations of SNe Ia, namely the Constitution and SDSS samples, both calibrated with the MLCS2k2 fitter, and for the power spectrum we use the 2dFGRS catalogue. The model parameters to be adjusted are the present Hubble parameter, the present matter density and the Chaplygin gas parameter α. The joint analysis best fit gives α ≈ - 0.5, which corresponds to a constant-rate energy flux from dark energy to dark matter, with the dark energy density decaying linearly with the Hubble parameter. The ΛCDM model, equivalent to α = 0, stands outside the 3σ confidence interval.
Classical analog for electronic degrees of freedom in nonadiabatic collision processes
Meyer, H.; Miller, W.H.
1979-01-01
It is shown how a formally exact classical analog can be defined for a finite dimensional (in Hilbert space) quantum mechanical system. This approach is then used to obtain a classical model for the electronic degrees of freedom in a molecular collision system, and the combination of this with the usual classical description of the heavy particle (i.e., nuclear) motion provides a completely classical model for the electronic and heavy particle degrees of freedom. The resulting equations of motion are shown to be equivalent to describing the electronic degrees of freedom by the time-dependent Schroedinger equation, the time dependence arising from the classical motion of the nuclei, the trajectory of which is determined by the quantum mechanical average (i.e., Ehrenfest) force on the nuclei. Quantizing the system via classical S-matrix theory is shown to provide a dynamically consistent description of nonadiabatic collision processes; i.e., different electronic transitions have different heavy particle trajectories and, for example, the total energy of the electronic and heavy particle degrees of freedom is conserved. Application of this classical model for the electronic degrees of freedom (plus classical S-matrix theory) to the two-state model problem shows that the approach provides a good description of the electronic dynamics
Nonequilibrium Green's function theory for nonadiabatic effects in quantum electron transport
Kershaw, Vincent F.; Kosov, Daniel S.
2017-12-01
We develop nonequilibrium Green's function-based transport theory, which includes effects of nonadiabatic nuclear motion in the calculation of the electric current in molecular junctions. Our approach is based on the separation of slow and fast time scales in the equations of motion for Green's functions by means of the Wigner representation. Time derivatives with respect to central time serve as a small parameter in the perturbative expansion enabling the computation of nonadiabatic corrections to molecular Green's functions. Consequently, we produce a series of analytic expressions for non-adiabatic electronic Green's functions (up to the second order in the central time derivatives), which depend not solely on the instantaneous molecular geometry but likewise on nuclear velocities and accelerations. An extended formula for electric current is derived which accounts for the non-adiabatic corrections. This theory is concisely illustrated by the calculations on a model molecular junction.
Nonadiabatic heating of the central plasma sheet at substorm onset
Huang, C.Y.; Frank, L.A.; Rostoker, G.; Fennell, J.; Mitchell, D.G.
1992-01-01
Heating events in the plasma sheet boundary layer and central plasma sheet are found to occur at the onset of expansive phase activity. The main effect is a dramatic increase in plasma temperature, coincident with a partial dipolarization of the magnetic field. Fluxes of energetic particles increase without dispersion during these events which occur at all radial distances up to 23 R E , the apogee of the ISEIE spacecraft. A major difference between these heating events and those observed at geosynchronous distances lies in the heating mechanism which is nonadiabatic beyond 10 R E but may be adiabatic closer to Earth. The energy required to account for the increase in plasma thermal energy is comparable with that required for Joule heating of the ionosphere. The plasma sheet must be considered as a major sink in the energy balance of substorm. The authors estimate lobe magnetic pressures during these events. Changes in lobe pressure are generally not correlated with onsets or intensifications of expansive phase activity
Nonadiabatic charged spherical evolution in the postquasistatic approximation
Rosales, L.; Barreto, W.; Peralta, C.; Rodriguez-Mueller, B.
2010-01-01
We apply the postquasistatic approximation, an iterative method for the evolution of self-gravitating spheres of matter, to study the evolution of dissipative and electrically charged distributions in general relativity. The numerical implementation of our approach leads to a solver which is globally second-order convergent. We evolve nonadiabatic distributions assuming an equation of state that accounts for the anisotropy induced by the electric charge. Dissipation is described by streaming-out or diffusion approximations. We match the interior solution, in noncomoving coordinates, with the Vaidya-Reissner-Nordstroem exterior solution. Two models are considered: (i) a Schwarzschild-like shell in the diffusion limit; and (ii) a Schwarzschild-like interior in the free-streaming limit. These toy models tell us something about the nature of the dissipative and electrically charged collapse. Diffusion stabilizes the gravitational collapse producing a spherical shell whose contraction is halted in a short characteristic hydrodynamic time. The streaming-out radiation provides a more efficient mechanism for emission of energy, redistributing the electric charge on the whole sphere, while the distribution collapses indefinitely with a longer hydrodynamic time scale.
Determination of lifetimes and nonadiabatic correlations from measured dipole polarizabilities
Curtis, Lorenzo J
2007-01-01
In atomic systems for which the total oscillator strength of excitations from the ground state is dominated by the transition to the lowest resonance level, the f-sum rule provides a bracketing inequality connecting the lifetime τ of that level to the dipole polarizability α d . This relationship has been used previously to deduce α d from τ. It is shown here that improved spectroscopic accuracies now permit this procedure to be inverted, with τ deduced from a value for α d obtained spectroscopically using the core polarization model. A similar quantitative relationship exists connecting the nonadiabatic correlation factor β to τ, and thus also to α d . The method is applied to a recent measurement of α d for Kr 6+ to obtain the values τ(4s4p 1 P 1 ) 0.096 ± 0.003 ns and β(Kr 6+ ) = 1.71 ± 0.03a 5 0 . It is shown that the use of this method to make precision lifetime determinations for a small number of ions in an isoelectronic sequence permits the exploitation of observed semiempirical regularities to specify the lifetimes of all ions in that sequence
Nonadiabatic two-electron transfer mediated by an irregular bridge
Petrov, E.G.; Shevchenko, Ye.V.; May, V.
2004-01-01
Nonadiabatic two-electron transfer (TET) mediated by a linear molecular bridge is studied theoretically. Special attention is put on the case of a irregular distribution of bridge site energies as well as on the inter-site Coulomb interaction. Based on the unified description of electron transfer reactions [J. Chem. Phys. 115 (2001) 7107] a closed set of kinetic equations describing the TET process is derived. A reduction of this set to a single exponential donor-acceptor (D-A) TET is performed together with a derivation of an overall D-A TET rate. The latter contains a contribution of the stepwise as well as of the concerted route of D-A TET. The stepwise contribution is determined by two single-electron steps each of them associated with a sequential and a superexchange pathway. A two-electron unistep superexchange transition between the D and A forms the concerted contribution to the overall rate. Both contributions are analyzed in their dependency on the bridge length. The irregular distribution of the bridge site energies as well as the influence of the Coulomb interaction facilitates the D-A TET via a modification of the stepwise and the concerted part of the overall rate. At low temperatures and for short bridges with a single or two units the concerted contribution exceeds the stepwise contribution. If the bridge contains more than two units, the stepwise contribution dominates the overall rate
Pederson, Mark R
2015-04-14
It is tacitly accepted that, for practical basis sets consisting of N functions, solution of the two-electron Coulomb problem in quantum mechanics requires storage of O(N(4)) integrals in the small N limit. For localized functions, in the large N limit, or for planewaves, due to closure, the storage can be reduced to O(N(2)) integrals. Here, it is shown that the storage can be further reduced to O(N(2/3)) for separable basis functions. A practical algorithm, that uses standard one-dimensional Gaussian-quadrature sums, is demonstrated. The resulting algorithm allows for the simultaneous storage, or fast reconstruction, of any two-electron Coulomb integral required for a many-electron calculation on processors with limited memory and disk space. For example, for calculations involving a basis of 9171 planewaves, the memory required to effectively store all Coulomb integrals decreases from 2.8 Gbytes to less than 2.4 Mbytes.
Non-adiabatic effect on Laughlin's argument of the quantum Hall effect
Maruyama, I; Hatsugai, Y
2009-01-01
We have numerically studied a non-adiabatic charge transport in the quantum Hall system pumped by a magnetic flux, as one of the simplest theoretical realizations of non-adiabatic Thouless pumping. In the adiabatic limit, a pumped charge is quantized, known as Laughlin's argument in a cylindrical lattice. In a uniform electric field, we obtained a formula connecting quantized pumping in the adiabatic limit and no-pumping in the sudden limit. The intermediate region between the two limits is determined by the Landau gap. A randomness or impurity effect is also discussed.
Quantum theory of nonadiabatic heavy-particle transfer processes in polar media
Kuznetsov, A.M.
1986-01-01
For the probability of nonadiabatic transfer of heavy particles, a calculating procedure is proposed which in the case of certain processes allows the interaction between motion of the particle undergoing transfer and motion along other degrees of freedom to be exactly accounted for. In the case of symmetric systems, explicit expressions are obtained for the free energy of activation of the transition and for the tunneling factor which allow for nonadiabaticity of motion of the particle undergoing transfer, both in the region beneath the barrier and in the region that is classically accessible
Quantum Nuclear Extension of Electron Nuclear Dynamics on Folded Effective-Potential Surfaces
Hall, B.; Deumens, E.; Ohrn, Y.
2014-01-01
A perennial problem in quantum scattering calculations is accurate theoretical treatment of low energy collisions. We propose a method of extracting a folded, nonadiabatic, effective potential energy surface from electron nuclear dynamics (END) trajectories; we then perform nuclear wave packet...
Observations of nonadiabatic acceleration of ions in Earth's magnetotail
Frank, L. A.; Paterson, W. R.; Kivelson, M. G.
1994-01-01
We present observations of the three-dimensional velocity distributions of protons in the energy range 20 eV to 52 keV at locations within and near the current sheet of Earth's magnetotail at geocentric radial distances 35 to 87 R(sub E). These measurements were acquired on December 8, 1990, with a set of electrostatic analyzers on board the Galileo spacecraft during its approach to Earth in order to obtain one of its gravitational assists to Jupiter. It is found that the velocity distributions are inadequately described as quasi-Maxwellian distributions such as those found in the central plasma sheet at positions nearer to Earth. Instead the proton velocity distributions can be categorized into two major types. The first type is the 'lima bean' shaped distribution with high-speed bulk flows and high temperatures that are similar to those found nearer to Earth in the plasma sheet boundary layer. The second type consists of colder protons with considerably lesser bulk flow speeds. Examples of velocity distributions are given for the plasma mantle, a region near the magnetic neutral line, positions earthward and tailward of the neutral line, and the plasma sheet boundary layer. At positions near the neutral line, only complex velocity distributions consisting of the colder protons are found, whereas both of the above types of distributions are found in and near the current sheet at earthward and tailward locations. Bulk flows are directed generally earthward and tailward at positions earthward and tailward of the neutral line, respectively. Only the high-speed, hot distribution is present in the plasma sheet boundary layer. The observations are interpreted in terms of the nonadiabatic acceleration of protons that flow into the current sheet from the plasma mantle. For this interpretation the hot, 'lima bean' shaped distributions are associated with meandering, or Speiser, orbits in the current sheet. It is suggested that the colder, lower-speed proton velocity
Ideal quantum gas in an expanding cavity: nature of nonadiabatic force.
Nakamura, K; Avazbaev, S K; Sobirov, Z A; Matrasulov, D U; Monnai, T
2011-04-01
We consider a quantum gas of noninteracting particles confined in the expanding cavity and investigate the nature of the nonadiabatic force which is generated from the gas and acts on the cavity wall. First, with use of the time-dependent canonical transformation, which transforms the expanding cavity to the nonexpanding one, we can define the force operator. Second, applying the perturbative theory, which works when the cavity wall begins to move at time origin, we find that the nonadiabatic force is quadratic in the wall velocity and thereby does not break the time-reversal symmetry, in contrast with general belief. Finally, using an assembly of the transitionless quantum states, we obtain the nonadiabatic force exactly. The exact result justifies the validity of both the definition of the force operator and the issue of the perturbative theory. The mysterious mechanism of nonadiabatic transition with the use of transitionless quantum states is also explained. The study is done for both cases of the hard- and soft-wall confinement with the time-dependent confining length. ©2011 American Physical Society
Pittner, Jiri; Lischka, Hans; Barbatti, Mario
2009-01-01
The usage of time-derivative non-adiabatic coupling terms and partially coupled time-dependent equations are investigated to accelerate non-adiabatic dynamics simulations at multireference configuration interaction (MRCI) level. The quality of the results and computational costs are compared against non-adiabatic benchmark dynamics calculations using non-adiabatic coupling vectors. In the comparison between the time-derivative couplings and coupling vectors, deviations in the adiabatic population of individual trajectories were observed in regions of rapid variation of the coupling terms. They, however, affected the average adiabatic population to only about 5%. For small multiconfiguration spaces, dynamics with time-derivative couplings are significantly faster than those with coupling vectors. This relation inverts for larger configuration spaces. The use of the partially coupled equations approach speeds up the simulations significantly while keeping the deviations in the population below few percent. Imidazole and the methaniminium cation are used as test examples
Development of a model for dimethyl ether non-adiabatic reactors to improve methanol conversion
Nasrollahi, Fatemeh [University of Tehran, Tehran (Iran, Islamic Republic of); Bakeri, Gholamreza; Rahimnejad, Mostafa [Babol Noshirvani University of Technology, Babol (Iran, Islamic Republic of); Ismail, Ahmad Fauzi [Universiti Teknologi Malaysia, Skudai (Malaysia); Imanian, Mahdi [Mohajer Technical University, Isfahan (Iran, Islamic Republic of)
2013-10-15
The modeling of adiabatic and non-adiabatic reactors, using three cooling mediums in the shell side of a shell and tube reactor in cocurrent and countercurrent flow regimes has been conducted. The cooling mediums used in this research are saturated water and methanol feed gas to a reactor which is preheated in the shell side and a special type of oil. The results of adiabatic reactor modeling show good compatibility with the data received from a commercial plant. The results of non-adiabatic reactor modeling showed that more methanol conversion can be achieved in a lower length of reactor, even though in some cases the maximum temperature in the tube side of the reactor is more than the deactivation temperature of the catalyst.
Warehime, Mick [Chemical Physics Program, University of Maryland, College Park, Maryland 20742-2021 (United States); Kłos, Jacek; Alexander, Millard H., E-mail: mha@umd.edu [Department of Chemistry and Biochemistry and Institute of Physical Science and Technology, University of Maryland, College Park, Maryland 20742-2021 (United States)
2015-01-21
This is the second in a series of papers detailing a MATLAB based implementation of the finite element method applied to collinear triatomic reactions. Here, we extend our previous work to reactions on coupled potential energy surfaces. The divergence of the probability current density field associated with the two electronically adiabatic states allows us to visualize in a novel way where and how nonadiabaticity occurs. A two-dimensional investigation gives additional insight into nonadiabaticity beyond standard one-dimensional models. We study the F({sup 2}P) + HCl and F({sup 2}P) + H{sub 2} reactions as model applications. Our publicly available code (http://www2.chem.umd.edu/groups/alexander/FEM) is general and easy to use.
Coïsson, M. [INRIM, strada delle Cacce 91, 10135 Torino (Italy); Barrera, G. [INRIM, strada delle Cacce 91, 10135 Torino (Italy); University of Torino, Chemistry Department, via P. Giuria 7, 10125 Torino (Italy); Celegato, F.; Martino, L.; Vinai, F. [INRIM, strada delle Cacce 91, 10135 Torino (Italy); Martino, P. [Politronica srl, via Livorno 60, 10144 Torino (Italy); Ferraro, G. [Center for Space Human Robotics, Istituto Italiano di Tecnologia - IIT, corso Trento 21, 10129 Torino (Italy); Tiberto, P. [INRIM, strada delle Cacce 91, 10135 Torino (Italy)
2016-10-01
An experimental setup for magnetic hyperthermia operating in non-adiabatic conditions is described. A thermodynamic model that takes into account the heat exchanged by the sample with the surrounding environment is developed. A suitable calibration procedure is proposed that allows the experimental validation of the model. Specific absorption rate can then be accurately determined just from the measurement of the sample temperature at the equilibrium steady state. The setup and the measurement procedure represent a simplification with respect to other systems requiring calorimeters or crucial corrections for heat flow. Two families of magnetic nanoparticles, one superparamagnetic and one characterised by larger sizes and static hysteresis, have been characterised as a function of field intensity, and specific absorption rate and intrinsic loss power have been obtained. - Highlights: • Development and thermodynamic modelling of a hyperthermia setup operating in non-adiabatic conditions. • Calibration of the experimental setup and validation of the model. • Accurate measurement of specific absorption rate and intrinsic loss power in non-adiabatic conditions.
Impact of Turbocharger Non-Adiabatic Operation on Engine Volumetric Efficiency and Turbo Lag
S. Shaaban
2012-01-01
Full Text Available Turbocharger performance significantly affects the thermodynamic properties of the working fluid at engine boundaries and hence engine performance. Heat transfer takes place under all circumstances during turbocharger operation. This heat transfer affects the power produced by the turbine, the power consumed by the compressor, and the engine volumetric efficiency. Therefore, non-adiabatic turbocharger performance can restrict the engine charging process and hence engine performance. The present research work investigates the effect of turbocharger non-adiabatic performance on the engine charging process and turbo lag. Two passenger car turbochargers are experimentally and theoretically investigated. The effect of turbine casing insulation is also explored. The present investigation shows that thermal energy is transferred to the compressor under all circumstances. At high rotational speeds, thermal energy is first transferred to the compressor and latter from the compressor to the ambient. Therefore, the compressor appears to be “adiabatic” at high rotational speeds despite the complex heat transfer processes inside the compressor. A tangible effect of turbocharger non-adiabatic performance on the charging process is identified at turbocharger part load operation. The turbine power is the most affected operating parameter, followed by the engine volumetric efficiency. Insulating the turbine is recommended for reducing the turbine size and the turbo lag.
Panholzer, Martin; Gatti, Matteo; Reining, Lucia
2018-04-01
The charge-density response of extended materials is usually dominated by the collective oscillation of electrons, the plasmons. Beyond this feature, however, intriguing many-body effects are observed. They cannot be described by one of the most widely used approaches for the calculation of dielectric functions, which is time-dependent density functional theory (TDDFT) in the adiabatic local density approximation (ALDA). Here, we propose an approximation to the TDDFT exchange-correlation kernel which is nonadiabatic and nonlocal. It is extracted from correlated calculations in the homogeneous electron gas, where we have tabulated it for a wide range of wave vectors and frequencies. A simple mean density approximation allows one to use it in inhomogeneous materials where the density varies on a scale of 1.6 rs or faster. This kernel contains effects that are completely absent in the ALDA; in particular, it correctly describes the double plasmon in the dynamic structure factor of sodium, and it shows the characteristic low-energy peak that appears in systems with low electronic density. It also leads to an overall quantitative improvement of spectra.
Engel, D.; Klews, M.; Wunner, G.
2009-02-01
and to provide a program which allows users to calculate as comprehensively as possible energies, wavelengths, and oscillator strengths of medium-Z atoms and ions up to Z=26 in neutron star magnetic field strengths. Obviously, the method for achieving this goal must be highly efficient since for the calculation of synthetic spectra data of many thousands or even millions of atomic transitions may be required. Solution method: As in previous work on the problem (cf. [3,7]) we exploit the fact that a strong magnetic field results in an approximate decoupling of the dynamics of the electrons parallel and perpendicular to the field. In this adiabatic approximation the single-particle wave functions take the form: ψ(ρ,φ,z)=ϕ(ρ,φ)ṡP(z), where ϕ(ρ,φ) are Landau wave functions, describing the (fast) motion perpendicular to the field, and the P(z) are the longitudinal wave functions, describing the (slow) bound motion along the direction of the field. The spins of the electrons are all aligned antiparallel to the magnetic field and need not be accounted for explicitly. The total N-electron wave function is constructed as a Slater determinant of the single-particle wave functions, and the unknown longitudinal wave functions are determined from the Hartree-Fock equations, which follow from inserting the total N-electron wave function into Schrödinger's variational principle for the total energy. The novel feature of our approach [8] is to use finite-element and B-spline techniques to solve the Hartree-Fock equations for atoms in strong magnetic fields. This is accomplished through the following steps: 1) decomposition of the z-axis into finite elements with quadratically widening element borders; 2) sixth-order B-spline expansion of the single-particle wave functions on the individual finite elements; 3) formulation of the variational principle equivalent to the Hartree-Fock equations in terms of the expansion coefficients. This leads to a simple system of linear
Janke, Svenja M; Auerbach, Daniel J; Wodtke, Alec M; Kandratsenka, Alexander
2015-09-28
We have constructed a potential energy surface (PES) for H-atoms interacting with fcc Au(111) based on fitting the analytic form of the energy from Effective Medium Theory (EMT) to ab initio energy values calculated with density functional theory. The fit used input from configurations of the H-Au system with Au atoms at their lattice positions as well as configurations with the Au atoms displaced from their lattice positions. It reproduces the energy, in full dimension, not only for the configurations used as input but also for a large number of additional configurations derived from ab initio molecular dynamics (AIMD) trajectories at finite temperature. Adiabatic molecular dynamics simulations on this PES reproduce the energy loss behavior of AIMD. EMT also provides expressions for the embedding electron density, which enabled us to develop a self-consistent approach to simulate nonadiabatic electron-hole pair excitation and their effect on the motion of the incident H-atoms. For H atoms with an energy of 2.7 eV colliding with Au, electron-hole pair excitation is by far the most important energy loss pathway, giving an average energy loss ≈3 times that of the adiabatic case. This increased energy loss enhances the probability of the H-atom remaining on or in the Au slab by a factor of 2. The most likely outcome for H-atoms that are not scattered also depends prodigiously on the energy transfer mechanism; for the nonadiabatic case, more than 50% of the H-atoms which do not scatter are adsorbed on the surface, while for the adiabatic case more than 50% pass entirely through the 4 layer simulation slab.
Soudackov, Alexander V; Hammes-Schiffer, Sharon
2015-11-21
Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton
Soudackov, Alexander V.; Hammes-Schiffer, Sharon
2015-01-01
Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at high temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton
Nonadiabatic population transfer in a driven four-level system
Prants, S.V.
1994-01-01
The coherent dynamics of a four-level quantum system with an arbitrary level configuration is described analytically in the modulated polychromatic laser field. The method of dynamical symmetries is invoked to develop the formalism for explicit calculation of the evolution matrix of the system in the resonance fields. The method is free of the usual adiabatic-passage, weak-field approximations, and approximation of the slowly varying amplitudes. The conditions for occurrence of the coherent effects of the total inversion and the total depletion of the initial level of a system driven simultaneously driven simultaneously at several transitions by the laser pulses of arbitrary shape are derived analytically. The obtained results can be applied to problems of the control of quantum processes in multilevel atoms and molecules. 14 refs
Many-electron effects in photoelectron spectroscopy
Martin, R.L.
1976-06-01
The deviations from Koopmans' one-electron model of photoionization which lead to satellite structure in the photoelectron spectrum are examined within the formalism of configuration interaction (CI). The mechanisms which contribute to satellite intensity may be classified as continuum state configuration interaction, final ionic state configuration interaction, and initial state configuration interaction. The discussion centers around the last two mechanisms, these being the prime contributors to the satellite intensity well above threshold. Specific examples of theoretical ''spectra'' are presented for the F(1s) region of HF and the 1s region of neon. The agreement between theory and experiment is found to be excellent. In these two instances, initial state configuration interaction contributions increase the satellite intensity and are of nearly equal importance to the final ionic state mixing
Many electron effects in semiconductor quantum dots
Semiconductor quantum dots (QDs) exhibit shell structures, very similar to atoms. Termed as 'artificial atoms' by some, they are much larger (1 100 nm) than real atoms. One can study a variety of manyelectron effects in them, which are otherwise difficult to observe in a real atom. We have treated these effects within the ...
Implementation of surface hopping molecular dynamics using semiempirical methods
Fabiano, E.; Keal, T.W.; Thiel, W.
2008-01-01
A molecular dynamics driver and surface hopping algorithm for nonadiabatic dynamics has been implemented in a development version of the MNDO semiempirical electronic structure package. The required energies, gradients and nonadiabatic couplings are efficiently evaluated on the fly using semiempirical configuration interaction methods. The choice of algorithms for the time evolution of the nuclear motion and quantum amplitudes is discussed, and different schemes for the computation of nonadiabatic couplings are analysed. The importance of molecular orbital tracking and electronic state following is underlined in the context of configuration interaction calculations. The method is applied to three case studies (ethylene, methaniminium ion, and methanimine) using the orthogonalization corrected OM2 Hamiltonian. In all three cases decay times and dynamics paths similar to high-level ab initio results are obtained
Zareh, Masoud; Heidari, Mohammad Ghorbani [Islamic Azad University, Tehran (Iran, Islamic Republic of)
2016-07-15
This research represents an experimental investigation of the metastable flow and re-condensation phenomenon through non-adiabatic lateral helical capillary tubes and suction tube heat exchanger. The results show that mass flux ratio has a vital role: It affects metastable flow and also reverse heat transfer phenomenon through non-adiabatic helical capillary tube. Therefore, by increasing of the mass flux ratio, the rate of heat transfer between them decreases. In contrast to the strong rate condition of heat transfer between them, reverse heat transfer or re-condensation maybe happen. Moreover, experimental results show that for R134 flow with mass flux ratio more than 57.84, metastable flow exists in non-adiabatic capillary tube with 0.9144 mm inner diameter, 30 mm coil diameter, 6.18 m length, 4 mm inner diameter of compressor suction tube.
Propagation and diffusion-limited extinction of nonadiabatic heterogeneous flame in the SHS process
Makino, Atsushi
1994-01-01
Nonadiabatic heterogeneous flame propagation and extinction in self-propagating high-temperature synthesis (SHS) are analyzed based on a premixed mode of propagation for the bulk flame supported by the nonpremixed reaction of dispersed nonmetals in the liquid metal. The formulation allows for volumetric heat loss throughout the bulk flame, finite-rate Arrhenius reaction at the particle surface, and temperature-sensitive Arrhenius mass diffusion in the liquid. Results show that, subsequent to melting of the metal, the flame structure consists of a relatively thin diffusion-consumption/convection zone followed by a relatively thick convection-loss zone, that the flame propagation rate decreases with increasing heat loss, that at a critical heat-loss rate the flame extinguishes as indicated by the characteristic turning-point behavior, that the surface reaction is diffusion limited such that the nonlinear, temperature-sensitive nature of the system is actually a consequence of the Arrhenius mass diffusion, and that extinction is sensitively affected by the mixture ratio, the degree of dilution, the initial temperature of the compact, and the size of the nonmetal particles. An explicit expression is derived for the normalized mass burning rate, which exhibits the characteristic turning point and shows that extinction occurs when this value is reduced to e -1/2 , which is the same as that for the nonadiabatic gaseous premixed flame. It is further shown that the theoretical results agree well with available experimental data, indicating that the present formulation captures the essential features of the nonadiabatic heterogeneous SHS processes and its potential for extension to describe other SHS phenomena
Non-adiabatic description of proton emission from the odd-odd nucleus 130Eu
Patial Monika
2014-03-01
Full Text Available We discuss the non-adiabatic quasiparticle approach for calculating the rotational spectra and decay width of odd-odd proton emitters. The Coriolis effects are incorporated in both the parent and daughter wave functions. Results for the two probable ground states (1+ and 2+ of the proton emitter 130Eu are discussed. With our calculations, we confirm the proton emitting state to be the Iπ = 1+ state, irrespective of the strength of the Coriolis interaction. This study provides us with an opportunity to look into the details of wave functions of deformed odd-odd nuclei to which the proton emission halflives are quite sensitive.
Segre, Gavriel
2005-01-01
It is shown that the non-adiabatic Hannay's angle of an integrable non-degenerate classical hamiltonian dynamical system may be related to the Aharonov-Anandan phase it develops when it is looked mathematically as a quantum dynamical system.
Kumar, D. Sanjeev [School of Physics, University of Hyderabad, Hyderabad 500046 (India); Mukhopadhyay, Soma [H & S Department of Physics, CMR College of Engineering and Technology, Kandlakoya, Medchal Road, Hyderabad 501 401 (India); Chatterjee, Ashok [School of Physics, University of Hyderabad, Hyderabad 500046 (India)
2016-11-15
The effect of electron–electron interaction and the Rashba and Dresselhaus spin–orbit interactions on the electronic properties of a many-electron system in a parabolically confined quantum dot placed in an external magnetic field is studied. With a simple and physically reasonable model potential for electron–electron interaction term, the problem is solved exactly to second-order in the spin–orbit coupling constants to obtain the energy spectrum, the chemical potential, addition energy and the spin-splitting energy.
Kumar, D. Sanjeev; Mukhopadhyay, Soma; Chatterjee, Ashok
2016-01-01
The effect of electron–electron interaction and the Rashba and Dresselhaus spin–orbit interactions on the electronic properties of a many-electron system in a parabolically confined quantum dot placed in an external magnetic field is studied. With a simple and physically reasonable model potential for electron–electron interaction term, the problem is solved exactly to second-order in the spin–orbit coupling constants to obtain the energy spectrum, the chemical potential, addition energy and the spin-splitting energy.
Hydrogen collisions with transition metal surfaces: Universal electronically nonadiabatic adsorption
Dorenkamp, Yvonne; Jiang, Hongyan; Köckert, Hansjochen; Hertl, Nils; Kammler, Marvin; Janke, Svenja M.; Kandratsenka, Alexander; Wodtke, Alec M.; Bünermann, Oliver
2018-01-01
Inelastic scattering of H and D atoms from the (111) surfaces of six fcc transition metals (Au, Pt, Ag, Pd, Cu, and Ni) was investigated, and in each case, excitation of electron-hole pairs dominates the inelasticity. The results are very similar for all six metals. Differences in the average kinetic energy losses between metals can mainly be attributed to different efficiencies in the coupling to phonons due to the different masses of the metal atoms. The experimental observations can be reproduced by molecular dynamics simulations based on full-dimensional potential energy surfaces and including electronic excitations by using electronic friction in the local density friction approximation. The determining factors for the energy loss are the electron density at the surface, which is similar for all six metals, and the mass ratio between the impinging atoms and the surface atoms. Details of the electronic structure of the metal do not play a significant role. The experimentally validated simulations are used to explore sticking over a wide range of incidence conditions. We find that the sticking probability increases for H and D collisions near normal incidence—consistent with a previously reported penetration-resurfacing mechanism. The sticking probability for H or D on any of these metals may be represented as a simple function of the incidence energy, Ein, metal atom mass, M, and incidence angle, 𝜗i n. S =(S0+a ṡEi n+b ṡM ) *(1 -h (𝜗i n-c ) (1 -cos(𝜗 i n-c ) d ṡh (Ei n-e ) (Ei n-e ) ) ) , where h is the Heaviside step function and for H, S0 = 1.081, a = -0.125 eV-1, b =-8.40 ṡ1 0-4 u-1, c = 28.88°, d = 1.166 eV-1, and e = 0.442 eV; whereas for D, S0 = 1.120, a = -0.124 eV-1, b =-1.20 ṡ1 0-3 u-1, c = 28.62°, d = 1.196 eV-1, and e = 0.474 eV.
Approximations to the non-adiabatic particle response in toroidal geometry
Schep, T.J.; Braams, B.J.
1981-08-01
The non-adiabatic part of the particle response to low-frequency electromagnetic modes with long parallel wavelengths is discussed. Analytic approximations to the kernels of the integrals that relate the amplitudes of the perturbed potentials to the non-adiabatic part of the perturbed density in an axisymmetric toroidal configuration are presented and the results are compared with numerical calculations. It is shown that both in the plane slab and in toroidal geometry the kernel contains a logarithmic singularity. This singularity is associated with particles with vanishing parallel velocity so that, in toroidal geometry, it is related with the behaviour of trapped particles near their turning points. In contrast to the plane slab, in toroidal geometry this logarithmic singularity is mainly real and associated with non-resonant particles. Apart from this logarithmic term, the kernel contains a complex regular part arising from resonant as well as from non-resonant particles. The analytic approximations that will be presented make the dispersion relation of drift-type modes in toroidal geometry amenable to analytic as well as to simpler numerical calculation of the growth rate and of the spatial mode structure
Non-adiabatic pressure loss boundary condition for modelling turbocharger turbine pulsating flow
Chiong, M.S.; Rajoo, S.; Romagnoli, A.; Costall, A.W.; Martinez-Botas, R.F.
2015-01-01
Highlights: • Bespoke non-adiabatic pressure loss boundary for pulse flow turbine modelling. • Predictions show convincing results against experimental and literature data. • Predicted pulse pressure propagation is in good agreement with literature data. • New methodology is time efficient and requires minimal geometrical inputs. - Abstract: This paper presents a simplified methodology of pulse flow turbine modelling, as an alternative over the meanline integrated methodology outlined in previous work, in order to make its application to engine cycle simulation codes much more straight forward. This is enabled through the development of a bespoke non-adiabatic pressure loss boundary to represent the turbine rotor. In this paper, turbocharger turbine pulse flow performance predictions are presented along with a comparison of computation duration against the previously established integrated meanline method. Plots of prediction deviation indicate that the mass flow rate and actual power predictions from both methods are highly comparable and are reasonably close to experimental data. However, the new boundary condition required significantly lower computational time and rotor geometrical inputs. In addition, the pressure wave propagation in this simplified unsteady turbine model at different pulse frequencies has also been found to be in agreement with data from the literature, thereby supporting the confidence in its ability to simulate the wave action encountered in turbine pulse flow operation
Coulomb Repulsion Effect in Two-electron Non-adiabatic Tunneling through a One-level redox Molecule
Medvedev, Igor M.; Kuznetsov, Alexander M.; Ulstrup, Jens
2009-01-01
We investigated Coulomb repulsion effects in nonadiabatic (diabatic) two-electron tunneling through a redox molecule with a single electronic level in a symmetric electrochemical contact under ambient conditions, i.e., room temperature and condensed matter environment. The electrochemical contact...
Ghosh, Jayanta; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in
2016-01-13
Highlights: • Decomposition mechanisms of model energetic salt, guanidium triazolate, are explored. • Decomposition pathways are electronically nonadiabatic. • CASPT2, CASMP2 and CASSCF methodologies are employed. • N{sub 2} and NH{sub 3} are predicted to be the most possible initial decomposition products. - Abstract: Electronically nonadiabatic decomposition pathways of guanidium triazolate are explored theoretically. Nonadiabatically coupled potential energy surfaces are explored at the complete active space self-consistent field (CASSCF) level of theory. For better estimation of energies complete active space second order perturbation theories (CASPT2 and CASMP2) are also employed. Density functional theory (DFT) with B3LYP functional and MP2 level of theory are used to explore subsequent ground state decomposition pathways. In comparison with all possible stable decomposition products (such as, N{sub 2}, NH{sub 3}, HNC, HCN, NH{sub 2}CN and CH{sub 3}NC), only NH{sub 3} (with NH{sub 2}CN) and N{sub 2} are predicted to be energetically most accessible initial decomposition products. Furthermore, different conical intersections between the S{sub 1} and S{sub 0} surfaces, which are computed at the CASSCF(14,10)/6-31G(d) level of theory, are found to play an essential role in the excited state deactivation process of guanidium triazolate. This is the first report on the electronically nonadiabatic decomposition mechanisms of isolated guanidium triazolate salt.
Nonadiabatic quantum wave packet dynamics of the H + H2 reaction ...
Administrator
intersections of the two JT split component states. The energetically ... between the theory and experiment,. 1 there remains ..... overhead raises by a factor of two for each WP .... Herzberg G and Longuet-Higgins H C 1963 Disscuss. Faraday.
Newton-X: a surface-hopping program for nonadiabatic molecular dynamics
Barbatti, M.; Ruckenbauer, M.; Plasser, F.; Pittner, Jiří; Granucci, G.; Persico, M.; Lischka, H.
2014-01-01
Roč. 4, č. 1 (2014), s. 26-33 ISSN 1759-0876 R&D Projects: GA ČR(CZ) GAP208/12/0559 Institutional support: RVO:61388955 Keywords : Absorption and emission spectra * Excited-state energy * Multi reference configuration interactions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 11.885, year: 2014
On the Magnitude of the Nonadiabatic Error for Highly Coupled Radicals
Stanton, J. F.
2009-06-01
A review is given of recent advances in the construction of (quasi)diabatic model Hamiltonians and their application to analyzing the spectroscopy of molecules with strong vibronic coupling. A numerical application to the vibronic levels of the BNB radical below 0.6 eV is presented, together with corresponding adiabatic (quantum chemistry) calculations. The agreement with the experimental levels is nearly quantitative with the model Hamiltonian, attesting to the power of the approach. On the contrary, it is also revealed that the magnitude of the nonadiabatic contributions to the zero-point energy and the lowest fundamental frequency of the coupling mode are considerably larger than expected, at least by your narrator.
Nonadiabatic calculations for tdμ relevant for muon catalyzed fusion
Szalewicz, K.; Jeziorski, B.
1991-01-01
Due to the mass effect, muonic molecular ions are about 200 times smaller than their electronic counterparts. The proximity of the nuclei in the tdμ ion results in fusion taking place within a picosecond. The properties of this ion are central to understanding the phenomenon of muon catalysis. The authors developed a computational method of solving the nonadiabatic Schroedinger equation for the bound and resonance states of tdμ and its isotopic analogues. The method takes into account both the Coulomb interactions and the strong nuclear forces responsible for the fusion reaction. The wave functions obtained from this method were used to predict very accurately branching ratios and transition rates relevant for various stages of the muon catalytic cycle. Knowledge of these quantities will guide the experiments and help to answer the question of feasibility of net energy production via muon catalysis
Generalization of the geometric optical series approach for nonadiabatic scattering problems
Herman, M.F.
1982-01-01
The geometric optical series approach of Bremmer is generalized for multisurface nonadiabatic scattering problems. This method yields the formal solution of the Schroedinger equation as an infinite series of multiple integrals. The zeroth order term corresponds to WKB propagation on a single adiabatic surface, while the general Nth order term involves N reflections and/or transitions between surfaces accompanied by ''free,'' single surface semiclassical propagation between the points of reflection and transition. Each term is integrated over all possible transition and reflection points. The adiabatic and diabatic limits of this expression are discussed. Numerical results, in which all reflections are ignored, are presented for curve crossing and noncrossing problems. These results are compared to exact quantum results and are shown to be highly accurate
Nonadiabatic theory of strong-field atomic effects under elliptical polarization
Wang Xu; Eberly, J. H.
2012-01-01
Elliptically polarized laser fields provide a new channel for access to strong-field processes that are either suppressed or not present under linear polarization. Quantum theory is mostly unavailable for their analysis, and we report here results of a systematic study based on a classical ensemble theory with solution of the relevant ab inito time-dependent Newton equations for selected model atoms. The study's approach is necessarily nonadiabatic, as it follows individual electron trajectories leading to single, double, and triple ionizations. Of particular interest are new results bearing on open questions concerning experimental reports of unexplained species dependences as well as double-electron release times that are badly matched by a conventional adiabatic quantum tunneling theory. We also report the first analysis of electron trajectories for sequential and non-sequential triple ionization.
Li, Keqiao; Cai, Dehua; Liu, Yue; Jiang, Jingkai; Sun, Wei; He, Guogeng
2017-01-01
Graphical abstract: A novel air-cooled non-adiabatic ejection-absorption refrigeration cycle using R290/refrigeration oil has been thermodynamically analyzed. Influences of the ejector and the non-adiabatic absorber applications on the system performance and other system operation parameters have been investigated. The simulation results will be of great help to the miniaturization and practical application of the air-cooled absorption refrigeration system. - Highlights: • A novel air-cooled non-adiabatic ejection-absorption refrigeration cycle is proposed. • Influences of the ejector and the air-cooled non-adiabatic absorber applications on the system performance are investigated. • Variations of system performance and other system operation parameters are investigated. • R290/refrigeration oil mixture used as working pairs is analyzed. - Abstract: This paper thermodynamically analyzes a novel air-cooled non-adiabatic ejection-absorption refrigeration cycle with R290/oil mixture driven by exhaust heat. An ejector located at the upstream of the non-adiabatic absorber is employed to improve the cycle performance. Variations of COP, circulation ratio and component heat load of the system as a function of generating temperature, pressure ratio, absorption temperature, condensing temperature and evaporating temperature have been investigated in this work. The simulation results show that, compared with the conventional absorption refrigeration cycle, this non-adiabatic ejection-absorption refrigeration cycle has higher absorption efficiency, better performance, wider working condition range and lower total heat load and its COP can reach as high as 0.5297. The implementation of the ejector and the non-adiabatic absorber helps to realize the miniaturization and wider application of the absorption refrigeration system. In addition, R290/oil mixture is a kind of highly potential working pairs for absorption refrigeration.
Kroeger, J
2008-01-01
Three aspects of electron-phonon coupling at metal surfaces are reviewed. One aspect is the Kohn effect, which describes an anomalous dispersion relation of surface phonons due to quasi-one-dimensional nesting of Fermi surface contours. The combination of electron energy loss spectroscopy and angle-resolved photoelectron spectroscopy allows us to unambiguously characterize Kohn anomaly systems. A second aspect is the nonadiabatic damping of adsorbate vibrations. Characteristic spectroscopic line shapes of vibrational modes allow us to estimate the amount of energy transfer between the vibrational mode and electron-hole pairs. Case studies of a Kohn anomaly and nonadiabatic damping are provided by the hydrogen- and deuterium-covered Mo(110) surface. As a third aspect of interaction between electrons and phonons, local heating of a C 60 molecule adsorbed on Cu(100) and in contact with the tip of a scanning tunnelling microscope is covered
Bak, Keld L.; Jørgensen, Poul; Jensen, H.J.A.
1992-01-01
A new scheme for obtaining first-order nonadiabatic coupling matrix elements (FO-NACME) for multiconfigurational self-consistent-field (MCSCF) wave functions is presented. The FO-NACME are evaluated from residues of linear response functions. The residues involve the geometrical response of a ref......A new scheme for obtaining first-order nonadiabatic coupling matrix elements (FO-NACME) for multiconfigurational self-consistent-field (MCSCF) wave functions is presented. The FO-NACME are evaluated from residues of linear response functions. The residues involve the geometrical response...... to the full configuration interaction limit. Comparisons are made with state-averaged MCSCF results for MgH2 and finite-difference configuration interaction by perturbation with multiconfigurational zeroth-order wave function reflected by interactive process (CIPSI) results for BH....
Non-adiabatic quantum state preparation and quantum state transport in chains of Rydberg atoms
Ostmann, Maike; Minář, Jiří; Marcuzzi, Matteo; Levi, Emanuele; Lesanovsky, Igor
2017-12-01
Motivated by recent progress in the experimental manipulation of cold atoms in optical lattices, we study three different protocols for non-adiabatic quantum state preparation and state transport in chains of Rydberg atoms. The protocols we discuss are based on the blockade mechanism between atoms which, when excited to a Rydberg state, interact through a van der Waals potential, and rely on single-site addressing. Specifically, we discuss protocols for efficient creation of an antiferromagnetic GHZ state, a class of matrix product states including a so-called Rydberg crystal and for the state transport of a single-qubit quantum state between two ends of a chain of atoms. We identify system parameters allowing for the operation of the protocols on timescales shorter than the lifetime of the Rydberg states while yielding high fidelity output states. We discuss the effect of positional disorder on the resulting states and comment on limitations due to other sources of noise such as radiative decay of the Rydberg states. The proposed protocols provide a testbed for benchmarking the performance of quantum information processing platforms based on Rydberg atoms.
Non-adiabatic quantum evolution: The S matrix as a geometrical phase factor
Saadi, Y., E-mail: S_yahiadz@yahoo.fr [Laboratoire de Physique Quantique et Systèmes Dynamiques, Faculté des Sciences, Université Ferhat Abbas de Sétif, Sétif 19000 (Algeria); Maamache, M. [Laboratoire de Physique Quantique et Systèmes Dynamiques, Faculté des Sciences, Université Ferhat Abbas de Sétif, Sétif 19000 (Algeria)
2012-03-19
We present a complete derivation of the exact evolution of quantum mechanics for the case when the underlying spectrum is continuous. We base our discussion on the use of the Weyl eigendifferentials. We show that a quantum system being in an eigenstate of an invariant will remain in the subspace generated by the eigenstates of the invariant, thereby acquiring a generalized non-adiabatic or Aharonov–Anandan geometric phase linked to the diagonal element of the S matrix. The modified Pöschl–Teller potential and the time-dependent linear potential are worked out as illustrations. -- Highlights: ► In this Letter we study the exact quantum evolution for continuous spectra problems. ► We base our discussion on the use of the Weyl eigendifferentials. ► We give a generalized Lewis and Riesenfeld phase for continuous spectra. ► This generalized phase or Aharonov–Anandan geometric phase is linked to the S matrix. ► The modified Pöschl–Teller and the linear potential are worked out as illustrations.
Raymond, Neil; Iouchtchenko, Dmitri; Roy, Pierre-Nicholas; Nooijen, Marcel
2018-05-01
We introduce a new path integral Monte Carlo method for investigating nonadiabatic systems in thermal equilibrium and demonstrate an approach to reducing stochastic error. We derive a general path integral expression for the partition function in a product basis of continuous nuclear and discrete electronic degrees of freedom without the use of any mapping schemes. We separate our Hamiltonian into a harmonic portion and a coupling portion; the partition function can then be calculated as the product of a Monte Carlo estimator (of the coupling contribution to the partition function) and a normalization factor (that is evaluated analytically). A Gaussian mixture model is used to evaluate the Monte Carlo estimator in a computationally efficient manner. Using two model systems, we demonstrate our approach to reduce the stochastic error associated with the Monte Carlo estimator. We show that the selection of the harmonic oscillators comprising the sampling distribution directly affects the efficiency of the method. Our results demonstrate that our path integral Monte Carlo method's deviation from exact Trotter calculations is dominated by the choice of the sampling distribution. By improving the sampling distribution, we can drastically reduce the stochastic error leading to lower computational cost.
The effect of nonadiabaticity on the efficiency of quantum memory based on an optical cavity
Veselkova, N. G.; Sokolov, I. V.
2017-07-01
Quantum efficiency is an important characteristic of quantum memory devices that are aimed at recording the quantum state of light signals and its storing and reading. In the case of memory based on an ensemble of cold atoms placed in an optical cavity, the efficiency is restricted, in particular, by relaxation processes in the system of active atomic levels. We show how the effect of the relaxation on the quantum efficiency can be determined in a regime of the memory usage in which the evolution of signals in time is not arbitrarily slow on the scale of the field lifetime in the cavity and when the frequently used approximation of the adiabatic elimination of the quantized cavity mode field cannot be applied. Taking into account the effect of the nonadiabaticity on the memory quality is of interest in view of the fact that, in order to increase the field-medium coupling parameter, a higher cavity quality factor is required, whereas storing and processing of sequences of many signals in the memory implies that their duration is reduced. We consider the applicability of the well-known efficiency estimates via the system cooperativity parameter and estimate a more general form. In connection with the theoretical description of the memory of the given type, we also discuss qualitative differences in the behavior of a random source introduced into the Heisenberg-Langevin equations for atomic variables in the cases of a large and a small number of atoms.
The role of magnetic field fluctuations in nonadiabatic acceleration of ions during dipolarization
Ono, Y.; Nosé, M.; Christon, S. P.; Lui, A. T. Y.
2009-05-01
We statistically examine changes in the composition of two different ion species, proton and oxygen ions, in the near-Earth plasma sheet (X = -16 R E ˜ -6 R E ) during substorm-associated dipolarization. We use 10 years of energetic (9-212 keV/e) ion data obtained by the suprathermal ion composition spectrometer (STICS) sensor of the energetic particles and ion composition (EPIC) instrument on board the Geotail spacecraft. The results are as follows: (1) Although the percentage increase in the energy density of O+ ions before and after a dipolarization exceeds that of H+ ions in the low-energy range (9-36 keV/e), this property is not evident in the high-energy range (56-212 keV/e); (2) the energy spectrum of H+ and that of O+ become harder after dipolarization in almost all events; and (3) in some events the energy spectrum of O+ becomes harder than that of H+ as reported by previous studies, and, importantly, in other events, the spectrum of H+ becomes harder than that of O+. In order to investigate what mechanism causes these observational results, we focus on magnetic field fluctuations during dipolarization. It is found that the increase of the spectrum slope is positively correlated with the power of waves whose frequencies are close to the gyrofrequency of H+ or O+, respectively (the correlation coefficient is 0.48 for H+ and 0.68 for O+). In conclusion, ions are nonadiabatically accelerated by the electric field induced by the magnetic field fluctuations whose frequencies are close to their gyrofrequencies.
Mandal, Anirban; Hunt, Katharine L. C.
2018-05-01
For a perturbed quantum system initially in the ground state, the coefficient ck(t) of excited state k in the time-dependent wave function separates into adiabatic and nonadiabatic terms. The adiabatic term ak(t) accounts for the adjustment of the original ground state to form the new ground state of the instantaneous Hamiltonian H(t), by incorporating excited states of the unperturbed Hamiltonian H0 without transitions; ak(t) follows the adiabatic theorem of Born and Fock. The nonadiabatic term bk(t) describes excitation into another quantum state k; bk(t) is obtained as an integral containing the time derivative of the perturbation. The true transition probability is given by |bk(t)|2, as first stated by Landau and Lifshitz. In this work, we contrast |bk(t)|2 and |ck(t)|2. The latter is the norm-square of the entire excited-state coefficient which is used for the transition probability within Fermi's golden rule. Calculations are performed for a perturbing pulse consisting of a cosine or sine wave in a Gaussian envelope. When the transition frequency ωk0 is on resonance with the frequency ω of the cosine wave, |bk(t)|2 and |ck(t)|2 rise almost monotonically to the same final value; the two are intertwined, but they are out of phase with each other. Off resonance (when ωk0 ≠ ω), |bk(t)|2 and |ck(t)|2 differ significantly during the pulse. They oscillate out of phase and reach different maxima but then fall off to equal final values after the pulse has ended, when ak(t) ≡ 0. If ωk0 ω. While the transition probability is rising, the midpoints between successive maxima and minima fit Gaussian functions of the form a exp[-b(t - d)2]. To our knowledge, this is the first analysis of nonadiabatic transition probabilities during a perturbing pulse.
Golibrzuch, Kai; Shirhatti, Pranav R.; Kandratsenka, Alexander; Wodtke, Alec M.; Bartels, Christof [Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077 (Germany); Max Planck Institute for Biophysical Chemistry, Göttingen 37077 (Germany); Rahinov, Igor [Department of Natural Sciences, The Open University of Israel, Ra' anana 4353701 (Israel); Auerbach, Daniel J. [Institute for Physical Chemistry, Georg August University of Göttingen, Göttingen 37077 (Germany); Max Planck Institute for Biophysical Chemistry, Göttingen 37077 (Germany); Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106 (United States)
2014-01-28
We present a combined experimental and theoretical study of NO(v = 3 → 3, 2, 1) scattering from a Au(111) surface at incidence translational energies ranging from 0.1 to 1.2 eV. Experimentally, molecular beam–surface scattering is combined with vibrational overtone pumping and quantum-state selective detection of the recoiling molecules. Theoretically, we employ a recently developed first-principles approach, which employs an Independent Electron Surface Hopping (IESH) algorithm to model the nonadiabatic dynamics on a Newns-Anderson Hamiltonian derived from density functional theory. This approach has been successful when compared to previously reported NO/Au scattering data. The experiments presented here show that vibrational relaxation probabilities increase with incidence energy of translation. The theoretical simulations incorrectly predict high relaxation probabilities at low incidence translational energy. We show that this behavior originates from trajectories exhibiting multiple bounces at the surface, associated with deeper penetration and favored (N-down) molecular orientation, resulting in a higher average number of electronic hops and thus stronger vibrational relaxation. The experimentally observed narrow angular distributions suggest that mainly single-bounce collisions are important. Restricting the simulations by selecting only single-bounce trajectories improves agreement with experiment. The multiple bounce artifacts discovered in this work are also present in simulations employing electronic friction and even for electronically adiabatic simulations, meaning they are not a direct result of the IESH algorithm. This work demonstrates how even subtle errors in the adiabatic interaction potential, especially those that influence the interaction time of the molecule with the surface, can lead to an incorrect description of electronically nonadiabatic vibrational energy transfer in molecule-surface collisions.
Energetics and dynamics of excess electrons in simple fluids
Space, B.
1992-01-01
Excess electronic dynamical and equilibrium properties are modeled in both polarizable and nonpolarizable noble gas fluids. Explicit dynamical calculations are carried out for excess electrons in fluid helium, where excess electronic eigenstates are localized. Energetics and dynamics are considered for fluids which span the entire range of polarizability present in the rare gases. Excess electronic eigenstates and eigenvalues are calculated for fluids of helium, argon and xenon. Both equilibrium and dynamical information is obtained from the calculation of these wavefunctions. A surface hopping trajectory method for studying nonadiabatic excess electronic relaxation in condensed systems is used to explore the nonadiabatic relaxation after photoexciting an equilibrated excess electron in dense fluid helium. The different types on nonadiabatic phenomena which are important in excess electronic relaxation are surveyed. The same surface hopping trajectory method is also used to study the rapid nonadiabatic relaxation after an excess electron is injected into unperturbed fluid helium. Several distinctively different relaxation processes, characterized by their relative importance at different times during the relaxation to a localized equilibrium state, are detailed. Though the dynamical properties of excess electrons under the conditions considered here have never been studied before, the behavior is remarkably similar to that observed in both experimental and theoretical studies of electron hydration dynamics, indicating that the processes described may be very general relaxation mechanisms for localization and trapping in fluids. Additionally, ground state energies of an excess electron, e 0 , are computed as a function of solvent density using model electron-atom pseudopotentials in fluid helium, argon, and xenon. The nonuniqueness of the pseudopotential description of electron-molecule interactions is demonstrated
Surface Hopping Dynamics with Correlated Single-Reference Methods: 9H-Adenine as a Case Study
Plasser, F.; Crespo-Otero, R.; Pederzoli, Marek; Pittner, Jiří; Lischka, H.; Barbatti, M.
2014-01-01
Roč. 10, č. 4 (2014), s. 1395-1405 ISSN 1549-9618 R&D Projects: GA ČR(CZ) GAP208/12/0559 Institutional support: RVO:61388955 Keywords : density-functional theory * resolved photoelectron spectroscopy * nonadiabatic molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.498, year: 2014
Flow of CO2 ethanol and of CO2 methanol in a non-adiabatic microfluidic T-junction at high pressures
Blanch Ojea, R.; Tiggelaar, Roald M.; Pallares, J.; Grau, F.X.; Gardeniers, Johannes G.E.
2012-01-01
In this work, an experimental investigation of the single- and multiphase flows of two sets of fluids, CO2–ethanol and CO2–methanol, in a non-adiabatic microfluidic T-junction is presented. The operating conditions ranged from 7 to 18 MPa, and from 294 to 474 K. The feed mass fraction of CO2 in the
Structural Influence on Excited State Dynamics in Simple Amines
Klein, Liv Bærenholdt
experiments with calculations, provides new insight into the nature of the internal conversion processes that mediate the dynamical evolution between Rydberg states, and how structural variations in simple amine system have a large impact on the non-adiabatic processes. The experimental method of choice...... is femtosecond time-resolved photoelectron velocity map imaging (VMI), which is a newtechnique in the Copenhagen lab. The design, building and implementation of the VMI spectrometer has been a very substantial part of the thesis work. This techniques oers enhanced information content in the form of ecient...... and sensitive collection of photoelectron spectra. In particular, the angleresolved data available from the VMI approach provides highly detailed mechanistic insight about the relaxation pathways. One striking novel nding is that for tertiary amines, the critical factor driving the non-adiabatic dynamics...
Balucani, Nadia; Leonori, Francesca; Casavecchia, Piergiorgio; Fu, Bina; Bowman, Joel M
2015-12-17
The combustion relevant O((3)P) + C2H4 reaction stands out as a prototypical multichannel nonadiabatic reaction involving both triplet and singlet potential energy surfaces (PESs), which are strongly coupled. Crossed molecular beam (CMB) scattering experiments with universal soft electron ionization mass spectrometric detection have been used to characterize the dynamics of this reaction at the relatively high collision energy Ec of 13.7 kcal/mol, attained by crossing the reactant beams at an angle of 135°. This work is a full report of the data at the highest Ec investigated for this reaction. From laboratory product angular and velocity distribution measurements, angular and translational energy distributions in the center-of-mass system have been obtained for the five observed exothermic competing reaction channels leading to H + CH2CHO, H + CH3CO, CH3 + HCO, CH2 + H2CO, and H2 + CH2CO. The product branching ratios (BRs) have been derived. The elucidation of the reaction dynamics is assisted by synergic full-dimensional quasiclassical trajectory surface-hopping calculations of the reactive differential cross sections on coupled ab initio triplet/singlet PESs. This joint experimental/theoretical study extends and complements our previous combined CMB and theoretical work at the lower collision energy of 8.4 kcal/mol. The theoretically derived BRs and extent of intersystem crossing (ISC) are compared with experimental results. In particular, the predictions of the QCT results for the three main channels (those leading to vinoxy + H, methyl + HCO and methylene + H2CO formation) are compared directly with the experimental data in the laboratory frame. Good overall agreement is noted between theory and experiment, although some small, yet significant shortcomings of the theoretical differential cross section are noted. Both experiment and theory find almost an equal contribution from the triplet and singlet surfaces to the reaction, with a clear tendency of the
Li, Jiaru; Joubert-Doriol, Loïc; Izmaylov, Artur F.
2017-08-01
We investigate geometric phase (GP) effects in nonadiabatic transitions through a conical intersection (CI) in an N-dimensional linear vibronic coupling (ND-LVC) model. This model allows for the coordinate transformation encompassing all nonadiabatic effects within a two-dimensional (2D) subsystem, while the other N - 2 dimensions form a system of uncoupled harmonic oscillators identical for both electronic states and coupled bi-linearly with the subsystem coordinates. The 2D subsystem governs ultra-fast nonadiabatic dynamics through the CI and provides a convenient model for studying GP effects. Parameters of the original ND-LVC model define the Hamiltonian of the transformed 2D subsystem and thus influence GP effects directly. Our analysis reveals what values of ND-LVC parameters can introduce symmetry breaking in the 2D subsystem that diminishes GP effects.
Mitrić, R.; Bonačič-Koutecký, V.; Pittner, Jiří; Lischka, H.
2006-01-01
Roč. 125, č. 2 (2006), 021303 ISSN 0021-9606 Grant - others:Deutsche Forschungsgemeinschaft(DE) SFB 450; Austrian Science Fund(AT) P18411-N19 Institutional research plan: CEZ:AV0Z40400503 Keywords : alkali-halide clusters * optical-responce properties * sodium - fluoride clusters Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.166, year: 2006
Calculation of decay widths of pp{mu}{sub {nu}}{sub ,J}{sup *} ion in non-adiabatic approach
Gheisari, R. [Persian Gulf Univ., Physics Dept., Bushehr (Iran, Islamic Republic of)
2009-06-15
We calculate decay widths of the metastable pp{mu}{sub {nu}}{sub ,J}{sup *} molecular ion in non-adiabatic approach. The muonic molecular ion can be formed in collision of the excited p{mu}(2s) atoms with H{sub 2}. Then, the decay of the pp{mu}{sub {nu}}{sub ,J}{sup *} system opens a path for the muon from p{mu}(2s) to p{mu}(1s). We employ trial wave function which includes non-adiabatic terms to calculate some radiationless decay widths. The present results of the widths do not agree well with those given in our previous work, however they are more close to recent data of other researchers. (author)
DFT reactivity indices in confined many-electron atoms + ∫
Unknown
Functional Theory (DFT) based global descriptors of chemical reactivity for atoms .... interesting due to its utility as a model in the wide variety of applications ... hydrogen atom at Rc = 2⋅0 au is expected to correspond to the energy value of ...
Goodman, Lawrence E
2001-01-01
Beginning text presents complete theoretical treatment of mechanical model systems and deals with technological applications. Topics include introduction to calculus of vectors, particle motion, dynamics of particle systems and plane rigid bodies, technical applications in plane motions, theory of mechanical vibrations, and more. Exercises and answers appear in each chapter.
Lahiri, B. B.; Ranoo, Surojit; Philip, John
2017-11-01
Magnetic fluid hyperthermia (MFH) is becoming a viable cancer treatment methodology where the alternating magnetic field induced heating of magnetic fluid is utilized for ablating the cancerous cells or making them more susceptible to the conventional treatments. The heating efficiency in MFH is quantified in terms of specific absorption rate (SAR), which is defined as the heating power generated per unit mass. In majority of the experimental studies, SAR is evaluated from the temperature rise curves, obtained under non-adiabatic experimental conditions, which is prone to various thermodynamic uncertainties. A proper understanding of the experimental uncertainties and its remedies is a prerequisite for obtaining accurate and reproducible SAR. Here, we study the thermodynamic uncertainties associated with peripheral heating, delayed heating, heat loss from the sample and spatial variation in the temperature profile within the sample. Using first order approximations, an adiabatic reconstruction protocol for the measured temperature rise curves is developed for SAR estimation, which is found to be in good agreement with those obtained from the computationally intense slope corrected method. Our experimental findings clearly show that the peripheral and delayed heating are due to radiation heat transfer from the heating coils and slower response time of the sensor, respectively. Our results suggest that the peripheral heating is linearly proportional to the sample area to volume ratio and coil temperature. It is also observed that peripheral heating decreases in presence of a non-magnetic insulating shielding. The delayed heating is found to contribute up to ~25% uncertainties in SAR values. As the SAR values are very sensitive to the initial slope determination method, explicit mention of the range of linear regression analysis is appropriate to reproduce the results. The effect of sample volume to area ratio on linear heat loss rate is systematically studied and the
Lahiri, B B; Ranoo, Surojit; Philip, John
2017-01-01
Magnetic fluid hyperthermia (MFH) is becoming a viable cancer treatment methodology where the alternating magnetic field induced heating of magnetic fluid is utilized for ablating the cancerous cells or making them more susceptible to the conventional treatments. The heating efficiency in MFH is quantified in terms of specific absorption rate (SAR), which is defined as the heating power generated per unit mass. In majority of the experimental studies, SAR is evaluated from the temperature rise curves, obtained under non-adiabatic experimental conditions, which is prone to various thermodynamic uncertainties. A proper understanding of the experimental uncertainties and its remedies is a prerequisite for obtaining accurate and reproducible SAR. Here, we study the thermodynamic uncertainties associated with peripheral heating, delayed heating, heat loss from the sample and spatial variation in the temperature profile within the sample. Using first order approximations, an adiabatic reconstruction protocol for the measured temperature rise curves is developed for SAR estimation, which is found to be in good agreement with those obtained from the computationally intense slope corrected method. Our experimental findings clearly show that the peripheral and delayed heating are due to radiation heat transfer from the heating coils and slower response time of the sensor, respectively. Our results suggest that the peripheral heating is linearly proportional to the sample area to volume ratio and coil temperature. It is also observed that peripheral heating decreases in presence of a non-magnetic insulating shielding. The delayed heating is found to contribute up to ∼25% uncertainties in SAR values. As the SAR values are very sensitive to the initial slope determination method, explicit mention of the range of linear regression analysis is appropriate to reproduce the results. The effect of sample volume to area ratio on linear heat loss rate is systematically studied and
Calculation of non-adiabatic coupling vectors in a local-orbital basis set
Abad, E.; Lewis, J.P.; Zobač, Vladimír; Hapala, Prokop; Jelínek, Pavel; Ortega, J.
2013-01-01
Roč. 138, č. 15 (2013), "154106-1"-"154106-8" ISSN 0021-9606 R&D Projects: GA ČR GAP204/10/0952; GA MŠk ME09048 Institutional support: RVO:68378271 Keywords : non adiabatic couplings * molecular dynamics * DFT Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.122, year: 2013
Pseudorotational dynamics of small molecular species
Hagelberg, F.
2002-01-01
The electron nuclear dynamics (END) theory was designed to provide a full description of the dynamic development of the electronic system. It is independent of any potential energy surface constructions. The dynamic behavior of molecules close to the threshold of dissociation was the objective of this study. Thus, simulations based on END theory were performed with the aim to extend the current understanding of the dynamic features of pseudorotational into a non-adiabatic regime. Electron dynamics of triatomic species (H 3 + and Li 3 + ) in terms of electronic angular momentum expectation values were characterized. Finally, it is shown that the expansion coefficients which carry the information about the excitation content of the electronic system at any stage of the motional process can be calculated. (nevyjel)
On the fly quantum dynamics of electronic and nuclear wave packets
Komarova, Ksenia G.; Remacle, F.; Levine, R. D.
2018-05-01
Multielectronic states quantum dynamics on a grid is described in a manner motivated by on the fly classical trajectory computations. Non stationary electronic states are prepared by a few cycle laser pulse. The nuclei respond and begin moving. We solve the time dependent Schrödinger equation for the electronic and nuclear dynamics for excitation from the ground electronic state. A satisfactory accuracy is possible using a localized description on a discrete grid. This enables computing on the fly for both the nuclear and electronic dynamics including non-adiabatic couplings. Attosecond dynamics in LiH is used as an example.
Golibrzuch, Kai; Shirhatti, Pranav R; Altschäffel, Jan; Rahinov, Igor; Auerbach, Daniel J; Wodtke, Alec M; Bartels, Christof
2013-09-12
Translational motion is believed to be a spectator degree of freedom in electronically nonadiabatic vibrational energy transfer between molecules and metal surfaces, but the experimental evidence available to support this view is limited. In this work, we have experimentally determined the translational inelasticity in collisions of NO molecules with a single-crystal Au(111) surface-a system with strong electronic nonadiabaticity. State-to-state molecular beam surface scattering was combined with an IR-UV double resonance scheme to obtain high-resolution time-of-flight data. The measurements include vibrationally elastic collisions (v = 3→3, 2→2) as well as collisions where one or two quanta of molecular vibration are excited (2→3, 2→4) or de-excited (2→1, 3→2, 3→1). In addition, we have carried out comprehensive measurements of the effects of rotational excitation on the translational energy of the scattered molecules. We find that under all conditions of this work, the NO molecules lose a large fraction (∼0.45) of their incidence translational energy to the surface. Those molecules that undergo vibrational excitation (relaxation) during the collision recoil slightly slower (faster) than vibrationally elastically scattered molecules. The amount of translational energy change depends on the surface temperature. The translation-to-rotation coupling, which is well-known for v = 0→0 collisions, is found to be significantly weaker for vibrationally inelastic than elastic channels. Our results clearly show that the spectator view of the translational motion in electronically nonadiabatic vibrational energy transfer between NO and Au(111) is only approximately correct.
Dynamics of coupled electron-nuclei-systems in laser fields
Falge, Mirjam
2012-01-01
This work aimed at the theoretical analysis of high harmonic generation in molecules and the influence of coupled electron and nuclear dynamics on ultra-short pulse ionization processes. In the first part of this thesis, the isotope effect and influence of vibrational excitation on high harmonic generation were investigated for the isotope pairs H 2 O/D 2 O and H 2 /D 2 . It was shown that on the one hand high harmonic intensities strongly depend on the vibrational quantum number of the initial state of the water molecule and on the other hand the spectra of H 2 O and D 2 O exhibit a clear isotope effect for certain vibrationally excited states. Also it was shown that high harmonics of vibrationally excited states show an even more pronounced isotope effect than the ground state. The second and third part of this work treats the influence of coupled electron and nuclear dynamics on photoelectron spectra. In order to facilitate a numerically exact description of this dynamics, a simple one-dimensional model system (Shin-Metiu model) was used. It consists of only a single electronic and nuclear degree-of-freedom and allows for a switching between adiabatic and strongly non-adiabatic dynamics by its parameterization. This model served for the analysis of the dynamics of three different cases ranging from weak over intermediate to strong electron-nuclear coupling. To investigate the influence of non-adiabatic effects on photoelectron spectra, time-resolved photoelectron spectra were calculated applying two methods: a numerically exact treatment and an adiabatic approach neglecting the electron-nuclear coupling. Subsequently, the dependence of the efficiency of a non-adiabatic transition on the nuclear mass was analysed. To this end, the population dynamics and photoelectron spectra were calculated numerically exactly for a strong electron and nuclear coupling. Thereafter the asymmetry in forward and backward direction of time-resolved photoelectron spectra and the
Non-adiabatic transition of the fissioning nucleus at scission: the time scale
Carjan, N.; Rizea, M.
2012-01-01
The sudden approximation has been recently used to calculate the microscopic scission-properties during low-energy fission of 236 U. In this approach the scission process, i.e., the transition from two fragments connected by a thin neck to two separated fragments was considered to happen suddenly. The approach is stationary (the time evolution is not explicitly treated) and it only involves the two sets of neutron eigenstates for the two nuclear configurations considered: just before scission (α i ) and immediately after scission (α f ). The purpose of the present paper is to go beyond this mathematical approximation considering the real physical situation in which the above mentioned transition takes place in a time interval ΔT ≠ 0. For this we need to follow the evolution from α i to αf of all occupied neutron states by solving numerically the two-dimensional time-dependent Schroedinger equation with time-dependent potential. Calculations are performed for mass divisions from A L = 70 to A L = 118 (A L being the light fragment mass) taking into account all the neutron states (Ω = 1/2, 3/2,..., 11/2) that are bound in 236 U at α i . The diabatic-dissipative dynamics of the neck rupture is very complicated and its exact duration is un-known. ΔT is therefore taken as parameter having values from 0.25 x 10 -22 to 6 x 10 -22 sec. The resulting scission neutron multiplicities - sc and primary fragments' excitation energies E sc * are compared with those obtained in the frame of the sudden approximation (that corresponds to ΔT = 0). As expected, shorter is the transition time more excited are the fragments and more neutrons are emitted, the sudden approximation being an upper limit. For ΔT = 10 -22 sec, which is a realistic value, the time dependent results are 20% below this limit. For transition times longer than 5 x 10 -22 sec the adiabatic limit is reached: no scission neutrons are emitted anymore and the excitation energy at α f is negligible. The
Faraji, Shirin; Matsika, Spiridoula; Krylov, Anna I.
2018-01-01
We report an implementation of non-adiabatic coupling (NAC) forces within the equation-of-motion coupled-cluster with single and double excitations (EOM-CCSD) framework via the summed-state approach. Using illustrative examples, we compare NAC forces computed with EOM-CCSD and multi-reference (MR) wave functions (for selected cases, we also consider configuration interaction singles). In addition to the magnitude of the NAC vectors, we analyze their direction, which is important for the calculations of the rate of non-adiabatic transitions. Our benchmark set comprises three doublet radical-cations (hexatriene, cyclohexadiene, and uracil), neutral uracil, and sodium-doped ammonia clusters. When the characters of the states agree among different methods, we observe good agreement between the respective NAC vectors, both in the Franck-Condon region and away. In the cases of large discrepancies between the methods, the disagreement can be attributed to the difference in the states' character, which, in some cases, is very sensitive to electron correlation, both within single-reference and multi-reference frameworks. The numeric results confirm that the accuracy of NAC vectors depends critically on the quality of the underlying wave functions. Within their domain of applicability, EOM-CC methods provide a viable alternative to MR approaches.
Dislocation Dynamics During Plastic Deformation
Messerschmidt, Ulrich
2010-01-01
The book gives an overview of the dynamic behavior of dislocations and its relation to plastic deformation. It introduces the general properties of dislocations and treats the dislocation dynamics in some detail. Finally, examples are described of the processes in different classes of materials, i.e. semiconductors, ceramics, metals, intermetallic materials, and quasicrystals. The processes are illustrated by many electron micrographs of dislocations under stress and by video clips taken during in situ straining experiments in a high-voltage electron microscope showing moving dislocations. Thus, the users of the book also obtain an immediate impression and understanding of dislocation dynamics.
Effects of chirping on the dissociation dynamics of H2 in a two-frequency laser field
Datta, Avijit; Bhattacharyya, S.S.; Kim, Bongsoo
2002-01-01
We present the effects of frequency chirping of laser pulses on (1+1)-photon resonance-enhanced dissociation dynamics of H 2 . The dissociation occurs via two closely spaced nonadiabatically coupled intermediate levels which are in one-photon resonance or near resonance with the initial level. Predissociating levels embedded into continua are considered. When the first laser field is sufficiently intense and suitably chirped, the dissociation probability is enhanced by adiabatic rapid passage through the avoided crossing arising from the frequency swept radiative interaction. The whole population of the ground level can be effectively transferred to the intermediate levels by this technique facilitating the dissociation process by the second field. We also report the effect of frequency detuning and chirp width on the dissociation probability. Widths of the two peaks of the dissociation line shape increase with an increase in chirp width, resulting in the possibility of control in the dissociation yield. When the first field is a laser pulse of low intensity and constant frequency and the second laser frequency is chirped, predissociating levels take important parts in the dissociation dynamics and we obtain a signature of the nonadiabatic effect of the first step on the second step of photodissociation dynamics. This feature is due to the presence of the predissociating levels and the nonadiabatic mixing of two intermediate levels. All these results can be explained in terms of the adiabatic dressed levels
Control of chemical dynamics by lasers: theoretical considerations.
Kondorskiy, Alexey; Nanbu, Shinkoh; Teranishi, Yoshiaki; Nakamura, Hiroki
2010-06-03
Theoretical ideas are proposed for laser control of chemical dynamics. There are the following three elementary processes in chemical dynamics: (i) motion of the wave packet on a single adiabatic potential energy surface, (ii) excitation/de-excitation or pump/dump of wave packet, and (iii) nonadiabatic transitions at conical intersections of potential energy surfaces. A variety of chemical dynamics can be controlled, if we can control these three elementary processes as we desire. For (i) we have formulated the semiclassical guided optimal control theory, which can be applied to multidimensional real systems. The quadratic or periodic frequency chirping method can achieve process (ii) with high efficiency close to 100%. Concerning process (iii) mentioned above, the directed momentum method, in which a predetermined momentum vector is given to the initial wave packet, makes it possible to enhance the desired transitions at conical intersections. In addition to these three processes, the intriguing phenomenon of complete reflection in the nonadiabatic-tunneling-type of potential curve crossing can also be used to control a certain class of chemical dynamics. The basic ideas and theoretical formulations are provided for the above-mentioned processes. To demonstrate the effectiveness of these controlling methods, numerical examples are shown by taking the following processes: (a) vibrational photoisomerization of HCN, (b) selective and complete excitation of the fine structure levels of K and Cs atoms, (c) photoconversion of cyclohexadiene to hexatriene, and (d) photodissociation of OHCl to O + HCl.
Dynamics of Photoexcited State of Semiconductor Quantum Dots
Trivedi, Dhara J.
In this thesis, non-adiabatic molecular dynamics (NAMD) of excited states in semiconductor quantum dots are investigated. Nanoscale systems provide important opportunities for theory and computation for research because the experimental tools often provide an incomplete picture of the structure and/or function of nanomaterials, and theory can often fill in missing features crucial in understanding what is being measured. The simulation of NAMD is an indispensable tool for understanding complex ultrafast photoinduced processes such as charge and energy transfer, thermal relaxation, and charge recombination. Based on the state-of-the-art ab initio approaches in both the energy and time domains, the thesis presents a comprehensive discussion of the dynamical processes in quantum dots, ranging from the initial photon absorption to the final emission. We investigate the energy relaxation and transfer rates in pure and surface passivated quantum dots of different sizes. The study establishes the fundamental mechanisms of the electron and hole relaxation processes with and without hole traps. We develop and implement more accurate and efficient methods for NAMD. These methods are advantageous over the traditional ones when one encounters classically forbidden transitions. We also explore the effect of decoherence and non-adiabatic couplings on the dynamics. The results indicate significant influence on the accuracy and related computational cost of the simulated dynamics.
Benabbas, Abdelkrim; Salna, Bridget; Sage, J. Timothy; Champion, Paul M., E-mail: champ@neu.edu [Department of Physics and Center for Interdisciplinary Research on Complex Systems,Northeastern University, Boston, Massachusetts 02115 (United States)
2015-03-21
Analytical models describing the temperature dependence of the deep tunneling rate, useful for proton, hydrogen, or hydride transfer in proteins, are developed and compared. Electronically adiabatic and non-adiabatic expressions are presented where the donor-acceptor (D-A) motion is treated either as a quantized vibration or as a classical “gating” distribution. We stress the importance of fitting experimental data on an absolute scale in the electronically adiabatic limit, which normally applies to these reactions, and find that vibrationally enhanced deep tunneling takes place on sub-ns timescales at room temperature for typical H-bonding distances. As noted previously, a small room temperature kinetic isotope effect (KIE) does not eliminate deep tunneling as a major transport channel. The quantum approach focuses on the vibrational sub-space composed of the D-A and hydrogen atom motions, where hydrogen bonding and protein restoring forces quantize the D-A vibration. A Duschinsky rotation is mandated between the normal modes of the reactant and product states and the rotation angle depends on the tunneling particle mass. This tunnel-mass dependent rotation contributes substantially to the KIE and its temperature dependence. The effect of the Duschinsky rotation is solved exactly to find the rate in the electronically non-adiabatic limit and compared to the Born-Oppenheimer (B-O) approximation approach. The B-O approximation is employed to find the rate in the electronically adiabatic limit, where we explore both harmonic and quartic double-well potentials for the hydrogen atom bound states. Both the electronically adiabatic and non-adiabatic rates are found to diverge at high temperature unless the proton coupling includes the often neglected quadratic term in the D-A displacement from equilibrium. A new expression is presented for the electronically adiabatic tunnel rate in the classical limit for D-A motion that should be useful to experimentalists working
Diniz, Leonardo G.; Kirnosov, Nikita; Alijah, Alexander; Mohallem, José R.; Adamowicz, Ludwik
2016-04-01
A very accurate dipole moment curve (DMC) for the ground X1Σ+ electronic state of the 7LiH molecule is reported. It is calculated with the use of all-particle explicitly correlated Gaussian functions with shifted centers. The DMC - the most accurate to our knowledge - and the corresponding highly accurate potential energy curve are used to calculate the transition energies, the transition dipole moments, and the Einstein coefficients for the rovibrational transitions with ΔJ = - 1 and Δv ⩽ 5 . The importance of the non-adiabatic effects in determining these properties is evaluated using the model of a vibrational R-dependent effective reduced mass in the rovibrational calculations introduced earlier (Diniz et al., 2015). The results of the present calculations are used to assess the quality of the two complete linelists of 7LiH available in the literature.
Dobbyn, Abigail J.; Knowles, Peter J.
A number of established techniques for obtaining diabatic electronic states in small molecules are critically compared for the example of the X and B states in the water molecule, which contribute to the two lowest-energy conical intersections. Integration of the coupling matrix elements and analysis of configuration mixing coefficients both produce reliable diabatic states globally. Methods relying on diagonalization of dipole moment and angular momentum operators are shown to fail in large regions of coordinate space. However, the use of transition angular momentum matrix elements involving the A state, which is degenerate with B at the conical intersections, is successful globally, provided that an appropriate choice of coordinates is made. Long range damping of non-adiabatic coupling to give correct asymptotic mixing angles also is investigated.
Kittell, Aaron W.; Hyde, James S.
2015-01-01
Non-adiabatic rapid passage (NARS) electron paramagnetic resonance (EPR) spectroscopy was introduced by Kittell, A.W., Camenisch, T.G., Ratke, J.J. Sidabras, J.W., Hyde, J.S., 2011 as a general purpose technique to collect the pure absorption response. The technique has been used to improve sensitivity relative to sinusoidal magnetic field modulation, increase the range of inter-spin distances that can be measured under near physiological conditions, and enhance spectral resolution in copper (II) spectra. In the present work, the method is extended to CW microwave power saturation of spin-labeled T4 Lysozyme (T4L). As in the cited papers, rapid triangular sweep of the polarizing magnetic field was superimposed on slow sweep across the spectrum. Adiabatic rapid passage (ARP) effects were encountered in samples undergoing very slow rotational diffusion as the triangular magnetic field sweep rate was increased. The paper reports results of variation of experimental parameters at the interface of adiabatic and non-adiabatic rapid sweep conditions. Comparison of the forward (up) and reverse (down) triangular sweeps is shown to be a good indicator of the presence of rapid passage effects. Spectral turning points can be distinguished from spectral regions between turning points in two ways: differential microwave power saturation and differential passage effects. Oxygen accessibility data are shown under NARS conditions that appear similar to conventional field modulation data. However, the sensitivity is much higher, permitting, in principle, experiments at substantially lower protein concentrations. Spectral displays were obtained that appear sensitive to rotational diffusion in the range of rotational correlation times of 10−3 to 10−7 s in a manner that is analogous to saturation transfer spectroscopy. PMID:25917132
Søndergaard, Anders Aspegren; Shepperson, Benjamin; Stapelfeldt, Henrik
2017-07-07
We present an efficient, noise-robust method based on Fourier analysis for reconstructing the three-dimensional measure of the alignment degree, ⟨cos 2 θ⟩, directly from its two-dimensional counterpart, ⟨cos 2 θ 2D ⟩. The method applies to nonadiabatic alignment of linear molecules induced by a linearly polarized, nonresonant laser pulse. Our theoretical analysis shows that the Fourier transform of the time-dependent ⟨cos 2 θ 2D ⟩ trace over one molecular rotational period contains additional frequency components compared to the Fourier transform of ⟨cos 2 θ⟩. These additional frequency components can be identified and removed from the Fourier spectrum of ⟨cos 2 θ 2D ⟩. By rescaling of the remaining frequency components, the Fourier spectrum of ⟨cos 2 θ⟩ is obtained and, finally, ⟨cos 2 θ⟩ is reconstructed through inverse Fourier transformation. The method allows the reconstruction of the ⟨cos 2 θ⟩ trace from a measured ⟨cos 2 θ 2D ⟩ trace, which is the typical observable of many experiments, and thereby provides direct comparison to calculated ⟨cos 2 θ⟩ traces, which is the commonly used alignment metric in theoretical descriptions. We illustrate our method by applying it to the measurement of nonadiabatic alignment of I 2 molecules. In addition, we present an efficient algorithm for calculating the matrix elements of cos 2 θ 2D and any other observable in the symmetric top basis. These matrix elements are required in the rescaling step, and they allow for highly efficient numerical calculation of ⟨cos 2 θ 2D ⟩ and ⟨cos 2 θ⟩ in general.
Constructing quantum dynamics from mixed quantum-classical descriptions
Barsegov, V.; Rossky, P.J.
2004-01-01
The influence of quantum bath effects on the dynamics of a quantum two-level system linearly coupled to a harmonic bath is studied when the coupling is both diagonal and off-diagonal. It is shown that the pure dephasing kernel and the non-adiabatic quantum transition rate between Born-Oppenheimer states of the subsystem can be decomposed into a contribution from thermally excited bath modes plus a zero point energy contribution. This quantum rate can be modewise factorized exactly into a product of a mixed quantum subsystem-classical bath transition rate and a quantum correction factor. This factor determines dynamics of quantum bath correlations. Quantum bath corrections to both the transition rate and the pure dephasing kernel are shown to be readily evaluated via a mixed quantum-classical simulation. Hence, quantum dynamics can be recovered from a mixed quantum-classical counterpart by incorporating the missing quantum bath corrections. Within a mixed quantum-classical framework, a simple approach for evaluating quantum bath corrections in calculation of the non-adiabatic transition rate is presented
Photocarrier dynamics in monolayer phosphorene and bulk black phosphorus.
Zereshki, Peymon; Wei, Yaqing; Ceballos, Frank; Bellus, Matthew Z; Lane, Samuel D; Pan, Shudi; Long, Run; Zhao, Hui
2018-06-13
We report a combined theoretical and experimental study on photocarrier dynamics in monolayer phosphorene and bulk black phosphorus. Samples of monolayer phosphorene and bulk black phosphorus were fabricated by mechanical exfoliation, identified according to their reflective contrasts, and protected by covering them with hexagonal boron nitride layers. Photocarrier dynamics in these samples was studied by an ultrafast pump-probe technique. The photocarrier lifetime of monolayer phosphorene was found to be about 700 ps, which is about 9 times longer than that of bulk black phosphorus. This trend was reproduced in our calculations based on ab initio nonadiabatic molecular dynamics combined with time-domain density functional theory in the Kohn-Sham representation, and can be attributed to the smaller bandgap and stronger nonadiabatic coupling in bulk. The transient absorption response was also found to be dependent on the sample orientation with respect to the pump polarization, which is consistent with the previously reported anisotropic absorption of phosphorene. In addition, an oscillating component of the differential reflection signal at early probe delays was observed in the bulk sample and was attributed to the layer-breathing phonon mode with an energy of about 1 meV and a decay time of about 1.35 ps. These results provide valuable information for application of monolayer phosphorene in optoelectronics.
Direct View of Hot Carrier Dynamics in Graphene
Johannsen, Jens Christian; Ulstrup, Søren; Cilento, Federico
2013-01-01
The ultrafast dynamics of excited carriers in graphene is closely linked to the Dirac spectrum and plays a central role for many electronic and optoelectronic applications. Harvesting energy from excited electron-hole pairs, for instance, is only possible if these pairs can be separated before th...
INTRODUCING CAFein, A NEW COMPUTATIONAL TOOL FOR STELLAR PULSATIONS AND DYNAMIC TIDES
Valsecchi, F.; Farr, W. M.; Willems, B.; Rasio, F. A.; Kalogera, V.
2013-01-01
Here we present CAFein, a new computational tool for investigating radiative dissipation of dynamic tides in close binaries and of non-adiabatic, non-radial stellar oscillations in isolated stars in the linear regime. For the latter, CAFein computes the non-adiabatic eigenfrequencies and eigenfunctions of detailed stellar models. The code is based on the so-called Riccati method, a numerical algorithm that has been successfully applied to a variety of stellar pulsators, and which does not suffer from the major drawbacks of commonly used shooting and relaxation schemes. Here we present an extension of the Riccati method to investigate dynamic tides in close binaries. We demonstrate CAFein's capabilities as a stellar pulsation code both in the adiabatic and non-adiabatic regimes, by reproducing previously published eigenfrequencies of a polytrope, and by successfully identifying the unstable modes of a stellar model in the β Cephei/SPB region of the Hertzsprung-Russell diagram. Finally, we verify CAFein's behavior in the dynamic tides regime by investigating the effects of dynamic tides on the eigenfunctions and orbital and spin evolution of massive main sequence stars in eccentric binaries, and of hot Jupiter host stars. The plethora of asteroseismic data provided by NASA's Kepler satellite, some of which include the direct detection of tidally excited stellar oscillations, make CAFein quite timely. Furthermore, the increasing number of observed short-period detached double white dwarfs (WDs) and the observed orbital decay in the tightest of such binaries open up a new possibility of investigating WD interiors through the effects of tides on their orbital evolution
State-to-state photodissociation dynamics of triatomic molecules: H2O in the B band
Jiang Bin; Xie Daiqian; Guo Hua
2012-01-01
State-to-state photodissociation dynamics of H 2 O in its B band has been investigated quantum mechanically on a new set of non-adiabatically coupled potential energy surfaces for the lowest two 1 A' states of H 2 O, which are developed at the internally contracted multi-reference configuration interaction level with the aug-cc-pVQZ basis set. Quantum dynamical calculations carried out using the Chebyshev propagator yield absorption spectra, product state distributions, branching ratios, and differential cross sections, which are in reasonably good agreement with the latest experimental results. Particular focus is placed here on the dependence of various dynamical observables on the photon energy. Detailed analyses of the dynamics have assigned the diffuse structure in absorption spectrum to short-time recurring dynamics near the HOH conical intersection. The non-adiabatic dissociation to the ground state OH product via the HOH conical intersection is facile, direct, fast, and produces rotationally hot OH(X-tilde) products. On the other hand, the adiabatic channel on the excited state leading to the OH(A-tilde) product is dominated by long-lived resonances, which depend sensitively on the potential energy surfaces.
Thompson, K.; Martinez, T.J.
1999-01-01
We present a new approach to first-principles molecular dynamics that combines a general and flexible interpolation method with ab initio evaluation of the potential energy surface. This hybrid approach extends significantly the domain of applicability of ab initio molecular dynamics. Use of interpolation significantly reduces the computational effort associated with the dynamics over most of the time scale of interest, while regions where potential energy surfaces are difficult to interpolate, for example near conical intersections, are treated by direct solution of the electronic Schroedinger equation during the dynamics. We demonstrate the concept through application to the nonadiabatic dynamics of collisional electronic quenching of Li(2p). Full configuration interaction is used to describe the wave functions of the ground and excited electronic states. The hybrid approach agrees well with full ab initio multiple spawning dynamics, while being more than an order of magnitude faster. copyright 1999 American Institute of Physics
Fechner, Peer Cornelis
2015-01-01
The central topic of this thesis is the experimental observation and the theoretical modeling of non-adiabatic three-body dissociation of H_3 and D_3 neutral triatomic hydrogen molecules. Our goal is to lend a meaning to the observed momentum vector correlation (MVC) of the three emerging ground state hydrogen atoms, for example H_3→H(1s)+H(1s)+H(1s), in terms of symmetries of the nuclear molecular wave function and of the non-adiabatic coupling which initiates this decay. In many experiments carried out over the years, a wealth of state specific MVCs was collected by different research groups. The MVCs are imaged in form of so-called Dalitz plots which show a rich structure of maxima and nodal lines, depending on the initial state of the triatomic hydrogen neutral. Theory was slow to catch up with experiment and only by this year, 2015, a general agreement was accomplished. Nevertheless, these models lack of an easy understanding of the underlying physics as many numerical calculations are involved. The theoretical model presented in this thesis follows a different approach which is more guided by the imaging character of our experiments. We concentrate on a rather qualitative treatment by limiting ourselves to the essential ingredients only. This proceeding contributes to giving a physical interpretation of the structures in the Dalitz plots in the following form: Three-particle coincident imaging offers a direct view of the emerging spatial continuum wave function of a predissociating triatomic molecule as it evolves from molecular spatial dimensions into the realm of independent free particles. This latter result is discussed in the context of the so-called Imaging Theorem, the second main part of this work. A third major part of this thesis pertains to obtaining molecular momentum wave functions in separated degrees-of-freedom via Fourier transformation. Even for triatomic hydrogen - the most simple polyatomic molecule - this is a challenging task. The
Interaction dynamics of electrostatic solitary waves
V. L. Krasovsky
1999-01-01
Full Text Available Interaction of nonlinear electrostatic pulses associated with electron phase density holes moving in a collisionless plasma is studied. An elementary event of the interaction is analyzed on the basis of the energy balance in the system consisting of two electrostatic solitary waves. It is established that an intrinsic property of the system is a specific irreversibility caused by a nonadiabatic modification of the internal structure of the holes and their effective heating in the process of the interaction. This dynamical irreversibility is closely connected with phase mixing of the trapped electrons comprising the holes and oscillating in the varying self-consistent potential wells. As a consequence of the irreversibility, the "collisions" of the solitary waves should be treated as "inelastic" ones. This explains the general tendency to the merging of the phase density holes frequently observed in numerical simulation and to corresponding coupling of the solitary waves.
Ion motion in the current sheet with sheared magnetic field – Part 2: Non-adiabatic effects
A. V. Artemyev
2013-10-01
Full Text Available We investigate dynamics of charged particles in current sheets with the sheared magnetic field. In our previouspaper (Artemyev et al., 2013 we studied the particle motion in such magnetic field configurations on the basis of the quasi-adiabatic theory and conservation of the quasi-adiabatic invariant. In this paper we concentrate on violation of the adiabaticity due to jumps of this invariant and the corresponding effects of stochastization of a particle motion. We compare effects of geometrical and dynamical jumps, which occur due to the presence of the separatrix in the phase plane of charged particle motion. We show that due to the presence of the magnetic field shear, the average value of dynamical jumps is not equal to zero. This effect results in the decrease of the time interval necessary for stochastization of trapped particle motion. We investigate also the effect of the magnetic field shear on transient trajectories, which cross the current sheet boundaries. Presence of the magnetic field shear leads to the asymmetry of reflection and transition of particles in the current sheet. We discuss the possible influence of single-particle effects revealed in this paper on the current sheet structure and dynamics.
Classical and macroquantum dynamics of charged particles in a magnetic field
Varma, R.K.
2003-01-01
The investigations relating to the dynamics of charged particles in a magnetic field carried out over more than 40 years have been reviewed with special reference to the problem of nonadiabaticity due to field inhomogeneity, and time dependence. A detailed overview is presented of the standard approaches to one of the main problems namely the determination of the residence times of charged particles in an adiabatic magnetic trap which involves nonadiabaticity in a crucial way. In a major departure from the standard approach, a new paradigm described here as 'macroquantum dynamics' was advanced by the author to address the problem of residence times. The evolution and development of this new paradigm is next presented as the main focus of the review. This consists of a probability amplitude Schroedinger-like formalism for the classical macrodomain, which has been shown to be a description of the system in the correspondence limit of large Landau quantum numbers. It is demonstrated that this represents a remarkable persistence of matter wave behaviour well into the classical macrodomain, leading to unexpected experimental consequences. Experimental results confirming some of the spectacular predictions of this formalism are presented. These refer to the existence of macroscopic matter wave interference phenomena and the observation of the curl-free vector potential a la Aharonov-Bohm in the macrodomain. The problem of the nonadiabatic leakage of particles from an adiabatic trap takes the appearance here of the quantum-like tunneling of the adiabatic potential. The multiplicity of residence times predicted by the set of Schroedinger-like equations have been well confirmed by experiments. A critical comparison is finally presented of the classical vs. macroquantum description of the system in the macrodomain. The new paradigm thus represents an entirely new and unexpected manifestation of quantum dynamics in the classical macrodomain
Kittell, Aaron W.; Camenisch, Theodore G.; Ratke, Joseph J.; Sidabras, Jason W.; Hyde, James S.
2011-01-01
A continuous wave (CW) electron paramagnetic resonance (EPR) spectrum is typically displayed as the first harmonic response to the application of 100 kHz magnetic field modulation, which is used to enhance sensitivity by reducing the level of 1/f noise. However, magnetic field modulation of any amplitude causes spectral broadening and sacrifices EPR spectral intensity by at least a factor of two. In the work presented here, a CW rapid-scan spectroscopic technique that avoids these compromises and also provides a means of avoiding 1/f noise is developed. This technique, termed non-adiabatic rapid sweep (NARS) EPR, consists of repetitively sweeping the polarizing magnetic field in a linear manner over a spectral fragment with a small coil at a repetition rate that is sufficiently high that receiver noise, microwave phase noise, and environmental microphonics, each of which has 1/f characteristics, are overcome. Nevertheless, the rate of sweep is sufficiently slow that adiabatic responses are avoided and the spin system is always close to thermal equilibrium. The repetitively acquired spectra from the spectral fragment are averaged. Under these conditions, undistorted pure absorption spectra are obtained without broadening or loss of signal intensity. A digital filter such as a moving average is applied to remove high frequency noise, which is approximately equivalent in bandwidth to use of an integrating time constant in conventional field modulation with lock-in detection. Nitroxide spectra at L- and X-band are presented. PMID:21741868
Falge, Mirjam
2012-07-01
This work aimed at the theoretical analysis of high harmonic generation in molecules and the influence of coupled electron and nuclear dynamics on ultra-short pulse ionization processes. In the first part of this thesis, the isotope effect and influence of vibrational excitation on high harmonic generation were investigated for the isotope pairs H{sub 2}O/D{sub 2}O and H{sub 2}/D{sub 2}. It was shown that on the one hand high harmonic intensities strongly depend on the vibrational quantum number of the initial state of the water molecule and on the other hand the spectra of H{sub 2}O and D{sub 2}O exhibit a clear isotope effect for certain vibrationally excited states. Also it was shown that high harmonics of vibrationally excited states show an even more pronounced isotope effect than the ground state. The second and third part of this work treats the influence of coupled electron and nuclear dynamics on photoelectron spectra. In order to facilitate a numerically exact description of this dynamics, a simple one-dimensional model system (Shin-Metiu model) was used. It consists of only a single electronic and nuclear degree-of-freedom and allows for a switching between adiabatic and strongly non-adiabatic dynamics by its parameterization. This model served for the analysis of the dynamics of three different cases ranging from weak over intermediate to strong electron-nuclear coupling. To investigate the influence of non-adiabatic effects on photoelectron spectra, time-resolved photoelectron spectra were calculated applying two methods: a numerically exact treatment and an adiabatic approach neglecting the electron-nuclear coupling. Subsequently, the dependence of the efficiency of a non-adiabatic transition on the nuclear mass was analysed. To this end, the population dynamics and photoelectron spectra were calculated numerically exactly for a strong electron and nuclear coupling. Thereafter the asymmetry in forward and backward direction of time
Compressibility Effects in the Dynamics of the Reversed-Field Pinch
Onofri, M.; Malara, F.; Veltri, P.
2008-01-01
We study the reversed-field pinch through the numerical solution of the compressible magnetohydrodynamic equations. Two cases are investigated: In the first case the pressure is derived from an adiabatic condition, and in the second case the pressure equation includes heating terms due to resistivity and viscosity. In the adiabatic case a single helicity state is observed, and the reversed-field pinch configuration is formed for short time intervals and is finally lost. In the nonadiabatic case the system reaches a multiple helicity state, and the reversal parameter remains negative for a longer time. The results show the importance of compressibility in determining the large scale dynamics of the system
Field- and current-driven domain wall dynamics: An experimental picture
Beach, G.S.D.; Knutson, C.; Tsoi, M.; Erskine, J.L.
2007-01-01
Field- and current-driven domain wall velocities are measured and discussed in terms of existing spin-torque models. A reversal in the roles of adiabatic and non-adiabatic spin-torque is shown to arise in those models below and above Walker breakdown. The measured dependence of velocity on current is the same in both regimes, indicating both spin-torque components have similar magnitude. However, the models on which these conclusions are based have serious quantitative shortcomings in describing the observed field-driven wall dynamics, for which they were originally developed. Hence, the applicability of simple one-dimensional models to most experimental conditions may be limited
Janeček, Ivan; Janča, T.; Naar, P.; Kalus, R.; Gadéa, F. X.
2013-01-01
Roč. 138, č. 4 (2013), s. 1-12 ISSN 0021-9606 R&D Projects: GA MŠk ED2.1.00/03.0082 Institutional support: RVO:68145535 Keywords : atomic clusters * electromagnetic decays * electron impact dissociation * electron impact ionisation * isomerism * krypton * nonradiative transitions * xenon Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.122, year: 2013 http://jcp.aip.org/resource/1/jcpsa6/v138/i4/p044303_s1?isAuthorized=no
Boudjada, Nazim; Segal, Dvira
2014-11-26
We study in a unified manner the dissipative dynamics and the transfer of heat in the two-bath spin-boson model. We use the Bloch-Redfield (BR) formalism, valid in the very weak system-bath coupling limit, the noninteracting-blip approximation (NIBA), applicable in the nonadiabatic limit, and iterative, numerically exact path integral tools. These methodologies were originally developed for the description of the dissipative dynamics of a quantum system, and here they are applied to explore the problem of quantum energy transport in a nonequilibrium setting. Specifically, we study the weak-to-intermediate system-bath coupling regime at high temperatures kBT/ħ > ε, with ε as the characteristic frequency of the two-state system. The BR formalism and NIBA can lead to close results for the dynamics of the reduced density matrix (RDM) in a certain range of parameters. However, relatively small deviations in the RDM dynamics propagate into significant qualitative discrepancies in the transport behavior. Similarly, beyond the strict nonadiabatic limit NIBA's prediction for the heat current is qualitatively incorrect: It fails to capture the turnover behavior of the current with tunneling energy and temperature. Thus, techniques that proved meaningful for describing the RDM dynamics, to some extent even beyond their rigorous range of validity, should be used with great caution in heat transfer calculations, because qualitative-serious failures develop once parameters are mildly stretched beyond the techniques' working assumptions.
Falge, Mirjam; Fröbel, Friedrich Georg; Engel, Volker; Gräfe, Stefanie
2017-08-02
If the adiabatic approximation is valid, electrons smoothly adapt to molecular geometry changes. In contrast, as a characteristic of diabatic dynamics, the electron density does not follow the nuclear motion. Recently, we have shown that the asymmetry in time-resolved photoelectron spectra serves as a tool to distinguish between these dynamics [Falge et al., J. Phys. Chem. Lett., 2012, 3, 2617]. Here, we investigate the influence of an additional, moderately intense infrared (IR) laser field, as often applied in attosecond time-resolved experiments, on such asymmetries. This is done using a simple model for coupled electronic-nuclear motion. We calculate time-resolved photoelectron spectra and their asymmetries and demonstrate that the spectra directly map the bound electron-nuclear dynamics. From the asymmetries, we can trace the IR field-induced population transfer and both the field-driven and intrinsic (non-)adiabatic dynamics. This holds true when considering superposition states accompanied by electronic coherences. The latter are observable in the asymmetries for sufficiently short XUV pulses to coherently probe the coupled states. It is thus documented that the asymmetry is a measure for phases in bound electron wave packets and non-adiabatic dynamics.
Quantum–classical correspondence in chaotic dynamics of laser-driven atoms
Prants, S V
2017-01-01
This paper is a review article on some aspects of quantum–classical correspondence in chaotic dynamics of cold atoms interacting with a standing-wave laser field forming an optical lattice. The problem is treated from both (semi)classical and quantum points of view. In both approaches, the interaction of an atomic electic dipole with the laser field is treated quantum mechanically. Translational motion is described, at first, classically (atoms are considered to be point-like objects) and then quantum mechanically as a propagation of matter waves. Semiclassical equations of motion are shown to be chaotic in the sense of classical dynamical chaos. Point-like atoms in an absolutely deterministic and rigid optical lattice can move in a random-like manner demonstrating a chaotic walking with typical features of classical chaos. This behavior is explained by random-like ‘jumps’ of one of the atomic internal variable when atoms cross nodes of the standing wave and occurs in a specific range of the atom-field detuning. When treating atoms as matter waves, we show that they can make nonadiabatic transitions when crossing the standing-wave nodes. The point is that atomic wave packets split at each node in the same range of the atom-field detuning where the classical chaos occurs. The key point is that the squared amplitude of those semiclassical ‘jumps’ equal to the quantum Landau–Zener parameter which defines the probability of nonadiabatic transitions at the nodes. Nonadiabatic atomic wave packets are much more complicated compared to adiabatic ones and may be called chaotic in this sense. A few possible experiments to observe some manifestations of classical and quantum chaos with cold atoms in horizontal and vertical optical lattices are proposed and discussed. (paper)
Lacroix D.
2010-03-01
Full Text Available Among the different theoretical approaches able to describe fission, microscopic ones can help us in the understanding of this process, as they have the advantage of describing the nuclear structure and the dynamics in a consistent manner. The sole input of the calculations is the nucleon-nucleon interaction. Such a microscopic time-dependent and quantum mechanical formalism has already been used, based on the Gaussian Overlap Approximation of the Generator Coordinate Method with the adiabatic approximation, to analyze the collective dynamics of low-energy fission in 238U [1]. However, at higher energies, a few MeV above the barrier, the adiabatic approximation doesn’t seem valid anymore. Indeed, manifestations of proton pair breaking have been observed in 238U and 239U for an excitation energy of 2.3 MeV above the barrier [2–4]. Taking the intrinsic excitations into account during the fission process will enable us to determine the coupling between collective and intrinsic degrees of freedom, in particular from saddle to scission. Guidelines of the new formalism under development are presented and some preliminary results on overlaps between non excited and excited states are discussed.
Bernard, R.; Goutte, H.; Gogny, D.; Dubray, N.; Lacroix, D.
2009-01-01
Among the different theoretical approaches able to describe fission, microscopic ones can help us in the understanding of this process, as they have the advantage of describing the nuclear structure and the dynamics in a consistent manner. The sole input of the calculations is the nucleon-nucleon interaction. Such a microscopic time-dependent and quantum mechanical formalism has already been used, based on the Gaussian Overlap Approximation of the Generator Coordinate Method with the adiabatic approximation, to analyze the collective dynamics of low-energy fission in 238 U. However, at higher energies, a few MeV above the barrier, the adiabatic approximation doesn't seem valid anymore. Indeed, manifestations of proton pair breaking have been observed in 238 U and 239 U for an excitation energy of 2.3 MeV above the barrier. Taking the intrinsic excitations into account during the fission process will enable us to determine the coupling between collective and intrinsic degrees of freedom, in particular from saddle to scission. Guidelines of the new formalism under development are presented and some preliminary results on overlaps between non excited and excited states are discussed.
Tully, John C. [Yale Univ., New Haven, CT (United States)
2017-06-10
Chemical reactions are often facilitated and steered when carried out on solid surfaces, essential for applications such as heterogeneous catalysis, solar energy conversion, corrosion, materials processing, and many others. A critical factor that can determine the rates and pathways of chemical reactions at surfaces is the efficiency and specificity of energy transfer; how fast does energy move around and where does it go? For reactions on insulator surfaces energy transfer generally moves in and out of vibrations of the adsorbed molecule and the underlying substrate. By contrast, on metal surfaces, metallic nanoparticles and semiconductors, another pathway for energy flow opens up, excitation and de-excitation of electrons. This so-called “nonadiabatic” mechanism often dominates the transfer of energy and can directly impact the course of a chemical reaction. Conventional computational methods such as molecular dynamics simulation do not account for this nonadiabatic behavior. The current DOE-BES funded project has focused on developing the underlying theoretical foundation and the computational methodology for the prediction of nonadiabatic chemical reaction dynamics at surfaces. The research has successfully opened up new methodology and new applications for molecular simulation. In particular, over the last three years, the “Electronic Friction” theory, pioneered by the PI, has now been developed into a stable and accurate computational method that is sufficiently practical to allow first principles “on-the-fly” simulation of chemical reaction dynamics at metal surfaces.
Kittell, Aaron W.; Hustedt, Eric J.; Hyde, James S.
2014-01-01
Site-directed spin-labeling electron paramagnetic resonance (SDSL EPR) provides insight into the local structure and motion of a spin probe strategically attached to a molecule. When a second spin is introduced to the system, macromolecular information can be obtained through measurement of inter-spin distances either by continuous wave (CW) or pulsed electron double resonance (ELDOR) techniques. If both methodologies are considered, inter-spin distances of 8 to 80 Å can be experimentally determined. However, there exists a region at the upper limit of the conventional X-band (9.5 GHz) CW technique and the lower limit of the four-pulse double electron-electron resonance (DEER) experiment where neither method is particularly reliable. The work presented here utilizes L-band (1.9 GHz) in combination with non-adiabatic rapid sweep (NARS) EPR to address this opportunity by increasing the upper limit of the CW technique. Because L-band linewidths are three to seven times narrower than those at X-band, dipolar broadenings that are small relative to the X-band inhomogeneous linewidth become observable, but the signal loss due to the frequency dependence of the Boltzmann factor, has made L-band especially challenging. NARS has been shown to increase sensitivity by a factor of five, and overcomes much of this loss, making L-band distance determination more feasible [1]. Two different systems are presented and distances of 18–30 Å have been experimentally determined at physiologically relevant temperatures. Measurements are in excellent agreement with a helical model and values determined by DEER. PMID:22750251
Dynamics of electron wave packet in a disordered chain with delayed nonlinear response
Zhu Hongjun; Xiong Shijie
2010-01-01
We investigate the dynamics of one electron wave packet in a linear chain with random on-site energies and a nonadiabatic electron-phonon interaction which is described by a delayed cubic nonlinear term in the time-dependent Schroedinger equation. We show that in the regime where the wave packet is delocalized in the case with only the delayed nonlinearity, the wave packet becomes localized when the disorder is added and the localization is enhanced by increasing the disorder. In the regime where the self-trapping phenomenon occurs in the case with only the delayed nonlinearity, by adding the disorder the general dynamical features of the wave packet do not change if the nonlinearity parameter is small, but the dynamics shows the subdiffusive behavior if the nonlinearity parameter is large. The numerical results demonstrate complicated wave packet dynamics of systems with both the disorder and nonlinearity.
Greentree, Andrew D.; Smith, T.B.; Echaniz, S.R. de; Durrant, A. V.; Marangos, J.P.; Segal, D.M.; Vaccaro, J.A.
2002-01-01
This paper presents a wide-ranging theoretical and experimental study of nonadiabatic transient phenomena in a Λ electromagnetically induced transparency system when a strong coupling field is rapidly switched on or off. The theoretical treatment uses a Laplace transform approach to solve the time-dependent density matrix equation. The experiments are carried out in a 87 Rb magneto-optical trap. The results show transient probe gain in parameter regions not previously studied, and provide insight into the transition dynamics between bare and dressed states
Charge and energy dynamics in photo-excited poly(para-phenylenevinylene) systems
Gisslen, L.; Johansson, A.; Stafstroem, S.
2004-01-01
We report results from simulations of charge and energy dynamics in poly(para-phenylenevinylene) (PPV) and PPV interacting with C 60 . The simulations were performed by solving the time-dependent Schroedinger equation and the lattice equation of motion simultaneously and nonadiabatically. The electronic system and the coupling of the electrons to the lattice were described by an extended three-dimensional version of the Su-Schrieffer-Heeger model, which also included an external electric field. Electron and lattice dynamics following electronic excitations at different energies have been simulated. The effect of additional lattice energy was also included in the simulations. Our results show that both exciton diffusion and transitions from high to lower lying excitations are stimulated by increasing the lattice energy. Also field induced charge separation occurs faster if the lattice energy is increased. This separation process is highly nonadiabatic and involves a significant rearrangement of the electron distribution. In the case of PPV coupled to C 60 , we observe a spontaneous charge separation. The separation time is in this case limited by the local concentration of C 60 molecules close to the PPV chain
Thermal dynamics of bomb calorimeters.
Lyon, Richard E
2015-12-01
The thermal dynamics of bomb calorimeters are modeled using a lumped heat transfer analysis in which heat is released in a pressure vessel/bomb immersed in a stirred water bath that is surrounded by a static air space bounded by an insulated (static) jacket, a constant/controlled temperature jacket (isoperibol), or a changing temperature (adiabatic) jacket. The temperature history of the water bath for each of these boundary conditions (methods) is well described by the two-term solution for the calorimeter response to a heat impulse (combustion), allowing the heat transfer coefficients and thermal capacities of the bomb and water bath to be determined parametrically. The validated heat transfer model provides an expression for direct calculation of the heat released in an arbitrary process inside a bomb calorimeter using the temperature history of the water bath for each of the boundary conditions (methods). This result makes possible the direct calculation of the heat of combustion of a sample in an isoperibol calorimeter from the recorded temperature history without the need for semi-empirical temperature corrections to account for non-adiabatic behavior. Another useful result is that the maximum temperature rise of the water bath in the static jacket method is proportional to the total heat generated, and the empirical proportionality constant, which is determined by calibration, accounts for all of the heat losses and thermal lags of the calorimeter.
Gorney, D.J.
1982-01-01
Analysis of the USAF S3-3 charged particle data and electric field observations has provided extensive quantitative understanding of the auroral particle acceleration process. The results of an effort to use energetic charged particle observations to probe the altitude profile of auroral electric potential structures by applying adiabatic mapping theory are presented here. In situ energetic charged particle measurements differ from local electric field observations in that charged particles execute dynamic trajectories along the magnetic field lines and retain information on the spatial electric potential distribution in their velocity space distribution function. Although a unique determination of the potential distribution is not possible, basic differences between local or non-local acceleration are readily apparent in the particle observations. Together, the charged particle and electric field measurements have enabled us to form a reasonable picture of the auroral ''inverted-V'' structure which can then be applied to study the nonadiabatic processes that occur in these strong acceleration regions, such as energy scattering of ion and electron beams. Specifically, this study shows that a large scale auroral electric field exists at all times in the evening sector with an altitude distribution that is fairly unstructured at altitudes near and above one earth radius. Significant parallel potential drop is not observed below about 4000 kilometers altitude. At times, however, a substantial portion of the potential drop appears to lie in the low altitude region (4000-10,000 km)
Photochemical Dynamics of Intramolecular Singlet Fission
Lin, Zhou; Iwasaki, Hikari; Van Voorhis, Troy
2017-06-01
Singlet fission (SF) converts a singlet exciton (S_1) into a pair of triplet ones (T_1) via a ``multi-exciton'' (ME) intermediate: S_1 \\longleftrightarrow ^1ME \\longleftrightarrow ^1(T_1T_1) \\longrightarrow 2T_1. In exothermic cases, e.g., crystalline pentacene or its derivatives, the quantum yield of SF can reach 200%. With SF doubling the electric current generated by an incident high-energy photon, the solar conversion efficiency in pentacene-based organic photovoltaics (OPVs) can exceed the Shockley-Queisser limit of 33.7%. The ME state is popularly considered to be a dimeric state with significant charge transfer (CT) character that is strongly coupled to both S_1 and ^1(T_1T_1), while this local model lacks strong support from full quantum dynamics studies. Intramolecular SF (ISF) occurring to covalently-bound dimers in the solution phase is an excellent model for a straightforward dynamics simulation of local excitons. In the present study, we investigate the ISF mechanisms for three covalently-bound dimers of pentacene derivatives, including ortho-, meta-, and para-bis(6,13-bis(triisopropylsilylethynyl)pentacene)benzene, in non-protic solvents. Specifically, we propagate the real-time, non-adiabatic quantum mechanical/molecular mechanical (QM/MM) dynamics on the potential energy surfaces associated with the states of S_1, ^1(T_1T_1) and CT. We explore how the energies of these ISF-relevant states and the non-adiabatic couplings between each other fluctuate with time and the instantaneous molecular configuration (e.g., intermonomer distance and orientation). We also quantitatively compare Condon and non-Condon ISF dynamics with solution-phase spectroscopic data. Our results allow us to understand the roles of CT energy levels in the ISF mechanism and propose a design strategy to maximize ISF efficiency. M. B. Smith and J. Michl, Chem. Rev. 110, 6891 (2010). W. Shockley and H. J. Queisser, J. Appl. Phys. 32, 510 (1961). T. C. Berkelbach, M. S. Hybertsen
Quantum dynamics in open quantum-classical systems.
Kapral, Raymond
2015-02-25
Often quantum systems are not isolated and interactions with their environments must be taken into account. In such open quantum systems these environmental interactions can lead to decoherence and dissipation, which have a marked influence on the properties of the quantum system. In many instances the environment is well-approximated by classical mechanics, so that one is led to consider the dynamics of open quantum-classical systems. Since a full quantum dynamical description of large many-body systems is not currently feasible, mixed quantum-classical methods can provide accurate and computationally tractable ways to follow the dynamics of both the system and its environment. This review focuses on quantum-classical Liouville dynamics, one of several quantum-classical descriptions, and discusses the problems that arise when one attempts to combine quantum and classical mechanics, coherence and decoherence in quantum-classical systems, nonadiabatic dynamics, surface-hopping and mean-field theories and their relation to quantum-classical Liouville dynamics, as well as methods for simulating the dynamics.
Variational coupling between q-number and c-number dynamics
Amaral, C.M. do; Joffily, S.
1984-01-01
The time-dependent quantum variational principle is generalized for the case of hamiltonian operators having real parameters and their time derivates. The obtained variational system is formed by a Schroedinger equation coupled to a Lagrange equation system, where the lagrangian is the average value of the parametrized hamiltonian operator. The consequent dynamics of the variational principle, describes the interaction between a q-number sub-dynamics with a c-number sub-dynamics. In the ((h/2π)) 0 -order W.K.B. approximation, the variational system reduces to a Hamilton-Jacobi-like equation, coupled to a Lagrange equation family. The formal features of the obtained variational system are appropriated for the description of, adiabatics and non-adiabatics, time-dependent q-number c-number interactions. (L.C.) [pt
Yudin, V I; Taichenachev, A V; Basalaev, M Yu; Kovalenko, D V
2017-02-06
We theoretically investigate the dynamic regime of coherent population trapping (CPT) in the presence of frequency modulation (FM). We have formulated the criteria for quasi-stationary (adiabatic) and dynamic (non-adiabatic) responses of atomic system driven by this FM. Using the density matrix formalism for Λ system, the error signal is exactly calculated and optimized. It is shown that the optimal FM parameters correspond to the dynamic regime of atomic-field interaction, which significantly differs from conventional description of CPT resonances in the frame of quasi-stationary approach (under small modulation frequency). Obtained theoretical results are in good qualitative agreement with different experiments. Also we have found CPT-analogue of Pound-Driver-Hall regime of frequency stabilization.
Reconciling semiclassical and Bohmian mechanics. V. Wavepacket dynamics
Poirier, Bill
2008-01-01
In previous articles [B. Poirier J. Chem. Phys. 121, 4501 (2004); C. Trahan and B. Poirier, ibid. 124, 034115 (2006); 124, 034116 (2006); B. Poirier and G. Parlant, J. Phys. Chem. A 111, 10400 (2007)] a bipolar counterpropagating wave decomposition, ψ=ψ + +ψ - , was presented for stationary states ψ of the one-dimensional Schroedinger equation, such that the components ψ ± approach their semiclassical Wentzel-Kramers-Brillouin analogs in the large action limit. The corresponding bipolar quantum trajectories are classical-like and well behaved, even when ψ has many nodes, or is wildly oscillatory. In this paper, the method is generalized for time-dependent wavepacket dynamics applications and applied to several benchmark problems, including multisurface systems with nonadiabatic coupling
Deterministic constant-temperature dynamics for dissipative quantum systems
Sergi, Alessandro
2007-01-01
A novel method is introduced in order to treat the dissipative dynamics of quantum systems interacting with a bath of classical degrees of freedom. The method is based upon an extension of the Nose-Hoover chain (constant temperature) dynamics to quantum-classical systems. Both adiabatic and nonadiabatic numerical calculations on the relaxation dynamics of the spin-boson model show that the quantum-classical Nose-Hoover chain dynamics represents the thermal noise of the bath in an accurate and simple way. Numerical comparisons, both with the constant-energy calculation and with the quantum-classical Brownian motion treatment of the bath, show that the quantum-classical Nose-Hoover chain dynamics can be used to introduce dissipation in the evolution of a quantum subsystem even with just one degree of freedom for the bath. The algorithm can be computationally advantageous in modelling, within computer simulation, the dynamics of a quantum subsystem interacting with complex molecular environments. (fast track communication)
Inelastic light scattering and the excited states of many-electron quantum dots
Delgado, Alain [Centro de Aplicaciones Tecnologicas y Desarrollo Nuclear, Calle 30 No 502, Miramar, Havana (Cuba); Gonzalez, Augusto [Instituto de Cibernetica, Matematica y Fisica, Calle E 309, Vedado, Havana (Cuba)
2003-06-25
A consistent calculation of resonant inelastic (Raman) scattering amplitudes for relatively large quantum dots, which takes account of valence band mixing, the discrete character of the spectrum in intermediate and final states, and interference effects, is presented. Raman peaks in charge and spin channels are compared with multipole strengths and with the density of energy levels in final states. A qualitative comparison with the available experimental results is given.
Incomplete basis-set problem. V. Application of CIBS to many-electron systems
McDowell, K.; Lewis, L.
1982-01-01
Five versions of CIBS (corrections to an incomplete basis set) theory are used to compute first and second corrections to Roothaan--Hartree--Fock energies via expansion of a given basis set. Version one is an order by order perturbation approximation which neglects virtual orbitals; version two is a full CIBS expansion which neglects virtual orbitals; version three is an order by order perturbation approximation which includes virtual orbitals; version four is a full CIBS expansion which includes orthogonalization to virtual orbitals but neglects virtual orbital coupling terms; and version five is a full CIBS expansion with inclusion of coupling to virtual orbitals. Results are presented for the atomic and molecular systems He, Be, H 2 , LiH, Li 2 , and H 2 O. Version five is shown to produce a corrected Hartree--Fock energy which is essentially in agreement with a comparable SCF result using the same expanded basis set. Versions one through four yield varying degrees of agreement; however, it is evident that the effect of the virtual orbitals must be included. From the results, CIBS version five is shown to be a viable quantitative procedure which can be used to expand or to study the use of basis sets in quantum chemistry
Study of confined many electron atoms by means of the POEP method
Sarsa, A; Buendía, E; Gálvez, F J
2014-01-01
The electronic structure of confined atoms under impenetrable spherical walls is studied by means of the parameterized optimized effective potential method. A cut-off factor is employed to account for Dirichlet boundary conditions. Two atomic basis sets commonly used for describing free atoms have been analyzed within this scheme. The accuracy of the method is similar to that achieved for the free atoms. The ground state electrostatic multiplet of the carbon atom as well as the ground state and both the [Ar]4s3d 7 5 F and [Ar]3d 8 3 F excited states of the iron atom are studied. The behaviour of the energy levels with the confinement has been analyzed in terms of the different contributions to the total energy of the atom. For the iron atom, the effect of confinement on the outermost orbitals is studied. (paper)
Farzanehpour, Mehdi; Tokatly, Ilya; Nano-Bio Spectroscopy Group; ETSF Scientific Development Centre Team
2015-03-01
We present a rigorous formulation of the time-dependent density functional theory for interacting lattice electrons strongly coupled to cavity photons. We start with an example of one particle on a Hubbard dimer coupled to a single photonic mode, which is equivalent to the single mode spin-boson model or the quantum Rabi model. For this system we prove that the electron-photon wave function is a unique functional of the electronic density and the expectation value of the photonic coordinate, provided the initial state and the density satisfy a set of well defined conditions. Then we generalize the formalism to many interacting electrons on a lattice coupled to multiple photonic modes and prove the general mapping theorem. We also show that for a system evolving from the ground state of a lattice Hamiltonian any density with a continuous second time derivative is locally v-representable. Spanish Ministry of Economy and Competitiveness (Grant No. FIS2013-46159-C3-1-P), Grupos Consolidados UPV/EHU del Gobierno Vasco (Grant No. IT578-13), COST Actions CM1204 (XLIC) and MP1306 (EUSpec).
Redfors, A.
1991-01-01
Magnesiumlike and aluminumlike spectra of the elements calcium - germanium have been obtained through the use of laser-produced plasmas (LPP) and a 3 m normal incidence vacuum spectrograph. The spectral analyses were mainly based on isoelectronic regularities. Intermediate ionization stages of cerium (Ce V) and silicon (SI VI) have also been studied. The light sources in these cases were a sliding spark and a modified version of the LPP. The Eagle spectrograph at the National Institute of Standards and Technology, Gaitherburg, Maryland was used to record the cerium spectrum. Ab initio calculations and least-squares fits of the Slater energy parameters to the experimental energy levels are reported for all investigated spectra. Theoretical predictions of oscillator strengths for Y III and Zr III in the region 1150-3200 AA are presented. The oscillator strengths are needed for abundance determinations of Y 2+ and Zr 2+ in chemically peculiar stars, Cp stars. (65 refs.)
Sarsa, A; Buendía, E; Gálvez, F J
2016-01-01
Explicitly correlated wave functions to study confined atoms under impenetrable spherical walls have been obtained. Configuration mixing and a correlation factor are included in the variational ansatz. The behaviors of the ground state and some low-lying excited states of He, Be, B and C atoms with the confinement size are analyzed. Level crossing with confinement is found for some cases. This effect is analyzed in terms of the single particle energy of the occupied orbitals. The multi-configuration parameterized optimized effective potential method is employed with a cut-off factor to account for Dirichlet boundary conditions. The variational Monte Carlo method is used to deal with explicitly correlated wave functions. (paper)
Coulomb correlations in many-electron systems on the level of self-consistent fields
Warken, M.
1991-06-01
It was the aim of this thesis to show means and ways, in order to regard Coulomb correlation already on the SCF level. As mean to facilitate this general averaged fields should serve. For this first in chapter I was shown, how by means of suitable gauge fixings terms into effective potentials of the Hartree-Fock or g-Hartree type are introduced, which permit an interpretation as correlation density or as effective coupling constant. The following considerations were exemplarily performed on the cases g-Hartree (in Coulomb gauge) and on f-Hartree-Fock. (orig./HSI) [de
Inelastic light scattering and the excited states of many-electron quantum dots
Delgado, Alain; Gonzalez, Augusto
2003-01-01
A consistent calculation of resonant inelastic (Raman) scattering amplitudes for relatively large quantum dots, which takes account of valence band mixing, the discrete character of the spectrum in intermediate and final states, and interference effects, is presented. Raman peaks in charge and spin channels are compared with multipole strengths and with the density of energy levels in final states. A qualitative comparison with the available experimental results is given
Many-electron effect in the resonant Auger electron spectroscopy spectra of adsorbates
Ohno, Masahide
2007-01-01
It is shown by a many-body theory that a resonantly excited core hole state in a chemisorbed molecule such as CO/Ni, CO/Pd, and CO/Pt relaxes to a fully relaxed one, i.e., the ionized core hole state of the smallest binding energy observed by photoelectron spectroscopy, before the core hole decays so that the resonant Auger electron spectroscopy (RAES) spectrum shows the normal Auger decay spectrum. It is shown by a many-body theory that the Auger peaks on the higher kinetic energy (K.E.) side in the RAES or AES spectrum, i.e., so called back-bonding peaks, are the two-hole states consisting of a valence hole and a hole in the adsorbate-substrate hybrid states below the substrate Fermi level. The latter hole is the change in the density of the hybrid states occupied by the screening electron from the core hole state to the valence-hole state. The difference between the back-bonding peak energy and the single valence-hole energy provides an important information about the change in the density of the hybrid states occupied by the screening electron from the core hole state to the valence-hole state. The difference between the RAES spectrum measured at the resonance energy and the AES spectrum measured at far above the ionization limit shows the competition between relaxation and decay of shakeup satellites such as the charge transfer (CT) shakeup. The relaxation rate of the CT shakeup state can be determined by Auger-photoelectron coincidence spectroscopy (APECS)
Liu, Fang, E-mail: fliu@lsec.cc.ac.cn [School of Statistics and Mathematics, Central University of Finance and Economics, Beijing 100081 (China); Lin, Lin, E-mail: linlin@math.berkeley.edu [Department of Mathematics, University of California, Berkeley, CA 94720 (United States); Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Vigil-Fowler, Derek, E-mail: vigil@berkeley.edu [Department of Physics, University of California, Berkeley, CA 94720 (United States); Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Lischner, Johannes, E-mail: jlischner597@gmail.com [Department of Physics, University of California, Berkeley, CA 94720 (United States); Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Kemper, Alexander F., E-mail: afkemper@lbl.gov [Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Sharifzadeh, Sahar, E-mail: ssharifz@bu.edu [Department of Electrical and Computer Engineering and Division of Materials Science and Engineering, Boston University, Boston, MA 02215 (United States); Jornada, Felipe H. da, E-mail: jornada@berkeley.edu [Department of Physics, University of California, Berkeley, CA 94720 (United States); Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Deslippe, Jack, E-mail: jdeslippe@lbl.gov [NERSC, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Yang, Chao, E-mail: cyang@lbl.gov [Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); and others
2015-04-01
We present a numerical integration scheme for evaluating the convolution of a Green's function with a screened Coulomb potential on the real axis in the GW approximation of the self energy. Our scheme takes the zero broadening limit in Green's function first, replaces the numerator of the integrand with a piecewise polynomial approximation, and performs principal value integration on subintervals analytically. We give the error bound of our numerical integration scheme and show by numerical examples that it is more reliable and accurate than the standard quadrature rules such as the composite trapezoidal rule. We also discuss the benefit of using different self energy expressions to perform the numerical convolution at different frequencies.
''Atomic'' Bremsstrahlung or polarizational radiation in collision of many-electron ions
Amusia, M.Ya.; Solov'yov, A.V.
1991-01-01
In this work the so-called ''Atomic'' bremsstrahlung (AB) or polarizational radiation, created in collisions of atoms or ions, is discussed. This kind of radiation arises due to the polarization of the electron shell of colliding particles. It is created by the structured projectiles and targets if the constituents are electrically charged. 6 refs, 2 figs
Quantum electrodynamic corrections for the valence shell in heavy many-electron atoms
Thierfelder, C.; Schwerdtfeger, P.
2010-01-01
We present quantum electrodynamic (QED) calculations within the picture of bound-state QED for the frequency-dependent Breit interaction between electrons, the vacuum polarization, and the electron self-energy correction starting from the Dirac-Coulomb Hamiltonian for the ionization potentials of the group 1, 2, 11, 12, 13, and 18 elements of the periodic table, and down to the superheavy elements up to nuclear charge Z=120. The results for the s-block elements are in very good agreement with earlier studies by Labzowsky et al. [Phys. Rev. A 59, 2707 (1999)]. We discuss the influence of the variational versus perturbative treatment of the Breit interaction for valence-space ionization potentials. We argue that the lowest-order QED contributions become as important as the Breit interaction for ionization potentials out of the valence s shell.
Insights inot the atomic many-particle dynamics of scattering processes by ab-initio calculations
Zapukhlyak, Myroslav
2008-01-01
The present thesis gives a theoretical contribution to the understanding of the many-particle dynamics in inelastic ion-atom collisions. Many-electron dynamics in ion-helium collisions and proton-sodium collisions was theoretically studied. The description is based on the semiclassical approximation with the straight orbit for the projectile motion. The ion-atom collision problem is by this reduced to a time-dependent many-electron problem and in the non-relativistic approximation described by the time-dependent Schroedinger equation. The solution of the many-electron problem pursues in the framework of the time-dependent density functional theory. The time-dependent Schroedinger equation for the interacting many-electron problem is transformed to the system of the time-dependent Kohn-Sham equations and solved by the two-center-basis generator method. The unknown time-dependent exchange-correlation one-particle potential forces different approximation int he time-dependent Kohn-Shan scheme. In this thesis the model of the independent electrons was applied as basis model, in which the electron-electron correlation is consistently neglected in all parts and in all steps. Differential cross sections for different one- and two-electron processes were calculated in the so-called eikonal approximation for the collisional systems p-He, He 2+ -He, and Ar q+ -He (q=15-18) [de
Fluids, superfluids and supersolids: dynamics and cosmology of self-gravitating media
Celoria, Marco [Gran Sasso Science Institute (INFN), Via Francesco Crispi 7, I-67100 L' Aquila (Italy); Comelli, Denis [INFN, Sezione di Ferrara, I-35131 Ferrara (Italy); Pilo, Luigi, E-mail: marco.celoria@gssi.infn.it, E-mail: comelli@fe.infn.it, E-mail: luigi.pilo@aquila.infn.it [Dipartimento di Fisica, Università di L' Aquila, I-67010 L' Aquila (Italy)
2017-09-01
We compute cosmological perturbations for a generic self-gravitating media described by four derivatively-coupled scalar fields. Depending on the internal symmetries of the action for the scalar fields, one can describe perfect fluids, superfluids, solids and supersolids media. Symmetries dictate both dynamical and thermodynamical properties of the media. Generically, scalar perturbations include, besides the gravitational potential, an additional non-adiabatic mode associated with the entropy per particle σ. While perfect fluids and solids are adiabatic with σ constant in time, superfluids and supersolids feature a non-trivial dynamics for σ. Special classes of isentropic media with zero σ can also be found. Tensor modes become massive for solids and supersolids. Such an effective approach can be used to give a very general and symmetry driven modelling of the dark sector.
Geometry effects on magnetization dynamics in circular cross-section wires
Sturma, M. [Univ. Grenoble Alpes, INAC-SPINTEC, F-38000 Grenoble (France); CNRS, SPINTEC, F-38000 Grenoble (France); CEA, INAC-SPINTEC, F-38000 Grenoble (France); Univ. Grenoble Alpes, I. Neel, F-38000 Grenoble (France); CNRS, I. Neel, F-38000 Grenoble (France); Toussaint, J.-C., E-mail: jean-christophe.toussaint@neel.cnrs.fr, E-mail: daria.gusakova@cea.fr [Univ. Grenoble Alpes, I. Neel, F-38000 Grenoble (France); CNRS, I. Neel, F-38000 Grenoble (France); Gusakova, D., E-mail: jean-christophe.toussaint@neel.cnrs.fr, E-mail: daria.gusakova@cea.fr [Univ. Grenoble Alpes, INAC-SPINTEC, F-38000 Grenoble (France); CNRS, SPINTEC, F-38000 Grenoble (France); CEA, INAC-SPINTEC, F-38000 Grenoble (France)
2015-06-28
Three-dimensional magnetic memory design based on circular-cross section nanowires with modulated diameter is the emerging field of spintronics. The consequences of the mutual interaction between electron spins and local magnetic moments in such non-trivial geometries are still open to debate. This paper describes the theoretical study of domain wall dynamics within such wires subjected to spin polarized current. We used our home-made finite element software to characterize the variety of domain wall dynamical regimes observed for different constriction to wire diameter ratios d/D. Also, we studied how sizeable geometry irregularities modify the internal micromagnetic configuration and the electron spin spatial distribution in the system, the geometrical reasons underlying the additional contribution to the system's nonadiabaticity, and the specific domain wall width oscillations inherent to fully three-dimensional systems.
Koeppel, H.; Gromov, E.V.; Trofimov, A.B.
2004-01-01
The multi-mode and multi-state vibronic interactions in the heterocyclic molecules furan, pyrrole, thiophene and their radical cations are investigated theoretically, employing a linear vibronic coupling scheme. The underlying system parameters are determined from large-scale ab initio computations. Previous time-independent dynamical calculations on the radical cations are extended by wave-packet propagations (using the MCTDH method) confirming the strong nonadiabatic coupling effects. For the singlet excited states of furan and thiophene quantum dynamical calculations are presented which go beyond the two-state approximation frequently applied in the literature. The characteristic spectral structures are well reproduced, especially in the case of furan. The implications of these results on the photochemical reaction dynamics of these species are discussed
Quantum State-Resolved Collision Dynamics of Nitric Oxide at Ionic Liquid and Molten Metal Surfaces
Zutz, Amelia Marie
Detailed molecular scale interactions at the gas-liquid interface are explored with quantum state-to-state resolved scattering of a jet-cooled beam of NO(2pi1/2; N = 0) from ionic liquid and molten metal surfaces. The scattered distributions are probed via laser-induced fluorescence methods, which yield rotational and spin-orbit state populations that elucidate the dynamics of energy transfer at the gas-liquid interface. These collision dynamics are explored as a function of incident collision energy, surface temperature, scattering angle, and liquid identity, all of which are found to substantially affect the degree of rotational, electronic and vibrational excitation of NO via collisions at the liquid surface. Rotational distributions observed reveal two distinct scattering pathways, (i) molecules that trap, thermalize and eventually desorb from the surface (trapping-desorption, TD), and (ii) those that undergo prompt recoil (impulsive scattering, IS) prior to complete equilibration with the liquid surface. Thermally desorbing NO molecules are found to have rotational temperatures close to, but slightly cooler than the surface temperature, indicative of rotational dependent sticking probabilities on liquid surfaces. Nitric oxide is a radical with multiple low-lying electronic states that serves as an ideal candidate for exploring nonadiabatic state-changing collision dynamics at the gas-liquid interface, which induce significant excitation from ground (2pi1/2) to excited (2pi 3/2) spin-orbit states. Molecular beam scattering of supersonically cooled NO from hot molten metals (Ga and Au, Ts = 300 - 1400 K) is also explored, which provide preliminary evidence for vibrational excitation of NO mediated by thermally populated electron-hole pairs in the hot, conducting liquid metals. The results highlight the presence of electronically nonadiabatic effects and build toward a more complete characterization of energy transfer dynamics at gas-liquid interfaces.
Yonehara, Takehiro; Takatsuka, Kazuo
2009-01-01
We report a theoretical study of non-adiabatic electrons-nuclei coupled dynamics of diborane H 2 BH 2 BH 2 under several types of short pulse lasers. This molecule is known to have particularly interesting geometrical and electronic structures, which originate from the electron-deficient chemical bondings. We revisit the chemical bonding of diborane from the view point of electron wavepacket dynamics coupled with nuclear motions, and attempt to probe the characteristics of it by examining its response to intense laser fields. We study in the following three aspects, (i) bond formation of diborane by collision between two monoboranes, (ii) attosecond electron wavepacket dynamics in the ground state and first excited state by circularly polarized laser pulse, and (iii) induced fragmentation back to monoborane molecules by linearly polarized laser. The wave lengths of two types of laser field employed are 200 nm (in UV range) and 800 nm (in IR range), and we track the dynamics from hundreds of attoseconds up to few tens of femtoseconds. To this end, we apply the ab initio semiclassical Ehrenfest theory, into which the classical vector potential of a laser field is introduced. Basic features of the non-adiabatic response of electrons to the laser fields is elucidated in this scheme. To analyze the electronic wavepackets thus obtained, we figure out bond order density that is a spatial distribution of the bond order and bond order flux density arising only from the bonding regions, and so on. Main findings in this work are: (i) dimerization of monoboranes to diborane is so efficient that even intense laser is hard to prevent it; (ii) collective motions of electron flux emerge in the central BHHB bonding area in response to the circularly polarized laser fields; (iii) laser polarization with the direction of central two BH bonding vector is efficient for the cleavage of BH 3 -BH 3 ; and (iv) nuclear derivative coupling plays a critical role in the field induced
Quantum dynamics of fast chemical reactions
Light, J.C. [Univ. of Chicago, IL (United States)
1993-12-01
The aims of this research are to explore, develop, and apply theoretical methods for the evaluation of the dynamics of gas phase collision processes, primarily chemical reactions. The primary theoretical tools developed for this work have been quantum scattering theory, both in time dependent and time independent forms. Over the past several years, the authors have developed and applied methods for the direct quantum evaluation of thermal rate constants, applying these to the evaluation of the hydrogen isotopic exchange reactions, applied wave packet propagation techniques to the dissociation of Rydberg H{sub 3}, incorporated optical potentials into the evaluation of thermal rate constants, evaluated the use of optical potentials for state-to-state reaction probability evaluations, and, most recently, have developed quantum approaches for electronically non-adiabatic reactions which may be applied to simplify calculations of reactive, but electronically adiabatic systems. Evaluation of the thermal rate constants and the dissociation of H{sub 3} were reported last year, and have now been published.
Klinkusch, Stefan; Saalfrank, Peter; Klamroth, Tillmann
2009-09-21
We report simulations of laser-pulse driven many-electron dynamics by means of a simple, heuristic extension of the time-dependent configuration interaction singles (TD-CIS) approach. The extension allows for the treatment of ionizing states as nonstationary states with a finite, energy-dependent lifetime to account for above-threshold ionization losses in laser-driven many-electron dynamics. The extended TD-CIS method is applied to the following specific examples: (i) state-to-state transitions in the LiCN molecule which correspond to intramolecular charge transfer, (ii) creation of electronic wave packets in LiCN including wave packet analysis by pump-probe spectroscopy, and, finally, (iii) the effect of ionization on the dynamic polarizability of H(2) when calculated nonperturbatively by TD-CIS.
Collision dynamics of H+ + N2 at low energies based on time-dependent density-functional theory
Yu, W.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Gao, C.-Z.; Wei, B.
2018-02-01
Using time-dependent density-functional theory at the level of local density approximation augmented by a self-interaction correction and coupled non-adiabatically to molecular dynamics, we study, from a theoretical perspective, scattering dynamics of the proton in collisions with the N2 molecule at 30 eV. Nine different collision configurations are employed to analyze the proton energy loss spectra, electron depletion, scattering angles and self-interaction effects. Our results agree qualitatively with the experimental data and previous theoretical calculations. The discrepancies are ascribed to the limitation of the theoretical models in use. We find that self-interaction effects can significantly influence the electron capture and the excited diatomic vibrational motion, which is in consistent with other calculations. In addition, it is found that the molecular structure can be readily retrieved from the proton energy loss spectra due to a significant momentum transfer in head-on collisions.
Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.
2015-01-01
The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism
Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.
2015-06-01
The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.
Elkins, Madeline H.; Williams, Holly L. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Neumark, Daniel M. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)
2015-06-21
The charge-transfer-to-solvent dynamics (CTTS) and excited state relaxation mechanism of the solvated electron in methanol are studied by time-resolved photoelectron spectroscopy on a liquid methanol microjet by means of two-pulse and three-pulse experiments. In the two-pulse experiment, CTTS excitation is followed by a probe photoejection pulse. The resulting time-evolving photoelectron spectrum reveals multiple time scales characteristic of relaxation and geminate recombination of the initially generated electron which are consistent with prior results from transient absorption. In the three-pulse experiment, the relaxation dynamics of the solvated electron following electronic excitation are measured. The internal conversion lifetime of the excited electron is found to be 130 ± 40 fs, in agreement with extrapolated results from clusters and the non-adiabatic relaxation mechanism.
Contrasting dynamics of electrons and protons in the near-Earth plasma sheet during dipolarization
Malykhin, Andrey Y.; Grigorenko, Elena E.; Kronberg, Elena A.; Koleva, Rositza; Ganushkina, Natalia Y.; Kozak, Ludmila; Daly, Patrick W.
2018-05-01
The fortunate location of Cluster and the THEMIS P3 probe in the near-Earth plasma sheet (PS) (at X ˜ -7-9 RE) allowed for the multipoint analysis of properties and spectra of electron and proton injections. The injections were observed during dipolarization and substorm current wedge formation associated with braking of multiple bursty bulk flows (BBFs). In the course of dipolarization, a gradual growth of the BZ magnetic field lasted ˜ 13 min and it was comprised of several BZ pulses or dipolarization fronts (DFs) with duration ≤ 1 min. Multipoint observations have shown that the beginning of the increase in suprathermal ( > 50 keV) electron fluxes - the injection boundary - was observed in the PS simultaneously with the dipolarization onset and it propagated dawnward along with the onset-related DF. The subsequent dynamics of the energetic electron flux was similar to the dynamics of the magnetic field during the dipolarization. Namely, a gradual linear growth of the electron flux occurred simultaneously with the gradual growth of the BZ field, and it was comprised of multiple short ( ˜ few minutes) electron injections associated with the BZ pulses. This behavior can be explained by the combined action of local betatron acceleration at the BZ pulses and subsequent gradient drifts of electrons in the flux pile up region through the numerous braking and diverting DFs. The nonadiabatic features occasionally observed in the electron spectra during the injections can be due to the electron interactions with high-frequency electromagnetic or electrostatic fluctuations transiently observed in the course of dipolarization. On the contrary, proton injections were detected only in the vicinity of the strongest BZ pulses. The front thickness of these pulses was less than a gyroradius of thermal protons that ensured the nonadiabatic acceleration of protons. Indeed, during the injections in the energy spectra of protons the pronounced bulge was clearly observed in a
Wang Haobin; Thoss, Michael
2010-01-01
Graphical abstract: □□□ - Abstract: The dynamics of the spin-boson model at zero temperature is studied for a bath characterized by a sub-Ohmic spectral density. Using the numerically exact multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method, the population dynamics of the two-level subsystem has been investigated in a broad range of parameter space. The results show the transition of the dynamics from weakly damped coherent motion to localization upon increase of the system-bath coupling strength. Comparison of the exact ML-MCTDH simulations with the non-interacting blip approximation (NIBA) shows that the latter performs rather poorly in the weak coupling regime with small Kondo parameters. However, NIBA improves significantly upon increase in the coupling strength and is quantitatively correct in the strong coupling, nonadiabatic limit. The transition from coherent motion to localization as a function of the different parameters of the model is analyzed in some detail.
Reduced dynamics in spin-boson models: A method for both slow and fast bath
Golosov, Andrei A.; Friesner, Richard A.; Pechukas, Philip
2000-01-01
We study a model for treating dissipative systems, a one dimensional quantum system coupled to a harmonic bath. The dynamics of such a system can be described by Feynman's path integral expression for the reduced density matrix. In this formulation the interaction of the system with the environment is stored in the influence functional. Recently we showed that fast environmental modes that give rise to correlations in the influence functional which are short range in time can be treated efficiently by a memory equation algorithm, which is a discretized version of a master equation. In this work we extend this approach to treat slow environmental modes as well, thereby efficiently linking adiabatic and nonadiabatic regimes. In this extended method the long range correlations in the influence functional arising from slow bath modes are taken into account through Stock's semiclassical self-consistent-field approach. (c) 2000 American Institute of Physics
Zheng Li
2016-07-01
Full Text Available The ultrafast nuclear and electronic dynamics of protonated water clusters H+(H2On after extreme ultraviolet photoionization is investigated. In particular, we focus on cluster cations with n = 3, 6, and 21. Upon ionization, two positive charges are present in the cluster related to the excess proton and the missing electron, respectively. A correlation is found between the cluster's geometrical conformation and initial electronic energy with the size of the final fragments produced. For situations in which the electron hole and proton are initially spatially close, the two entities become correlated and separate in a time-scale of 20 to 40 fs driven by strong non-adiabatic effects.
Li, Zheng; Vendrell, Oriol
2016-01-01
The ultrafast nuclear and electronic dynamics of protonated water clusters H+(H2O)n after extreme ultraviolet photoionization is investigated. In particular, we focus on cluster cations with n = 3, 6, and 21. Upon ionization, two positive charges are present in the cluster related to the excess proton and the missing electron, respectively. A correlation is found between the cluster's geometrical conformation and initial electronic energy with the size of the final fragments produced. For situations in which the electron hole and proton are initially spatially close, the two entities become correlated and separate in a time-scale of 20 to 40 fs driven by strong non-adiabatic effects. PMID:26798842
Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.
2016-05-01
The excited state relaxation dynamics of the solvated electron in H2O and D2O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H2O and 102 ± 8 fs in D2O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.
On the dynamical Casimir effect in 1 + 1 dimensions
Alves, D.T.; Farina, C.; Maia Neto, P.A.; Tort, A.C.
2000-01-01
Full text follows: Vacuum field fluctuations exert radiation pressure on boundaries placed in empty space. If we take only one boundary at rest in vacuum, the total pressure exerted by the vacuum on the boundary is null. For two boundaries at rest in vacuum there is a net pressure exerted on the boundaries known as the Casimir effect. It has also been recognized that the dynamical counterparts of this static force appear for moving boundaries. In the dynamical case the existence of a net vacuum radiation pressure does not require the presence of two boundaries as in static case. Vacuum pressure already exists for a single boundary moving with a nonuniform acceleration. For that type of motion, the field does not remain in the vacuum state, but the quanta of the field are produced through nonadiabatic processes. In 1982 Ford and Vilenkin developed a perturbation method based on the static solution to calculate in first approximation the vacuum pressure exerted on a non-relativistic moving boundary. Using the method of Ford-Vilenkin we compute in the two dimensional quantum theory of a real massless scalar field the pressure exerted by the vacuum on a perfectly reflecting boundary moving with nonuniform acceleration around the coordinate x = 0 , having another boundary fixed at x = L. This simple model can provide insight into more sophisticated processes, such as photon production by moving mirrors and particle production in cosmological models and exploding black holes. (author)
Molecular quantum dynamics. From theory to applications
Gatti, Fabien
2014-01-01
An educational and accessible introduction to the field of molecular quantum dynamics. Illustrates the importance of the topic for broad areas of science: from astrophysics and the physics of the atmosphere, over elementary processes in chemistry, to biological processes. Presents chosen examples of striking applications, highlighting success stories, summarized by the internationally renowned experts. Including a foreword by Lorenz Cederbaum (University Heidelberg, Germany). This book focuses on current applications of molecular quantum dynamics. Examples from all main subjects in the field, presented by the internationally renowned experts, illustrate the importance of the domain. Recent success in helping to understand experimental observations in fields like heterogeneous catalysis, photochemistry, reactive scattering, optical spectroscopy, or femto- and attosecond chemistry and spectroscopy underline that nuclear quantum mechanical effects affect many areas of chemical and physical research. In contrast to standard quantum chemistry calculations, where the nuclei are treated classically, molecular quantum dynamics can cover quantum mechanical effects in their motion. Many examples, ranging from fundamental to applied problems, are known today that are impacted by nuclear quantum mechanical effects, including phenomena like tunneling, zero point energy effects, or non-adiabatic transitions. Being important to correctly understand many observations in chemical, organic and biological systems, or for the understanding of molecular spectroscopy, the range of applications covered in this book comprises broad areas of science: from astrophysics and the physics and chemistry of the atmosphere, over elementary processes in chemistry, to biological processes (such as the first steps of photosynthesis or vision). Nevertheless, many researchers refrain from entering this domain. The book ''Molecular Quantum Dynamics'' offers them an accessible introduction. Although the
Molecular quantum dynamics. From theory to applications
Gatti, Fabien (ed.) [Montpellier 2 Univ. (France). Inst. Charles Gerhardt - CNRS 5253
2014-09-01
An educational and accessible introduction to the field of molecular quantum dynamics. Illustrates the importance of the topic for broad areas of science: from astrophysics and the physics of the atmosphere, over elementary processes in chemistry, to biological processes. Presents chosen examples of striking applications, highlighting success stories, summarized by the internationally renowned experts. Including a foreword by Lorenz Cederbaum (University Heidelberg, Germany). This book focuses on current applications of molecular quantum dynamics. Examples from all main subjects in the field, presented by the internationally renowned experts, illustrate the importance of the domain. Recent success in helping to understand experimental observations in fields like heterogeneous catalysis, photochemistry, reactive scattering, optical spectroscopy, or femto- and attosecond chemistry and spectroscopy underline that nuclear quantum mechanical effects affect many areas of chemical and physical research. In contrast to standard quantum chemistry calculations, where the nuclei are treated classically, molecular quantum dynamics can cover quantum mechanical effects in their motion. Many examples, ranging from fundamental to applied problems, are known today that are impacted by nuclear quantum mechanical effects, including phenomena like tunneling, zero point energy effects, or non-adiabatic transitions. Being important to correctly understand many observations in chemical, organic and biological systems, or for the understanding of molecular spectroscopy, the range of applications covered in this book comprises broad areas of science: from astrophysics and the physics and chemistry of the atmosphere, over elementary processes in chemistry, to biological processes (such as the first steps of photosynthesis or vision). Nevertheless, many researchers refrain from entering this domain. The book ''Molecular Quantum Dynamics'' offers them an accessible
Joubert-Doriol, Loïc; Ryabinkin, Ilya G.; Izmaylov, Artur F.
2013-01-01
In molecular systems containing conical intersections (CIs), a nontrivial geometric phase (GP) appears in the nuclear and electronic wave functions in the adiabatic representation. We study GP effects in nuclear dynamics of an N-dimensional linear vibronic coupling (LVC) model. The main impact of GP on low-energy nuclear dynamics is reduction of population transfer between the local minima of the LVC lower energy surface. For the LVC model, we proposed an isometric coordinate transformation that confines non-adiabatic effects within a two-dimensional subsystem interacting with an N − 2 dimensional environment. Since environmental modes do not couple electronic states, all GP effects originate from nuclear dynamics within the subsystem. We explored when the GP affects nuclear dynamics of the isolated subsystem, and how the subsystem-environment interaction can interfere with GP effects. Comparing quantum dynamics with and without GP allowed us to devise simple rules to determine significance of the GP for nuclear dynamics in this model
Hannibal, S.; Kettmann, P.; Croitoru, M. D.; Axt, V. M.; Kuhn, T.
2018-01-01
We present a numerical study of the Higgs mode in an ultracold confined Fermi gas after an interaction quench and find a dynamical vanishing of the superfluid order parameter. Our calculations are done within a microscopic density-matrix approach in the Bogoliubov-de Gennes framework which takes the three-dimensional cigar-shaped confinement explicitly into account. In this framework, we study the amplitude mode of the order parameter after interaction quenches starting on the BCS side of the BEC-BCS crossover close to the transition and ending in the BCS regime. We demonstrate the emergence of a dynamically vanishing superfluid order parameter in the spatiotemporal dynamics in a three-dimensional trap. Further, we show that the signal averaged over the whole trap mirrors the spatiotemporal behavior and allows us to systematically study the effects of the system size and aspect ratio on the observed dynamics. Our analysis enables us to connect the confinement-induced modifications of the dynamics to the pairing properties of the system. Finally, we demonstrate that the signature of the Higgs mode is contained in the dynamical signal of the condensate fraction, which, therefore, might provide a new experimental access to the nonadiabatic regime of the Higgs mode.
Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy
Mandal, Aritra; Tokmakoff, Andrei
2015-01-01
We employed ultrafast transient absorption and broadband 2DIR spectroscopy to study the vibrational dynamics of aqueous hydroxide solutions by exciting the O–H stretch vibrations of the strongly hydrogen-bonded hydroxide solvation shell water and probing the continuum absorption of the solvated ion between 1500 and 3800 cm −1 . We observe rapid vibrational relaxation processes on 150–250 fs time scales across the entire probed spectral region as well as slower vibrational dynamics on 1–2 ps time scales. Furthermore, the O–H stretch excitation loses its frequency memory in 180 fs, and vibrational energy exchange between bulk-like water vibrations and hydroxide-associated water vibrations occurs in ∼200 fs. The fast dynamics in this system originate in strong nonlinear coupling between intra- and intermolecular vibrations and are explained in terms of non-adiabatic vibrational relaxation. These measurements indicate that the vibrational dynamics of the aqueous hydroxide complex are faster than the time scales reported for long-range transport of protons in aqueous hydroxide solutions
Basler, Mathias; Gindensperger, Etienne; Meyer, Hans-Dieter; Cederbaum, Lorenz S.
2008-01-01
We address the nonadiabatic quantum dynamics of (macro)systems involving a vast number of nuclear degrees of freedom (modes) in the presence of conical intersections. The macrosystem is first decomposed into a system part carrying a few, strongly coupled modes, and an environment, comprising the remaining modes. By successively transforming the modes of the environment, a hierarchy of effective Hamiltonians for the environment can be constructed. Each effective Hamiltonian depends on a reduced number of effective modes, which carry cumulative effects. The environment is described by a few effective modes augmented by a residual environment. In practice, the effective modes can be added to the system's modes and the quantum dynamics of the entire macrosystem can be accurately calculated on a limited time-interval. For longer times, however, the residual environment plays a role. We investigate the possibility to treat fully quantum mechanically the system plus a few effective environmental modes, augmented by the dynamics of the residual environment treated by the time-dependent Hartree (TDH) approximation. While the TDH approximation is known to fail to correctly reproduce the dynamics in the presence of conical intersections, it is shown that its use on top of the effective-mode formalism leads to much better results. Two numerical examples are presented and discussed; one of them is known to be a critical case for the TDH approximation
Dynamical quantum Hall effect in the parameter space.
Gritsev, V; Polkovnikov, A
2012-04-24
Geometric phases in quantum mechanics play an extraordinary role in broadening our understanding of fundamental significance of geometry in nature. One of the best known examples is the Berry phase [M.V. Berry (1984), Proc. Royal. Soc. London A, 392:45], which naturally emerges in quantum adiabatic evolution. So far the applicability and measurements of the Berry phase were mostly limited to systems of weakly interacting quasi-particles, where interference experiments are feasible. Here we show how one can go beyond this limitation and observe the Berry curvature, and hence the Berry phase, in generic systems as a nonadiabatic response of physical observables to the rate of change of an external parameter. These results can be interpreted as a dynamical quantum Hall effect in a parameter space. The conventional quantum Hall effect is a particular example of the general relation if one views the electric field as a rate of change of the vector potential. We illustrate our findings by analyzing the response of interacting spin chains to a rotating magnetic field. We observe the quantization of this response, which we term the rotational quantum Hall effect.
Kim, Do Hun; Mun, Tae Hun; Kim, Dong Hwan
1999-02-01
This book introduces systems thinking and conceptual tool and modeling tool of dynamics system such as tragedy of single thinking, accessible way of system dynamics, feedback structure and causal loop diagram analysis, basic of system dynamics modeling, causal loop diagram and system dynamics modeling, information delay modeling, discovery and application for policy, modeling of crisis of agricultural and stock breeding products, dynamic model and lesson in ecosystem, development and decadence of cites and innovation of education forward system thinking.
A theory of electron baths: One-electron system dynamics
McDowell, H.K.
1992-01-01
The second-quantized, many-electron, atomic, and molecular Hamiltonian is partitioned both by the identity or labeling of the spin orbitals and by the dynamics of the spin orbitals into a system coupled to a bath. The electron bath is treated by a molecular time scale generalized Langevin equation approach designed to include one-electron dynamics in the system dynamics. The bath is formulated as an equivalent chain of spin orbitals through the introduction of equivalent-chain annihilation and creation operators. Both the dynamics and the quantum grand canonical statistical properties of the electron bath are examined. Two versions for the statistical properties of the bath are pursued. Using a weak bath assumption, a bath statistical average is defined which allows one to achieve a reduced dynamics description of the electron system which is coupled to the electron bath. In a strong bath assumption effective Hamiltonians are obtained which reproduce the dynamics of the bath and which lead to the same results as found in the weak bath assumption. The effective (but exact) Hamiltonian is found to be a one-electron Hamiltonian. A reduced dynamics equation of motion for the system population matrix is derived and found to agree with a previous version. This equation of motion is useful for studying electron transfer in the system when coupled to an electron bath
Ehrenfest dynamics is purity non-preserving: A necessary ingredient for decoherence
Alonso, J. L.; Clemente-Gallardo, J.; Cuchí, J. C.
2012-01-01
We discuss the evolution of purity in mixed quantum/classical approaches to electronic nonadiabatic dynamics in the context of the Ehrenfest model. As it is impossible to exactly determine initial conditions for a realistic system, we choose to work in the statistical Ehrenfest formalism that we introduced in Alonso et al. [J. Phys. A: Math. Theor. 44, 396004 (2011)]. From it, we develop a new framework to determine exactly the change in the purity of the quantum subsystem along with the evolution of a statistical Ehrenfest system. In a simple case, we verify how and to which extent Ehrenfest statistical dynamics makes a system with more than one classical trajectory, and an initial quantum pure state become a quantum mixed one. We prove this numerically showing how the evolution of purity depends on time, on the dimension of the quantum state space D, and on the number of classical trajectories N of the initial distribution. The results in this work open new perspectives for studying decoherence with Ehrenfest dynamics.
Ultrafast carrier thermalization and cooling dynamics in few-layer MoS2.
Nie, Zhaogang; Long, Run; Sun, Linfeng; Huang, Chung-Che; Zhang, Jun; Xiong, Qihua; Hewak, Daniel W; Shen, Zexiang; Prezhdo, Oleg V; Loh, Zhi-Heng
2014-10-28
Femtosecond optical pump-probe spectroscopy with 10 fs visible pulses is employed to elucidate the ultrafast carrier dynamics of few-layer MoS2. A nonthermal carrier distribution is observed immediately following the photoexcitation of the A and B excitonic transitions by the ultrashort, broadband laser pulse. Carrier thermalization occurs within 20 fs and proceeds via both carrier-carrier and carrier-phonon scattering, as evidenced by the observed dependence of the thermalization time on the carrier density and the sample temperature. The n(-0.37 ± 0.03) scaling of the thermalization time with carrier density suggests that equilibration of the nonthermal carrier distribution occurs via non-Markovian quantum kinetics. Subsequent cooling of the hot Fermi-Dirac carrier distribution occurs on the ∼ 0.6 ps time scale via carrier-phonon scattering. Temperature- and fluence-dependence studies reveal the involvement of hot phonons in the carrier cooling process. Nonadiabatic ab initio molecular dynamics simulations, which predict carrier-carrier and carrier-phonon scattering time scales of 40 fs and 0.5 ps, respectively, lend support to the assignment of the observed carrier dynamics.
Álvarez-Collado, José R; Cantarero, Andrés
2014-01-01
We have calculated the optical and magnetic properties of the four lowest many-body states for cyclic zigzag graphene nano-ribbons (GNRs). The results have been obtained within the semi-empirical restricted frozen Hartree–Fock approximation. Firstly, we obtained one-determinant numerical and analytical coincident results. We detected the existence of two degenerate open-shell molecular orbitals (MOs) o, o’. Due to this degeneracy, some of the mentioned results do depend on any (arbitrary) orthogonal transformation between these two MOs. We have improved these preliminary results by using linear combinations of two determinants, which are eigenfunctions of the operators, which commute with the electronic Hamiltonian. These eigenfunctions represent properly the wave functions of these four electronic states. These calculations show that there are two degenerate ground states. One of them is ferromagnetic and the other state is non magnetic. Finally, we have calculated these four states to full configuration interaction level studying the dependence of their properties on the size of the GNRs. (paper)
Álvarez-Collado, José R.; Cantarero, Andrés
2014-09-01
We have calculated the optical and magnetic properties of the four lowest many-body states for cyclic zigzag graphene nano-ribbons (GNRs). The results have been obtained within the semi-empirical restricted frozen Hartree-Fock approximation. Firstly, we obtained one-determinant numerical and analytical coincident results. We detected the existence of two degenerate open-shell molecular orbitals (MOs) o, o’. Due to this degeneracy, some of the mentioned results do depend on any (arbitrary) orthogonal transformation between these two MOs. We have improved these preliminary results by using linear combinations of two determinants, which are eigenfunctions of the operators, which commute with the electronic Hamiltonian. These eigenfunctions represent properly the wave functions of these four electronic states. These calculations show that there are two degenerate ground states. One of them is ferromagnetic and the other state is non magnetic. Finally, we have calculated these four states to full configuration interaction level studying the dependence of their properties on the size of the GNRs.
Many-electron effect in the resonant L23-M23V Auger-electron spectrum of Ti metal
Ohno, Masahide
2006-01-01
Above the L23 absorption edge the L 23 -M 23 V resonant Auger-electron spectroscopy (RAES) spectrum of Ti metal shows a normal L 23 -M 23 V Auger decay spectrum at a constant kinetic energy (K.E.). Here LX and MY are the atomic shells Lx and My, respectively. Apart from a weak spectral feature of the L2-M23V Auger transition appearing around the L2 edge, the RAES spectra of Ti meal show a very little difference between the L2 and L3 regions [P. Le Fevre, J. Danger, H. Magnan, D. Chandesris, J. Jupille, S. Bourgeois, M.-A. Arrio, R. Gotter, A. Verdini, A. Morgante, Phys. Rev. B69 (2004) 155421]. It is shown that the time scale of relaxation of the resonantly excited L23-hole state to the L23-electron ionized state is much shorter than that of the L23-hole decay so that the L 23 -M 23 V RAES spectrum of Ti metal resembles much the normal L 23 -M 23 V Auger decay spectrum. The relaxation of the resonantly excited L23-hole state to the fully relaxed L23-hole state before the L23-hole decays, explains the extra width which is the primary cause of the discrepancy between the experimental high resolution near edge X-ray absorption spectroscopy (XAS) spectrum of Ti metal and the one calculated by the particle-hole Green's function including the Coulomb exchange interaction between the 2p hole and the 3d electron. The time scale of relaxation of the L3V two-hole state created by the L2-L3V Coster-Kronig (CK) decay to the single L3-hole state is much shorter than that of the L3-hole decay so that the L2-L3V-L3-M23V CK preceded Auger decay spectrum resembles much the L3-M23V Auger decay one
Xie, Huimin
The following sections are included: * Definition of Dynamical Languages * Distinct Excluded Blocks * Definition and Properties * L and L″ in Chomsky Hierarchy * A Natural Equivalence Relation * Symbolic Flows * Symbolic Flows and Dynamical Languages * Subshifts of Finite Type * Sofic Systems * Graphs and Dynamical Languages * Graphs and Shannon-Graphs * Transitive Languages * Topological Entropy
Balazs, N.L.
1979-01-01
It is pointed out that in semiclassical dynamics one is encouraged to study the evolution of those curves in phase space which classically represent ensembles corresponding to wave functions. It is shown that the fixed points generate new time scales so that for times longer than the critical times, quantum dynamics will profoundly differ from classical dynamics. (P.L.)
Multi-arrangement quantum dynamics in 6D: cis-trans isomerization and 1,3-hydrogen transfer in HONO
Luckhaus, David
2004-01-01
The overtone spectrum and wave packet dynamics of nitrous acid (HONO) are studied with a global six-dimensional potential energy function interpolated directly from density functional calculations together with the corresponding dipole hypersurfaces. The quantum dynamics for the cis-trans isomerization and the symmetric 1,3-hydrogen transfer are treated in full dimensionality in terms of the generalized Z-matrix discrete variable representation. For the quantum mechanical description of complicated rearrangements a new approach to multi-arrangement quantum dynamics is introduced and applied to the symmetric hydrogen exchange tunneling in cis-HONO. The cis-trans isomerization is found to be dominated by adiabatic barrier crossing with only minor tunneling contributions, but with pronounced mode selectivity. The OH-stretching overtones of trans-HONO are adiabatically almost completely separated from the OH torsional dynamics with extremely slow intramolecular energy redistribution. The 1,3-hydrogen transfer, by contrast, proceeds largely via coherent tunneling even significantly below the barrier. The process is clearly non-adiabatic (at least in terms of valence coordinates) but remains highly state specific. While the absorption spectrum of trans-HONO remains largely unaffected, OH-stretching overtones of cis-HONO (above the barrier between 2ν OH and 3ν OH ) decompose into highly fragmented absorption patterns with corresponding tunneling periods on the picosecond time scale
Nonadiabatic effects in inelastic collisional processes
Belyaev, Andrey K
2009-01-01
The standard adiabatic Born-Oppenheimer approach to inelastic collisional processes is revised. It is shown that the widely used standard interpretation of this approach has fundamental limitations leading to physical artefacts or to uncertainties in numerical calculations due to neglecting the electron translation problem. It is demonstrated that the Born-Oppenheimer approach itself does not have such limitations. The particular full quantum solution of the electron translation problem within the Born-Oppenheimer approach by means of the reprojection procedure is discussed in the paper together with the practical applications.
Nonadiabatic Berry phase in nanocrystalline magnets
R. Skomski
2017-05-01
Full Text Available It is investigated how a Berry phase is created in polycrystalline nanomagnets and how the phase translates into an emergent magnetic field and into a topological Hall-effect contribution. The analysis starts directly from the spin of the conduction electrons and does not involve any adiabatic Hamiltonian. Completely random spin alignment in the nanocrystallites does not lead to a nonzero emergent field, but a modulation of the local magnetization does. As an explicit example, we consider a wire with a modulated cone angle.
Dynamical polarizability of graphene irradiated by circularly polarized ac electric fields
Busl, Maria; Platero, Gloria; Jauho, Antti-Pekka
2012-01-01
We examine the low-energy physics of graphene in the presence of a circularly polarized electric field in the terahertz regime. Specifically, we derive a general expression for the dynamical polarizability of graphene irradiated by an ac electric field. Several approximations are developed...... that allow one to develop a semianalytical theory for the weak-field regime. The ac field changes qualitatively the single- and many-electron excitations of graphene: Undoped samples may exhibit collective excitations (in contrast to the equilibrium situation), and the properties of the excitations in doped...
Discrete dynamics versus analytic dynamics
Toxværd, Søren
2014-01-01
For discrete classical Molecular dynamics obtained by the “Verlet” algorithm (VA) with the time increment h there exists a shadow Hamiltonian H˜ with energy E˜(h) , for which the discrete particle positions lie on the analytic trajectories for H˜ . Here, we proof that there, independent...... of such an analytic analogy, exists an exact hidden energy invariance E * for VA dynamics. The fact that the discrete VA dynamics has the same invariances as Newtonian dynamics raises the question, which of the formulations that are correct, or alternatively, the most appropriate formulation of classical dynamics....... In this context the relation between the discrete VA dynamics and the (general) discrete dynamics investigated by Lee [Phys. Lett. B122, 217 (1983)] is presented and discussed....
Coupled forward-backward trajectory approach for nonequilibrium electron-ion dynamics
Sato, Shunsuke A.; Kelly, Aaron; Rubio, Angel
2018-04-01
We introduce a simple ansatz for the wave function of a many-body system based on coupled forward and backward propagating semiclassical trajectories. This method is primarily aimed at, but not limited to, treating nonequilibrium dynamics in electron-phonon systems. The time evolution of the system is obtained from the Euler-Lagrange variational principle, and we show that this ansatz yields Ehrenfest mean-field theory in the limit that the forward and backward trajectories are orthogonal, and in the limit that they coalesce. We investigate accuracy and performance of this method by simulating electronic relaxation in the spin-boson model and the Holstein model. Although this method involves only pairs of semiclassical trajectories, it shows a substantial improvement over mean-field theory, capturing quantum coherence of nuclear dynamics as well as electron-nuclear correlations. This improvement is particularly evident in nonadiabatic systems, where the accuracy of this coupled trajectory method extends well beyond the perturbative electron-phonon coupling regime. This approach thus provides an attractive route forward to the ab initio description of relaxation processes, such as thermalization, in condensed phase systems.
Dynamics of elementary processes in the gas phase O2 and CO
Bacchus-Montabonel, M.C.; Tergiman, Y.S.; Vaeck, N.; Baloitcha, E.; Desouter-Lecomte, M.
2002-01-01
Complex reaction mechanisms are involved in the radiation of biomolecules, their dynamics may proceed by a series of elementary processes, induced often by a fast reaction step, followed by relaxation or reorganization of the molecular system. The time-dependent wave packet method tested on the Si 4+ + He system, provides a clear and physical insight into the dynamics of theses process. Photodissociation experiments were performed, in particular the dissociation of bromoacetylchloride Br-CH 2 -COCl, to study the competitive dissociation of C-Cl and C-Br bonds. The dissociation leaded preferentially to C- Cl breaking, although the C-Br bond is thermodynamically weaker. This result is in disagreement with statistical theories, as the branching ratio depends not only on the relative height of the corresponding barriers, but also on non-adiabatic transitions arising from interactions between the different excited states. The effects depends on the distance between the C=O and C-X chromophores and on the conforming molecule. (nevyjel)
Hole dynamics and spin currents after ionization in strong circularly polarized laser fields
Barth, Ingo; Smirnova, Olga
2014-01-01
We apply the time-dependent analytical R-matrix theory to develop a movie of hole motion in a Kr atom upon ionization by strong circularly polarized field. We find rich hole dynamics, ranging from rotation to swinging motion. The motion of the hole depends on the final energy and the spin of the photoelectron and can be controlled by the laser frequency and intensity. Crucially, hole rotation is a purely non-adiabatic effect, completely missing in the framework of quasistatic (adiabatic) tunneling theories. We explore the possibility to use hole rotation as a clock for measuring ionization time. Analyzing the relationship between the relative phases in different ionization channels we show that in the case of short-range electron-core interaction the hole is always initially aligned along the instantaneous direction of the laser field, signifying zero delays in ionization. Finally, we show that strong-field ionization in circular fields creates spin currents (i.e. different flow of spin-up and spin-down density in space) in the ions. This phenomenon is intimately related to the production of spin-polarized electrons in strong laser fields Barth and Smirnova (2013 Phys. Rev. A 88 013401). We demonstrate that rich spin dynamics of electrons and holes produced during strong field ionization can occur in typical experimental conditions and does not require relativistic intensities or strong magnetic fields. (paper)
Federal Laboratory Consortium — The Dynamics Lab replicates vibration environments for every Navy platform. Testing performed includes: Flight Clearance, Component Improvement, Qualification, Life...
Sternberg, Shlomo
2010-01-01
Celebrated mathematician Shlomo Sternberg, a pioneer in the field of dynamical systems, created this modern one-semester introduction to the subject for his classes at Harvard University. Its wide-ranging treatment covers one-dimensional dynamics, differential equations, random walks, iterated function systems, symbolic dynamics, and Markov chains. Supplementary materials offer a variety of online components, including PowerPoint lecture slides for professors and MATLAB exercises.""Even though there are many dynamical systems books on the market, this book is bound to become a classic. The the
Quantum dynamical study of low-energy photoelectron bands of 2 ...
gated theoretically, paying particular attention to the vibrational structure and to possible nonadiabatic coupling effects. ... the ground state, to the excitation of non-totally sym- ... (PENNA; see figure 1 for a schematic representation) has been ...
Grünbaum, Niels Nolsøe; Stenger, Marianne
2013-01-01
The findings reveal a positive relationship between dynamic capabilities and innovation performance in the case enterprises, as we would expect. It was, however, not possible to establish a positive relationship between innovation performance and profitability. Nor was there any positive...... relationship between dynamic capabilities and profitability....
Yao, Yao; Sun, Ke-Wei; Luo, Zhen; Ma, Haibo
2018-01-18
The accurate theoretical interpretation of ultrafast time-resolved spectroscopy experiments relies on full quantum dynamics simulations for the investigated system, which is nevertheless computationally prohibitive for realistic molecular systems with a large number of electronic and/or vibrational degrees of freedom. In this work, we propose a unitary transformation approach for realistic vibronic Hamiltonians, which can be coped with using the adaptive time-dependent density matrix renormalization group (t-DMRG) method to efficiently evolve the nonadiabatic dynamics of a large molecular system. We demonstrate the accuracy and efficiency of this approach with an example of simulating the exciton dissociation process within an oligothiophene/fullerene heterojunction, indicating that t-DMRG can be a promising method for full quantum dynamics simulation in large chemical systems. Moreover, it is also shown that the proper vibronic features in the ultrafast electronic process can be obtained by simulating the two-dimensional (2D) electronic spectrum by virtue of the high computational efficiency of the t-DMRG method.
Sannino, Francesco
2013-01-01
paradigm the physical scale and henceforth also the massive spectrum of the theory jump at the lower boundary of the conformal window. In particular we propose that a theory can suddenly jump from a Quantum Chromodynamics type spectrum, at the lower boundary of the conformal window, to a conformal one...... without particle interpretation. The jumping scenario, therefore, does not support a near-conformal dynamics of walking type. We will also discuss the impact of jumping dynamics on the construction of models of dynamical electroweak symmetry breaking....
Binney, James
2008-01-01
Since it was first published in 1987, Galactic Dynamics has become the most widely used advanced textbook on the structure and dynamics of galaxies and one of the most cited references in astrophysics. Now, in this extensively revised and updated edition, James Binney and Scott Tremaine describe the dramatic recent advances in this subject, making Galactic Dynamics the most authoritative introduction to galactic astrophysics available to advanced undergraduate students, graduate students, and researchers. Every part of the book has been thoroughly overhauled, and many section
Corno, S.E.
1995-01-01
Analytical methods for Space Dynamics of fission reactors, are presented. It is shown how a few sample problems in space dynamics can be solved, within the one and two group diffusion model, by purely analytical tools, essentially based on Laplace transform and complex Green function techniques. A quite suggestive generalization of this approach, applicable to the fluid core reactors, whose fuel is undergoing a violent mixing, is reported and briefly discussed. (author)
Kim, Du Gi
2005-08-01
This book introduces summary of structural dynamics, the reason of learning of structural dynamics, single-degree of freedom system, simple harmonic vibration and application, numerical analysis method, such as time domain and frequency domain and nonlinear system, multi-degree of freedom system random vibration over discrete distribution, continuous distribution and extreme value distribution, circumstance vibration, earth quake vibration, including input earthquake, and earthquake-resistant design and capacity spectrum method, wind oscillation wave vibration, vibration control and maintenance control.
Theoretical study of ultraviolet induced photodissociation dynamics of sulfuric acid
Murakami, Tatsuhiro; Ohta, Ayumi; Suzuki, Tomoya; Ikeda, Kumiko [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan); Danielache, Sebastian O. [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan); Earth-Life Science Institute (ELSI), Tokyo Institute of Technology (Japan); Department of Environmental Science and Techonology, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Yoohama 226-8502 (Japan); Nanbu, Shinkoh, E-mail: shinkoh.nanbu@sophia.ac.jp [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan)
2015-05-01
Highlights: • Photodissociation dynamics of H{sub 2}SO{sub 4} at low-lying electronically excited states were investigated. • Photochemical processes were simulated by on-the-fly ab initio MD. • Sulfuric acid after the excitation to the S{sub 1} state dissociated to HSO{sub 4}(1{sup 2}A″) + H({sup 2}S). • Sulfuric acid after the excitation to the S{sub 2} state dissociated to HSO{sub 4}(2{sup 2}A″) + H({sup 2}S). • The energy region of the UV spectra where NMD fractionation may occur is predicted. - Abstract: Photodissociation dynamics of sulfuric acid after excitation to the first and second excited states (S{sub 1} and S{sub 2}) were studied by an on-the-fly ab initio molecular dynamics simulations based on the Zhu–Nakamura version of the trajectory surface hopping (ZN-TSH). Forces acting on the nuclear motion were computed on-the-fly by CASSCF method with Dunning’s augmented cc-pVDZ basis set. It was newly found that the parent molecule dissociated into two reaction-channels (i) HSO{sub 4}(1{sup 2}A″) + H({sup 2}S) by S{sub 1}-excitation, and (ii) HSO{sub 4}(2{sup 2}A″) + H({sup 2}S) by S{sub 2}-excitation. The direct dissociation dynamics yield products different from the SO{sub 2} + 2OH fragments often presented in the literature. Both channels result in the same product and differs only in the electronic state of the HSO{sub 4} fragment{sub .} The trajectories running on S{sub 2} do not hop with S{sub 0} and a nonadiabatic transition happens at the S{sub 2}–S{sub 1} conical intersection located at a longer OH bond-length than the S{sub 1}–S{sub 0} intersection producing an electronic excited state (2{sup 2}A″) of HSO{sub 4} product.
Fragmentation dynamics of ionized neon clusters (Ne(n), n=3-14) embedded in helium nanodroplets.
Bonhommeau, David; Halberstadt, Nadine; Viel, Alexandra
2006-01-14
We report a theoretical study of the nonadiabatic fragmentation dynamics of ionized neon clusters embedded in helium nanodroplets for cluster sizes up to n=14 atoms. The dynamics of the neon atoms is modeled using the molecular dynamics with quantum transitions method of Tully [J. Chem. Phys. 93, 1061 (1990)] with the nuclei treated classically and transitions between electronic states quantum mechanically. The potential-energy surfaces are derived from a diatomics-in-molecules model to which induced dipole-induced dipole interactions are added. The effect of the spin-orbit interaction is also discussed. The helium environment is modeled by a friction force acting on charged atoms whose speed exceeds the critical Landau velocity. The dependence of the fragment size distribution on the friction strength and on the initial nanodroplet size is investigated. By comparing with the available experimental data obtained for Ne3+ and Ne4+, a reasonable value for the friction coefficient, the only parameter of the model, is deduced. This value is then used to predict the effect of the helium environment on the dissociation dynamics of larger neon clusters, n=5-14. The results show stabilization of larger fragments than in the gas phase, but fragmentation is not completely caged. In addition, two types of dynamics are characterized for Ne4+: fast and explosive, therefore leaving no time for friction to cool down the process when dynamics starts on one of the highest electronic states, and slower, therefore leading to some stabilization by helium when it starts on one of the lowest electronic states.
Doping effect on photoabsorption and charge-separation dynamics in light-harvesting organic molecule
Satoshi Ohmura
2016-01-01
Full Text Available Using ab-initio theoretical methods, we demonstrate possible enhancement of photo-conversion efficiency of an organic solar cell via intentional doping in molecular graphene-fullerene heterojunction [the hexabenzocoronene (HBC-triethylene glycol (TEG–C60 molecule]. Photoabsorption analysis indicates oxygen substitution into HBC leads to an extension of the spectra up to an infrared regime. A quantum-mechanical molecular dynamics simulation incorporating nonadiabatic electronic transitions reveals that a dissociated charge state (D+ and A- in the O-doped system is more stable than the pristine case due to the presence of an effective barrier by the TEG HOMO/LUMO level. We also find that oxygen doping in HBC enhances the intermolecular carrier mobility after charge separation. On the other hand, the pristine molecule undergoes rapid recombination between donor and acceptor charges at the interface. These analyses suggest that the graphene oxidation opens a new window in the application of organic super-molecules to solar cells.
Shamim, Tariq
2008-01-01
Automotive catalytic converters, which are employed to reduce engine exhaust emissions, are subjected to highly transient conditions during a typical driving cycle. These transient conditions arise from changes in driving mode, the hysteresis and flow lags of the feedback control system, and result in fluctuations of air-fuel ratio, exhaust gas flow rates and temperatures. The catalyst performance is also strongly influenced by the oxygen storage capacity. This paper presents a computational investigation of the effect of oxygen storage capacity on the dynamic behavior of an automotive catalytic converter subjected to modulations in exhaust gases. The modulations are generated by forcing the temporal variations in exhaust gases air-fuel ratio, gas flow rates and temperatures. The study employs a single-channel based, one-dimensional, non-adiabatic model. The results show that the imposed modulations cause a significant departure in the catalyst behavior from its steady behavior, and the oxygen storage capacity plays an important role in determining the catalyst's response to the imposed modulations. Modulations and oxygen storage capacity are found to have relatively greater influence on the catalyst's performance near stoichiometric conditions
Shamim, Tariq [Department of Mechanical Engineering, The University of Michigan-Dearborn, Dearborn, MI 48128-2406 (United States)
2008-11-15
Automotive catalytic converters, which are employed to reduce engine exhaust emissions, are subjected to highly transient conditions during a typical driving cycle. These transient conditions arise from changes in driving mode, the hysteresis and flow lags of the feedback control system, and result in fluctuations of air-fuel ratio, exhaust gas flow rates and temperatures. The catalyst performance is also strongly influenced by the oxygen storage capacity. This paper presents a computational investigation of the effect of oxygen storage capacity on the dynamic behavior of an automotive catalytic converter subjected to modulations in exhaust gases. The modulations are generated by forcing the temporal variations in exhaust gases air-fuel ratio, gas flow rates and temperatures. The study employs a single-channel based, one-dimensional, non-adiabatic model. The results show that the imposed modulations cause a significant departure in the catalyst behavior from its steady behavior, and the oxygen storage capacity plays an important role in determining the catalyst's response to the imposed modulations. Modulations and oxygen storage capacity are found to have relatively greater influence on the catalyst's performance near stoichiometric conditions. (author)
Elkins, Madeline H.; Williams, Holly L. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Neumark, Daniel M., E-mail: dneumark@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)
2016-05-14
The excited state relaxation dynamics of the solvated electron in H{sub 2}O and D{sub 2}O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H{sub 2}O and 102 ± 8 fs in D{sub 2}O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.
Doping effect on photoabsorption and charge-separation dynamics in light-harvesting organic molecule
Ohmura, Satoshi, E-mail: s.ohmura.m4@cc.it-hiroshima.ac.jp [Research Center for Condensed Matter Physics, Department of Civil Engineering and Urban Design, Hiroshima Institute of Technology, Hiroshima 731-5193 (Japan); Tsuruta, Kenji [Department of Electrical and Electronic Engineering, Okayama University, Okayama 700-8530 (Japan); Shimojo, Fuyuki [Department of Physics, Kumamoto University, Kumamoto 860-8555 Japan (Japan); Nakano, Aiichiro [Collaboratory for Advanced Computing and Simulations, Department of Computer Science, Department of Physics & Astronomy, Department of Chemical Engineering & Materials Science, Department of Biological Sciences, University of Southern California, CA90089-024 (United States)
2016-01-15
Using ab-initio theoretical methods, we demonstrate possible enhancement of photo-conversion efficiency of an organic solar cell via intentional doping in molecular graphene-fullerene heterojunction [the hexabenzocoronene (HBC)-triethylene glycol (TEG)–C{sub 60} molecule]. Photoabsorption analysis indicates oxygen substitution into HBC leads to an extension of the spectra up to an infrared regime. A quantum-mechanical molecular dynamics simulation incorporating nonadiabatic electronic transitions reveals that a dissociated charge state (D{sup +} and A{sup -}) in the O-doped system is more stable than the pristine case due to the presence of an effective barrier by the TEG HOMO/LUMO level. We also find that oxygen doping in HBC enhances the intermolecular carrier mobility after charge separation. On the other hand, the pristine molecule undergoes rapid recombination between donor and acceptor charges at the interface. These analyses suggest that the graphene oxidation opens a new window in the application of organic super-molecules to solar cells.
SELF-HEALING NANOMATERIALS: MULTIMILLION-ATOM REACTIVE MOLECULAR DYNAMICS SIMULATIONS
Hakamata, Tomoya [Kumamoto Univ., Kumamoto (Japan); Shimamura, Kohei [Kumamoto Univ., Kumamoto (Japan); Univ. of Southern California, Los Angeles, CA (United States); Kobe Univ., Kobe (Japan); Shimojo, Fuyuki [Kumamoto Univ., Kumamoto (Japan); Kalia, Rajiv K. [Univ. of Southern California, Los Angeles, CA (United States); Nakano, Aiichiro [Univ. of Southern California, Los Angeles, CA (United States); Vashishta, Priya [Univ. of Southern California, Los Angeles, CA (United States)
2017-10-20
Organometal halide perovskites are attracting great attention as promising material for solar cells because of their high power conversion efficiency. The high performance has been attributed to the existence of free charge carriers and their large diffusion lengths, but the nature of carrier transport at the atomistic level remains elusive. Here, nonadiabatic quantum molecular dynamics simulations elucidate the mechanisms underlying the excellent free-carrier transport in CH_{3}NH_{3}PbI_{3}. Pb and I sublattices act as disjunct pathways for rapid and balanced transport of photoexcited electrons and holes, respectively, while minimizing efficiency-degrading charge recombination. On the other hand, CH_{3}NH_{3} sublattice quickly screens out electrostatic electron-hole attraction to generate free carriers within 1 ps. Together this nano-architecture lets photoexcited electrons and holes dissociate instantaneously and travel far away to be harvested before dissipated as heat. As a result, this work provides much needed structure-property relationships and time-resolved information that potentially lead to rational design of efficient solar cells.
1991-01-01
Dynamical Bifurcation Theory is concerned with the phenomena that occur in one parameter families of dynamical systems (usually ordinary differential equations), when the parameter is a slowly varying function of time. During the last decade these phenomena were observed and studied by many mathematicians, both pure and applied, from eastern and western countries, using classical and nonstandard analysis. It is the purpose of this book to give an account of these developments. The first paper, by C. Lobry, is an introduction: the reader will find here an explanation of the problems and some easy examples; this paper also explains the role of each of the other paper within the volume and their relationship to one another. CONTENTS: C. Lobry: Dynamic Bifurcations.- T. Erneux, E.L. Reiss, L.J. Holden, M. Georgiou: Slow Passage through Bifurcation and Limit Points. Asymptotic Theory and Applications.- M. Canalis-Durand: Formal Expansion of van der Pol Equation Canard Solutions are Gevrey.- V. Gautheron, E. Isambe...
Sharifi, Reza; Anvari-Moghaddam, Amjad; Fathi, S. Hamid
2017-01-01
Dynamic pricing scheme, also known as real-time pricing (RTP), can be more efficient and technically beneficial than the other price-based schemes (such as flat-rate or time-of-use (TOU) pricing) for enabling demand response (DR) actions. Over the past few years, advantages of RTP-based schemes h...... of dynamic pricing can lead to increased willingness of consumers to participate in DR programs which in turn improve the operation of liberalized electricity markets.......Dynamic pricing scheme, also known as real-time pricing (RTP), can be more efficient and technically beneficial than the other price-based schemes (such as flat-rate or time-of-use (TOU) pricing) for enabling demand response (DR) actions. Over the past few years, advantages of RTP-based schemes...
Robe, Dominic M.; Boettcher, Stefan; Sibani, Paolo
2016-01-01
When quenched rapidly beyond their glass transition, colloidal suspensions fall out of equilibrium. The pace of their dynamics then slows down with the system age, i.e., with the time elapsed after the quench. This breaking of time translational invariance is associated with dynamical observables...... which depend on two time-arguments. The phenomenology is shared by a broad class of aging systems and calls for an equally broad theoretical description. The key idea is that, independent of microscopic details, aging systems progress through rare intermittent structural relaxations that are de......-facto irreversible and become increasingly harder to achieve. Thus, a progression of record-sized dynamical barriers are traversed in the approach to equilibration. Accordingly, the statistics of the events is closely described by a log-Poisson process. Originally developed for relaxation in spin glasses...
Wang, Lingling; Huan, Guo; Momen, Roya; Azizi, Alireza; Xu, Tianlv; Kirk, Steven R; Filatov, Michael; Jenkins, Samantha
2017-06-29
A quantum theory of atoms in molecules (QTAIM) and stress tensor analysis was applied to analyze intramolecular interactions influencing the photoisomerization dynamics of a light-driven rotary molecular motor. For selected nonadiabatic molecular dynamics trajectories characterized by markedly different S 1 state lifetimes, the electron densities were obtained using the ensemble density functional theory method. The analysis revealed that torsional motion of the molecular motor blades from the Franck-Condon point to the S 1 energy minimum and the S 1 /S 0 conical intersection is controlled by two factors: greater numbers of intramolecular bonds before the hop-time and unusually strongly coupled bonds between the atoms of the rotor and the stator blades. This results in the effective stalling of the progress along the torsional path for an extended period of time. This finding suggests a possibility of chemical tuning of the speed of photoisomerization of molecular motors and related molecular switches by reshaping their molecular backbones to decrease or increase the degree of coupling and numbers of intramolecular bond critical points as revealed by the QTAIM/stress tensor analysis of the electron density. Additionally, the stress tensor scalar and vector analysis was found to provide new methods to follow the trajectories, and from this, new insight was gained into the behavior of the S 1 state in the vicinity of the conical intersection.
Halász, Gábor J; Csehi, András; Vibók, Ágnes; Cederbaum, Lorenz S
2014-12-26
Previous works have shown that dressing of diatomic molecules by standing or by running laser waves gives rise to the appearance of so-called light-induced conical intersections (LICIs). Because of the strong nonadiabatic couplings, the existence of such LICIs may significantly change the dynamical properties of a molecular system. In our former paper (J. Phys. Chem. A 2013, 117, 8528), the photodissociation dynamics of the D(2)(+) molecule were studied in the LICI framework starting the initial vibrational nuclear wave packet from the superposition of all the vibrational states initially produced by ionizing D(2). The present work complements our previous investigation by letting the initial nuclear wave packets start from different individual vibrational levels of D(2)(+), in particular, above the energy of the LICI. The kinetic energy release spectra, the total dissociation probabilities, and the angular distributions of the photofragments are calculated and discussed. An interesting phenomenon has been found in the spectra of the photofragments. Applying the light-induced adiabatic picture supported by LICI, explanations are given for the unexpected structure of the spectra.
Birkhoff, George D
1927-01-01
His research in dynamics constitutes the middle period of Birkhoff's scientific career, that of maturity and greatest power. -Yearbook of the American Philosophical Society The author's great book€¦is well known to all, and the diverse active modern developments in mathematics which have been inspired by this volume bear the most eloquent testimony to its quality and influence. -Zentralblatt MATH In 1927, G. D. Birkhoff wrote a remarkable treatise on the theory of dynamical systems that would inspire many later mathematicians to do great work. To a large extent, Birkhoff was writing about his o
Jensen, Henrik J.; Sibani, Paolo
2007-01-01
The term glassy dynamics is often used to refer to the extremely slow relaxation observed in several types of many component systems. The time span needed to reach a steady, time independent, state will typically be far beyond experimentally accessible time scales. When melted alloys are cooled...... down they typically do not enter a crystalline ordered state. Instead the atoms retain the amorphous arrangement characteristic of the liquid high temperature phase while the mobility of the molecules decreases very many orders of magnitude. This colossal change in the characteristic dynamical time...
Frelich, Lee
2016-01-01
Forest dynamics encompass changes in stand structure, species composition, and species interactions with disturbance and environment over a range of spatial and temporal scales. For convenience, spatial scale is defined as individual tree, neighborhood, stand, and landscape. Whether a given canopy-leveling disturbance will initiate a sequence of development in structure with little change in composition or initiate an episode of succession depends on a match or mismatch, respectively, with traits of the dominant tree species that allow the species to survive disturbance. When these match, certain species-disturbance type combinations lock in a pattern of stand and landscape dynamics that can persist for several generations of trees; thus, dominant tree species regulate, as well as respond to, disturbance. A complex interaction among tree species, neighborhood effects, disturbance type and severity, landform, and soils determines how stands of differing composition form and the mosaic of stands that compose the landscape. Neighborhood effects (e.g., serotinous seed rain, sprouting, shading, leaf-litter chemistry, and leaf-litter physical properties) operate at small spatial extents of the individual tree and its neighbors but play a central role in forest dynamics by contributing to patch formation at stand scales and dynamics of the entire landscape. Dominance by tree species with neutral to negative neighborhood effects leads to unstable landscape dynamics in disturbance-prone regions, wherein most stands are undergoing succession; stability can only occur under very low-severity disturbance regimes. Dominance by species with positive effects leads to stable landscape dynamics wherein only a small proportion of stands undergo succession at any one time. Positive neighborhood effects are common in temperate and boreal zones, whereas negative effects are more common in tropical climates. Landscapes with positive dynamics have alternate categories of dynamics
Greenwood, Donald T
1997-01-01
Graduate-level text for science and technology students provides strong background in the more abstract and intellectually satisfying areas of dynamical theory. Topics include d'Alembert's principle and the idea of virtual work, Hamilton's equations, Hamilton-Jacobi theory, canonical transformations, more. Problems and references at chapter ends.
Knoll, J.
1985-10-01
A quantum dynamical model is suggested which describes the expansion and disassembly phase of highly excited compounds formed in energetic heavy-ion collisions. First applications in two space and one time dimensional model world are discussed and qualitatively compared to standard freeze-out concepts. (orig.)
Bendix, Pól Martin
2015-01-01
Current topics include membrane-protein interactions with regard to membrane deformation or curvature sensing by BAR domains. Also, we study the dynamics of membrane tubes of both cells and simple model membrane tubes. Finally, we study membrane phase behavior which has important implications...... for the lateral organization of membranes as wells as for physical properties like bending, permeability and elasticity...
Bennett, D.L.; Brene, N.; Nielsen, H.B.
1986-06-01
The goal of random dynamics is the derivation of the laws of Nature as we know them (standard model) from inessential assumptions. The inessential assumptions made here are expressed as sets of general models at extremely high energies: gauge glass and spacetime foam. Both sets of models lead tentatively to the standard model. (orig.)
Díez, F.J.; Gerven, M.A.J. van; Sucar, L.E.; Morales, E.F.; Hoey, J.
2011-01-01
One of the objectives of artificial intelligence is to build decision-support models for systems that evolve over time and include several types of uncertainty. Dynamic limited-memory influence diagrams (DLIMIDs) are a new type of model proposed recently for this kind of problems. DLIMIDs are
Morecroft, John
System dynamics is an approach for thinking about and simulating situations and organisations of all kinds and sizes by visualising how the elements fit together, interact and change over time. This chapter, written by John Morecroft, describes modern system dynamics which retains the fundamentals developed in the 1950s by Jay W. Forrester of the MIT Sloan School of Management. It looks at feedback loops and time delays that affect system behaviour in a non-linear way, and illustrates how dynamic behaviour depends upon feedback loop structures. It also recognises improvements as part of the ongoing process of managing a situation in order to achieve goals. Significantly it recognises the importance of context, and practitioner skills. Feedback systems thinking views problems and solutions as being intertwined. The main concepts and tools: feedback structure and behaviour, causal loop diagrams, dynamics, are practically illustrated in a wide variety of contexts from a hot water shower through to a symphony orchestra and the practical application of the approach is described through several real examples of its use for strategic planning and evaluation.
Roelvink, J.A.; Steetzel, H.J.; Bliek, A.; Rakhorst, H.D.; Roelse, P.; Bakker, W.T.
1998-01-01
This book deals on "Coastal Dynamics", which will be defined in a narrow sense as a mathematical theory, which starts from given equations of motion for the sediment, which leads with the continuity equation and given boundary conditions to a calculated (eventually schematized) coastal topography,
Strømmen, Einar N
2014-01-01
This book introduces to the theory of structural dynamics, with focus on civil engineering structures that may be described by line-like beam or beam-column type of systems, or by a system of rectangular plates. Throughout this book the mathematical presentation contains a classical analytical description as well as a description in a discrete finite element format, covering the mathematical development from basic assumptions to the final equations ready for practical dynamic response predictions. Solutions are presented in time domain as well as in frequency domain. Structural Dynamics starts off at a basic level and step by step brings the reader up to a level where the necessary safety considerations to wind or horizontal ground motion induced dynamic design problems can be performed. The special theory of the tuned mass damper has been given a comprehensive treatment, as this is a theory not fully covered elsewhere. For the same reason a chapter on the problem of moving loads on beams has been included.
Bennett, D.L.
1987-01-01
The goal of random dynamics is the derivation of the laws of Nature as we know them (standard model) from inessential assumptions. The inessential assumptions made here are expressed as sets of general models at extremely high energies: Gauge glass and spacetime foam. Both sets of models lead tentatively to the standard model. (orig.)
Bennett, D. L.; Brene, N.; Nielsen, H. B.
1987-01-01
The goal of random dynamics is the derivation of the laws of Nature as we know them (standard model) from inessential assumptions. The inessential assumptions made here are expressed as sets of general models at extremely high energies: gauge glass and spacetime foam. Both sets of models lead tentatively to the standard model.
Sodium Ion Dynamics in the Magnetospheric Flanks of Mercury
Aizawa, S.; Delcourt, D.; Terada, N.
2018-05-01
We examine the particle transport via the Kelvin-Helmholtz instability by using simulation. The heavy ions of planetary origin such as Na+ may experience prominent nonadiabatic energization as they ExB drift across large-scale rolled up vortices.
Imaging Spin Dynamics on the Nanoscale using X-Ray Microscopy
Hermann eStoll
2015-04-01
Full Text Available The dynamics of emergent magnetic quasiparticles, such as vortices, domain walls, and bubbles are studied by scanning transmission x-ray microscopy (STXM, combining magnetic (XMCD contrast with about 25 nm lateral resolution as well as 70 ps time resolution. Essential progress in the understanding of magnetic vortex dynamics is achieved by vortex core reversal observed by sub-GHz excitation of the vortex gyromode, either by ac magnetic fields or spin transfer torque. The basic switching scheme for this vortex core reversal is the generation of a vortex-antivortex pair. Much faster vortex core reversal is obtained by exciting azimuthal spin wave modes with (multi-GHz rotating magnetic fields or orthogonal monopolar field pulses in x and y direction, down to 45 ps in duration. In that way unidirectional vortex core reversal to the vortex core 'down' or 'up' state only can be achieved with switching times well below 100 ps. Coupled modes of interacting vortices mimic crystal properties. The individual vortex oscillators determine the properties of the ensemble, where the gyrotropic mode represents the fundamental excitation. By self-organized state formation we investigate distinct vortex core polarization configurations and understand these eigenmodes in an extended Thiele model. Analogies with photonic crystals are drawn. Oersted fields and spin-polarized currents are used to excite the dynamics of domain walls and magnetic bubbles. From the measured phase and amplitude of the displacement of domain walls we deduce the size of the non-adiabatic spin-transfer torque. For sensing applications, the displacement of domain walls is studied and a direct correlation between domain wall velocity and spin structure is found. Finally the synchronous displacement of multiple domain walls using perpendicular field pulses is demonstrated as a possible paradigm shift for magnetic memory and logic applications.
Dynamics of H+ + CO at ELab = 30 eV
Stopera, Christopher; Maiti, Buddhadev; Grimes, Thomas V.; McLaurin, Patrick M.; Morales, Jorge A.
2012-02-01
The astrophysically relevant system H+ + CO (vi = 0) → H+ + CO (vf) at ELab = 30 eV is studied with the simplest-level electron nuclear dynamics (SLEND) method. This investigation follows previous successful SLEND studies of H+ + H2 and H+ + N2 at ELab = 30 eV [J. Morales, A. Diz, E. Deumens, and Y. Öhrn, J. Chem. Phys. 103(23), 9968 (1995), 10.1063/1.469886; C. Stopera, B. Maiti, T. V. Grimes, P. M. McLaurin, and J. A. Morales, J. Chem. Phys. 134(22), 224308 (2011), 10.1063/1.3598511]. SLEND is a direct, time-dependent, variational, and non-adiabatic method that adopts a classical-mechanics description for the nuclei and a single-determinantal wavefunction for the electrons. A canonical coherent-states (CS) procedure associated with SLEND reconstructs quantum vibrational properties from the SLEND classical dynamics. Present SLEND results include reactivity predictions, snapshots of the electron density evolution, average vibrational energy transfers, rainbow angle predictions, total and vibrationally resolved differential cross sections (DCS), and average vibrational excitation probabilities. SLEND results are compared with available data from experiments and vibrational close-coupling rotational infinite-order sudden (VCC-RIOS) approximation calculations. Present simulations employ four basis sets: STO-3G, 6-31G, 6-31G**, and cc-pVDZ to determine their effect on the results. SLEND simulations predict non-charge-transfer scattering and CO collision-induced dissociation as the main reactions. SLEND/6-31G, /6-31G**, and /cc-pVDZ predict rainbow angles and total DCS in excellent agreement with experiments and more accurate than their VCC-RIOS counterparts. SLEND/6-31G** and /cc-pVDZ predict vibrationally resolved DCS for vf = 0-2 in satisfactory experimental agreement, but less accurate than their comparable H+ + CO VCC-RIOS and H+ + H2 and H+ + N2 SLEND results. SLEND/6-31G** and /cc-pVDZ predict qualitatively correct average vibrational excitation probabilities
Schiehlen, Werner
2014-01-01
Applied Dynamics is an important branch of engineering mechanics widely applied to mechanical and automotive engineering, aerospace and biomechanics as well as control engineering and mechatronics. The computational methods presented are based on common fundamentals. For this purpose analytical mechanics turns out to be very useful where D’Alembert’s principle in the Lagrangian formulation proves to be most efficient. The method of multibody systems, finite element systems and continuous systems are treated consistently. Thus, students get a much better understanding of dynamical phenomena, and engineers in design and development departments using computer codes may check the results more easily by choosing models of different complexity for vibration and stress analysis.
Bendixen, Mette
. The warming air temperature affects the soil temperature and permafrost thaws and destabilizes the material in the coastal zone. In Greenland, the warming temperature lowers the surface mass balance of the Greenland Ice Sheet and more material is transported to the coastal zone. The sea ice extent is thinning...... of a fjord and the second type is a wider fan-shaped open delta. Most deltas are directly coupled to the Greenland Ice Sheet or local icecaps and are highly influenced by the dynamics in the catchments. It is demonstrated how a modern changing climate directly affects delta dynamics, and that Greenlandic...... deltas are prograding, contrary to the global trend showing eroding Arctic coasts. Moreover, it is revealed that the increasing proglacial freshwater runoff, caused by a lowering of the surface mass balance of the Greenland Ice Sheet is the main determining agent in delta progradation. The final part...
Bernard, Peter S
2015-01-01
This book presents a focused, readable account of the principal physical and mathematical ideas at the heart of fluid dynamics. Graduate students in engineering, applied math, and physics who are taking their first graduate course in fluids will find this book invaluable in providing the background in physics and mathematics necessary to pursue advanced study. The book includes a detailed derivation of the Navier-Stokes and energy equations, followed by many examples of their use in studying the dynamics of fluid flows. Modern tensor analysis is used to simplify the mathematical derivations, thus allowing a clearer view of the physics. Peter Bernard also covers the motivation behind many fundamental concepts such as Bernoulli's equation and the stream function. Many exercises are designed with a view toward using MATLAB or its equivalent to simplify and extend the analysis of fluid motion including developing flow simulations based on techniques described in the book.
Gömöry, F [Bratislava, Inst. Elect. Eng. (Slovakia)
2014-07-01
Superconductors used in magnet technology could carry extreme currents because of their ability to keep the magnetic flux motionless. The dynamics of the magnetic flux interaction with superconductors is controlled by this property. The cases of electrical transport in a round wire and the magnetization of wires of various shapes (circular, elliptical, plate) in an external magnetic field are analysed. Resistance to the magnetic field penetration means that the field produced by the superconducting magnet is no longer proportional to the supplied current. It also leads to a dissipation of electromagnetic energy. In conductors with unequal transverse dimensions, such as flat cables, the orientation with respect to the magnetic field plays an essential role. A reduction of magnetization currents can be achieved by splitting the core of a superconducting wire into fine filaments; however, new kinds of electrical currents that couple the filaments consequently appear. Basic formulas allowing qualitative analyses of various flux dynamic cases are presented.
Abell, D; Adelmann, A; Amundson, J; Dragt, A; Mottershead, C; Neri, F; Pogorelov, I; Qiang, J; Ryne, R; Shalf, J; Siegerist, C; Spentzouris, P; Stern, E; Venturini, M; Walstrom, P
2006-01-01
We describe some of the accomplishments of the Beam Dynamics portion of the SciDAC Accelerator Science and Technology project. During the course of the project, our beam dynamics software has evolved from the era of different codes for each physical effect to the era of hybrid codes combining start-of-the-art implementations for multiple physical effects to the beginning of the era of true multi-physics frameworks. We describe some of the infrastructure that has been developed over the course of the project and advanced features of the most recent developments, the interplay betwen beam studies and simulations and applications to current machines at Fermilab. Finally we discuss current and future plans for simulations of the International Linear Collider
Vilasi, Gaetano
2001-01-01
This is both a textbook and a monograph. It is partially based on a two-semester course, held by the author for third-year students in physics and mathematics at the University of Salerno, on analytical mechanics, differential geometry, symplectic manifolds and integrable systems. As a textbook, it provides a systematic and self-consistent formulation of Hamiltonian dynamics both in a rigorous coordinate language and in the modern language of differential geometry. It also presents powerful mathematical methods of theoretical physics, especially in gauge theories and general relativity. As a m
Carleson, Lennart
1993-01-01
Complex dynamics is today very much a focus of interest. Though several fine expository articles were available, by P. Blanchard and by M. Yu. Lyubich in particular, until recently there was no single source where students could find the material with proofs. For anyone in our position, gathering and organizing the material required a great deal of work going through preprints and papers and in some cases even finding a proof. We hope that the results of our efforts will be of help to others who plan to learn about complex dynamics and perhaps even lecture. Meanwhile books in the field a. re beginning to appear. The Stony Brook course notes of J. Milnor were particularly welcome and useful. Still we hope that our special emphasis on the analytic side will satisfy a need. This book is a revised and expanded version of notes based on lectures of the first author at UCLA over several \\Vinter Quarters, particularly 1986 and 1990. We owe Chris Bishop a great deal of gratitude for supervising the production of cour...
Mondal, Padmabati; Granucci, Giovanni; Rastädter, Dominique; Persico, Maurizio; Burghardt, Irene
2018-05-28
The photoregulation of nucleic acids by azobenzene photoswitches has recently attracted considerable interest in the context of emerging biotechnological applications. To understand the mechanism of photoinduced isomerisation and conformational control in these complex biological environments, we employ a Quantum Mechanics/Molecular Mechanics (QM/MM) approach in conjunction with nonadiabatic Surface Hopping (SH) dynamics. Two representative RNA-azobenzene complexes are investigated, both of which contain the azobenzene chromophore covalently attached to an RNA double strand via a β-deoxyribose linker. Due to the pronounced constraints of the local RNA environment, it is found that trans -to- cis isomerization is slowed down to a time scale of ∼10-15 picoseconds, in contrast to 500 femtoseconds in vacuo , with a quantum yield reduced by a factor of two. By contrast, cis -to- trans isomerization remains in a sub-picosecond regime. A volume-conserving isomerization mechanism is found, similarly to the pedal-like mechanism previously identified for azobenzene in solution phase. Strikingly, the chiral RNA environment induces opposite right-handed and left-handed helicities of the ground-state cis -azobenzene chromophore in the two RNA-azobenzene complexes, along with an almost completely chirality conserving photochemical pathway for these helical enantiomers.
Tamura, Hiroyuki; Huix-Rotllant, Miquel; Burghardt, Irene; Olivier, Yoann; Beljonne, David
2015-09-01
Singlet excitons in π -stacked molecular crystals can split into two triplet excitons in a process called singlet fission that opens a route to carrier multiplication in photovoltaics. To resolve controversies about the mechanism of singlet fission, we have developed a first principles nonadiabatic quantum dynamical model that reveals the critical role of molecular stacking symmetry and provides a unified picture of coherent versus thermally activated singlet fission mechanisms in different acenes. The slip-stacked equilibrium packing structure of pentacene derivatives is found to enhance ultrafast singlet fission mediated by a coherent superexchange mechanism via higher-lying charge transfer states. By contrast, the electronic couplings for singlet fission strictly vanish at the C2 h symmetric equilibrium π stacking of rubrene. In this case, singlet fission is driven by excitations of symmetry-breaking intermolecular vibrations, rationalizing the experimentally observed temperature dependence. Design rules for optimal singlet fission materials therefore need to account for the interplay of molecular π -stacking symmetry and phonon-induced coherent or thermally activated mechanisms.
Ding Guoliang; Zhang Chunlu; Lu Zhili
2004-01-01
In order to reduce the greenhouse gas emissions, efficient household refrigerator/freezers (RFs) are required. Bypass two-circuit cycle RFs with one compressor are proved to be more efficient than two-evaporator in series cycle RFs. In order to study the characteristics and improve the design of bypass two-circuit cycle RFs, a dynamic model is developed in this paper. In part I, the mathematic models of all components are presented, considering not only the accuracy of the models but also the computation stability and speed to solve the models. An efficiency model that requires a single calorimeter data point at the standard test condition is employed for compressor. A multi-zone model is employed for condenser and for evaporator, with its wall thermal capacity considered by effective metal method. The approximate integral analytic model is employed for adiabatic capillary tube, and the effective inlet enthalpy method is used to transfer the non-adiabatic capillary tube to adiabatic capillary tube. The z-transfer function model is employed for cabinet load calculation
Photodissociation dynamics of H2O at 111.5 nm by a vacuum ultraviolet free electron laser
Wang, Heilong; Yu, Yong; Chang, Yao; Su, Shu; Yu, Shengrui; Li, Qinming; Tao, Kai; Ding, Hongli; Yang, Jaiyue; Wang, Guanglei; Che, Li; He, Zhigang; Chen, Zhichao; Wang, Xingan; Zhang, Weiqing; Dai, Dongxu; Wu, Guorong; Yuan, Kaijun; Yang, Xueming
2018-03-01
Photodissociation dynamics of H2O via the F ˜ state at 111.5 nm were investigated using the high resolution H-atom Rydberg "tagging" time-of-flight (TOF) technique, in combination with the tunable vacuum ultraviolet free electron laser at the Dalian Coherent Light Source. The product translational energy distributions and angular distributions in both parallel and perpendicular directions were derived from the recorded TOF spectra. Based on these distributions, the quantum state distributions and angular anisotropy parameters of OH (X) and OH (A) products have been determined. For the OH (A) + H channel, highly rotationally excited OH (A) products have been observed. These products are ascribed to a fast direct dissociation on the B ˜ 1A1 state surface after multi-step internal conversions from the initial excited F ˜ state to the B ˜ state. While for the OH (X) + H channel, very highly rotationally excited OH (X) products with moderate vibrational excitation are revealed and attributed to the dissociation via a nonadiabatic pathway through the well-known two conical intersections between the B ˜ -state and the X ˜ -state surfaces.
Tanaka, Midori; Tanimura, Yoshitaka
2010-01-01
Multiple displaced oscillators coupled to an Ohmic heat bath are used to describe electron transfer (ET) in a dissipative environment. By performing a canonical transformation, the model is reduced to a multilevel system coupled to a heat bath with the Brownian spectral distribution. A reduced hierarchy equations of motion approach is introduced for numerically rigorous simulation of the dynamics of the three-level system with various oscillator configurations, for different nonadiabatic coupling strengths and damping rates, and at different temperatures. The time evolution of the reduced density matrix elements illustrates the interplay of coherences between the electronic and vibrational states. The ET reaction rates, defined as a flux-flux correlation function, are calculated using the linear response of the system to an external perturbation as a function of activation energy. The results exhibit an asymmetric inverted parabolic profile in a small activation regime due to the presence of the intermediate state between the reactant and product states and a slowly decaying profile in a large activation energy regime, which arises from the quantum coherent transitions.
Cooch, E. G.
2004-06-01
Full Text Available Increases or decreases in the size of populations over space and time are, arguably, the motivation for much of pure and applied ecological research. The fundamental model for the dynamics of any population is straightforward: the net change over time in the abundance of some population is the simple difference between the number of additions (individuals entering the population minus the number of subtractions (individuals leaving the population. Of course, the precise nature of the pattern and process of these additions and subtractions is often complex, and population biology is often replete with fairly dense mathematical representations of both processes. While there is no doubt that analysis of such abstract descriptions of populations has been of considerable value in advancing our, there has often existed a palpable discomfort when the ‘beautiful math’ is faced with the often ‘ugly realities’ of empirical data. In some cases, this attempted merger is abandoned altogether, because of the paucity of ‘good empirical data’ with which the theoretician can modify and evaluate more conceptually–based models. In some cases, the lack of ‘data’ is more accurately represented as a lack of robust estimates of one or more parameters. It is in this arena that methods developed to analyze multiple encounter data from individually marked organisms has seen perhaps the greatest advances. These methods have rapidly evolved to facilitate not only estimation of one or more vital rates, critical to population modeling and analysis, but also to allow for direct estimation of both the dynamics of populations (e.g., Pradel, 1996, and factors influencing those dynamics (e.g., Nichols et al., 2000. The interconnections between the various vital rates, their estimation, and incorporation into models, was the general subject of our plenary presentation by Hal Caswell (Caswell & Fujiwara, 2004. Caswell notes that although interest has traditionally
Zhao, Li; Liu, Jian-Yong; Zhou, Pan-Wang
2017-11-01
A detailed theoretical investigation based on the ab initio on-the-fly surface hopping dynamics simulations and potential energy surfaces calculations has been performed to unveil the mechanism of the photoinduced non-adiabatic relaxation process of the isolated blue fluorescent protein (BFP) chromophore in gas phase. The data analysis presents that the dominant reaction coordinate of the BFP chromophore is driven by a rotation motion around the CC double bridging bond, which is in remarkable difference with a previous result which supports a Hula-Twist rotation pattern. Such behavior is consistent with the double bond rotation pattern of the GFP neutral chromophore. In addition, the dynamics simulations give an estimated decay time of 1.1 ps for the S1 state, which is agrees well with the experimental values measured in proteins. The present work offers a straightforward understanding for the decay mechanism of the BFP chromophore and suggestions of the photochemical properties of analogous protein chromophores. We hope the current work would be helpful for further exploration of the BFP photochemical and photophysical properties in various environments, and can provide guidance and prediction for rational design of the fluorescent proteins catering for different demands.
Harding, L.K.; Donovan, I.A.
1986-01-01
The availability of new biliary radiopharamaceutical led to the expectation that the physiology and the pathophysiology of bile would be resolved. Some aspects of the physiology of bile have clarified and it has been shown that nasogastric intubation does not cause bile reflux. Careful analysis of excretion patterns has allowed detection of obstruction of the bile duct after cholecystectomy, and the radiopharmaceuticals have proved helpful in the diagnosis of acute colecystitis. In chronic cholecystitis, however, varying results have been obtained. Information on the incidence and amount of reflux in normal subjects is also confused, since several different techniques have been used with widely varying results. The clinical value of biliary dynamic studies is at present limited in patients with chronic cholecystitis, peptic ulcer, or symptoms suggestive of bile reflux. More data, with appropriate control subjects, is required to identify abnormal reflux, determine its effects, and decide on appropriate treatment
Stopping dynamics of ions passing through correlated honeycomb clusters
Balzer, Karsten; Schlünzen, Niclas; Bonitz, Michael
2016-12-01
A combined nonequilibrium Green functions-Ehrenfest dynamics approach is developed that allows for a time-dependent study of the energy loss of a charged particle penetrating a strongly correlated system at zero and finite temperatures. Numerical results are presented for finite inhomogeneous two-dimensional Fermi-Hubbard models, where the many-electron dynamics in the target are treated fully quantum mechanically and the motion of the projectile is treated classically. The simulations are based on the solution of the two-time Dyson (Keldysh-Kadanoff-Baym) equations using the second-order Born, third-order, and T -matrix approximations of the self-energy. As application, we consider protons and helium nuclei with a kinetic energy between 1 and 500 keV/u passing through planar fragments of the two-dimensional honeycomb lattice and, in particular, examine the influence of electron-electron correlations on the energy exchange between projectile and electron system. We investigate the time dependence of the projectile's kinetic energy (stopping power), the electron density, the double occupancy, and the photoemission spectrum. Finally, we show that, for a suitable choice of the Hubbard model parameters, the results for the stopping power are in fair agreement with ab initio simulations for particle irradiation of single-layer graphene.
Kwac, Kijeong; Geva, Eitan
2012-03-08
We present a mixed quantum-classical molecular dynamics study of the hydrogen-bonding structure and dynamics of a vibrationally excited hydroxyl stretch in methanol/carbon-tetrachloride mixtures. The adiabatic Hamiltonian of the quantum-mechanical hydroxyl is diagonalized on-the-fly to obtain the ground and first-excited adiabatic energy levels and wave functions which depend parametrically on the instantaneous configuration of the classical degrees of freedom. The dynamics of the classical degrees of freedom are determined by Hellmann-Feynman forces obtained by taking the expectation value of the force with respect to the ground or excited vibrational wave functions. Polarizable force fields are used which were previously shown to reproduce the experimental infrared absorption spectrum rather well, for different isotopomers and over a wide composition range [Kwac, K.; Geva, E. J. Phys. Chem. B 2011, 115, 9184]. We show that the agreement of the absorption spectra with experiment can be further improved by accounting for the dependence of the dipole moment derivatives on the configuration of the classical degrees of freedom. We find that the propensity of a methanol molecule to form hydrogen bonds increases upon photoexcitation of its hydroxyl stretch, thereby leading to a sizable red-shift of the corresponding emission spectrum relative to the absorption spectrum. Treating the relaxation from the first excited to the ground state as a nonadiabatic process, and calculating its rate within the framework of Fermi's golden rule and the harmonic-Schofield quantum correction factor, we were able to predict a lifetime which is of the same order of magnitude as the experimental value. The experimental dependence of the lifetime on the transition frequency is also reproduced. Nonlinear mapping relations between the hydroxyl transition frequency and bond length in the excited state and the electric field along the hydroxyl bond axis are established. These mapping relations
Scandiffio, A L
1990-12-01
Group dynamics play a significant role within any organization, culture, or unit. The important thing to remember with any of these structures is that they are made up of people--people with different ideas, motivations, background, and sometimes different agendas. Most groups, formal or informal, look for a leader in an effort to maintain cohesiveness of the unit. At times, that cultural bond must be developed; once developed, it must be nurtured. There are also times that one of the group no longer finds the culture comfortable and begins to act out behaviorally. It is these times that become trying for the leader as she or he attempts to remain objective when that which was once in the building phase of group cohesiveness starts to fall apart. At all times, the manager must continue to view the employee creating the disturbance as an integral part of the group. It is at this time that it is beneficial to perceive the employee exhibiting problem behaviors as a special employee, as one who needs the benefit of your experience and skills, as one who is still part of the group. It is also during this time that the manager should focus upon her or his own views in the area of power, communication, and the corporate culture of the unit that one has established before attempting to understand another's point of view. Once we understand our own motivation and accept ourselves, it is then that we may move on to offer assistance to another. Once we understand our insecurities recognizing staff dysfunction as a symptom of system dysfunction will not be so threatening to the concept of the manager that we perceive ourselves to be. It takes a secure person to admit that she or he favors staff before deciding to do something to change things. The important thing to know is that it can be done. The favored staff can find a new way of relating to others, the special employee can find new modes of behavior (and even find self-esteem in the process), the group can find new ways
Ruban, Anatoly I
This is the first book in a four-part series designed to give a comprehensive and coherent description of Fluid Dynamics, starting with chapters on classical theory suitable for an introductory undergraduate lecture course, and then progressing through more advanced material up to the level of modern research in the field. The present Part 1 consists of four chapters. Chapter 1 begins with a discussion of Continuum Hypothesis, which is followed by an introduction to macroscopic functions, the velocity vector, pressure, density, and enthalpy. We then analyse the forces acting inside a fluid, and deduce the Navier-Stokes equations for incompressible and compressible fluids in Cartesian and curvilinear coordinates. In Chapter 2 we study the properties of a number of flows that are presented by the so-called exact solutions of the Navier-Stokes equations, including the Couette flow between two parallel plates, Hagen-Poiseuille flow through a pipe, and Karman flow above an infinite rotating disk. Chapter 3 is d...
Lukose, Rajan Mathew
The World Wide Web and the Internet are rapidly expanding spaces, of great economic and social significance, which offer an opportunity to study many phenomena, often previously inaccessible, on an unprecedented scale and resolution with relative ease. These phenomena are measurable on the scale of tens of millions of users and hundreds of millions of pages. By virtue of nearly complete electronic mediation, it is possible in principle to observe the time and ``spatial'' evolution of nearly all choices and interactions. This cyber-space therefore provides a view into a number of traditional research questions (from many academic disciplines) and creates its own new phenomena accessible for study. Despite its largely self-organized and dynamic nature, a number of robust quantitative regularities are found in the aggregate statistics of interesting and useful quantities. These regularities can be understood with the help of models that draw on ideas from statistical physics as well as other fields such as economics, psychology and decision theory. This thesis develops models that can account for regularities found in the statistics of Internet congestion and user surfing patterns and discusses some practical consequences. practical consequences.
Photoisomerization and photodissociation dynamics of reactive free radicals
Bise, Ryan T. [Univ. of California, Berkeley, CA (United States)
2000-08-01
The photofragmentation pathways of chemically reactive free radicals have been examined using the technique of fast beam photofragment translational spectroscopy. Measurements of the photodissociation cross-sections, product branching ratios, product state energy distributions, and angular distributions provide insight into the excited state potential energy surfaces and nonadiabatic processes involved in the dissociation mechanisms. Photodissociation spectroscopy and dynamics of the predissociative $\\tilde{A}$^{2}A_{1} and $\\tilde{B}$^{2}A_{2} states of CH_{3}S have been investigated. At all photon energies, CH_{3} + S(^{3}P_{j}), was the main reaction channel. The translational energy distributions reveal resolved structure corresponding to vibrational excitation of the CH_{3} umbrella mode and the S(^{3}P_{j}) fine-structure distribution from which the nature of the coupled repulsive surfaces is inferred. Dissociation rates are deduced from the photofragment angular distributions, which depend intimately on the degree of vibrational excitation in the C-S stretch. Nitrogen combustion radicals, NCN, CNN and HNCN have also been studied. For all three radicals, the elimination of molecular nitrogen is the primary reaction channel. Excitation to linear excited triplet and singlet electronic states of the NCN radical generates resolved vibrational structure of the N_{2} photofragment. The relatively low fragment rotational excitation suggests dissociation via a symmetric C_{2V} transition state. Resolved vibrational structure of the N_{2} photofragment is also observed in the photodissociation of the HNCN radical. The fragment vibrational and rotational distributions broaden with increased excitation energy. Simple dissociation models suggest that the HNCN radical isomerizes to a cyclic intermediate (c-HCNN) which then dissociates via a tight cyclic
Many-electron effects in Lγ/sub 2,3/ x-ray emission spectroscopy of rare-earth elements
Ohno, M.; LaVilla, R.E.
1989-01-01
The Lγ/sub 2,3/(2s/sup -1/→4p/sup -1/) x-ray emission spectra of Nd 2 O 3 and Sm 2 O 3 were measured in order to study the strong configuration interaction between a 4p hole level and the double 4d hole 4f/sup (//sup n//sup +1)/ electron levels. The spectra are calculated also using the Green's function method. The agreement between theory and experiment is qualitatively good. The spectrum can be interpreted in terms of the spectral function of the final 4p hole where it is shown that the one-electron picture of the 4p hole breaks down due to the strong 4p/sup -1/left-right-arrow4d/sup -2/4f/sup (n+1)/ super Coster-Kronig process
Babamoradi, Mohsen, E-mail: babamoradi@iust.ac.ir [Department of Physics, Iran University of Science and Technology, Narmak,16846-13114 Tehran (Iran, Islamic Republic of); Asgari, Sussan [Department of Physics, Iran University of Science and Technology, Narmak,16846-13114 Tehran (Iran, Islamic Republic of); Ranjbar, Ahmad [Computational Materials Science Research Team, RIKEN Advanced Institute for Computational Science, Kobe, Hyogo 650-0047 (Japan); Belosludov, Rodion V. [Institute for Materials Research, Tohoku University, Sendai 980-8577 (Japan); Yunoki, Seiji [Computational Materials Science Research Team, RIKEN Advanced Institute for Computational Science, Kobe, Hyogo 650-0047 (Japan); Computational Condensed Matter Physics Laboratory, RIKEN, Wako, Saitama 351-0198 (Japan); Computational Quantum Matter Research Team, RIKEN Center for Emergent Matter Science, Wako, Saitama 351-0198 (Japan)
2017-01-15
A new model is applied to calculate the many-body properties of the neutral N3 color center in diamond. This model is based on the first-principles density functional theory (DFT) and cluster method, which is combined with the generalized Hubbard model. In contrast to the previous models for N3 centers, our model does not require the configuration interaction (CI) and molecular orbital (MO) techniques. The N3 defect in diamond is simulated with an empty site next to three substitutional nitrogen atoms in the center of a hydrogen-terminated diamond cluster. The method is shown to be highly accurate for describing the symmetries and spin properties of the ground state and the first dipole-allowed excited state for the N3 center. We obtain the transition energy as 412 nm for the first dipole-allowed transition, which is in good agreement with the corresponding experimental value as 415 nm. We assigned the dipole-allowed transition between the first and second excited states as the N2 optical peak, and evaluated the N2 optical peak to be 463 nm, which is close to the experimental value as 478 nm.
Rosenberger, Martina
1997-05-15
Method development of the time-dependent numerical MCSCF and CI method for atoms, without and with inclusion of an oscillating electric field, linearly polarized (electric dipole approximation for light). In the CI method, the numerical orbitals are kept fixed (not time-dependent), and only the CI coefficients are propagated, whereas in the MCSCF method both the CI coefficients and the numerical orbitals in the CSFs are propagated. The basis for this work were the non-relativistic numerical atomic structure codes for free atoms and for atoms in a static electric field developed at Bielefeld. (orig.)
Ohno, Masahide
2006-01-01
The Si K-LL resonant Auger-electron spectroscopy (RAES) spectra of silicon delta dopped layers in GaAs with very thin capping layers show both normal Auger decay and resonant Auger decay, when the core-level electron is excited to the conduction band. The resonant Auger peak kinetic energy (KE) shows no dispersion with photon energy, except when excited by the highest energy photons [M.D. Jackson, J.M.C. Thornton, D. Lewis, A. Robinson, M. Fahy, A. Aviary, P. Weightman, Phys. Rev. B71 (2005) 075313]. The RAES spectra are analyzed using a many-body theory. The presence of resonant Auger decay and no dispersion of resonant Auger peak KE with photon energy is explained in terms of the relaxation of a metastable excited core-hole state to a stable one on the time scale of core-hole decay. The excited electron in the conduction band either delocalizes rapidly leaving the ionized Si to decay by a normal Auger decay or drops to a state localized in the Si delta layer before the core-hole decays so that the RAES spectrum has both normal Auger decay and resonant Auger decay. As a result of the relaxation, the resonant Auger peak KE does not show any dispersion with photon energy. The variations with photon energy of the normal or resonant Auger peak intensity, KE, and width are explained in a consistent manner by a many-body theory
Many-electron theory of x-ray photoelectron spectra: N-shell linewidths in the 46Pd to 92U range
Ohno, M.; Wendin, G.
1985-01-01
The linewidths and energies of 4d holes (main lines in x-ray photoelectron spectra) are calculated for a number of elements in the range 70 Yb to 92 U, with use of nonrelativistic atomic many-body theory. The nonrelativistic Hartree-Fock frozen-core approximation for one-electron wave functions and Auger energies gives very good agreement with experiment. In the case of 4s and 4p holes, the Auger (in particular, super-Coster-Kronig) energies have to be calculated with inclusion of relaxation and relativistic effects. Combined with frozen-core, nonrelativistic one-electron wave functions, this gives good agreement with experimental energies and widths for 4s and 4p holes in 80 Hg. In conclusion, it is very important to include the effects of two final-state holes on the Auger electron, as well as the polarization response which screens the Auger emission matrix element. This latter effect is largely equivalent to the so-called exchange interaction between the Auger electron and the final-state holes
Tumakov, Dmitry A.; Telnov, Dmitry A.; Maltsev, Ilia A.; Plunien, Günter; Shabaev, Vladimir M.
2017-10-01
We develop an efficient numerical implementation of the relativistic time-dependent density functional theory (RTDDFT) to study multielectron highly-charged ions subject to intense linearly-polarized laser fields. The interaction with the electromagnetic field is described within the electric dipole approximation. The resulting time-dependent relativistic Kohn-Sham (RKS) equations possess an axial symmetry and are solved accurately and efficiently with the help of the time-dependent generalized pseudospectral method. As a case study, we calculate multiphoton ionization probabilities of the neutral argon atom and argon-like xenon ion. Relativistic effects are assessed by comparison of our present results with existing non-relativistic data.
Dynamical explanation for the experimentally observed μs lifetime for D3O
McLoughlin, P.W.; Gellene, G.I.
1990-01-01
The minimum energy pathway (MEP) for H atom addition to H 2 O has been determined by ab initio calculations at the MP3 level using a large Rydberg basis set. In agreement with previous theoretical studies, a local minimum in a C 3v geometry was found lying about 18.4 kcal/mol above the energy of H 2 O + H, but separated from the products by a 3.9 kcal/mol barrier. The well depth is sufficient to contain a quasi-bound zero point level, however, tunneling lifetimes, estimated to be 10 -13 to 10 -12 s, contrast sharply with the experimental results of neutralized ion beam studies which indicate a ∼1 μs lifetime for D 3 O. Exploration of the region of the potential energy surface around the MEP, shows the pathway to preserve a symmetry plane containing the H fragment and bisecting the H 2 O fragment (i.e., C s symmetry) with the dissociation coordinate lying in the A' coordinate subspace. Vibrationally adiabatic potential curves correlating to H 2 O products with excitation in the asymmetric stretch are found to have increased dissociation barriers for increased excitation with ∼μs lifetimes occurring for v ≥ 3. The interpretation that the experimentally observed metastability of D 3 O arises from this essentially dynamical dissociation barrier makes the radical a remarkable example of a quasi-bound species, lasting ∼1 μs with 10.5 kcal/mol of internal energy in excess of the semiclassical dissociation barrier. Isotope effects on the magnitude of possible nonadiabatic kinetic and potential couplings are estimated and discussed in light of the experimental lifetime scaling D 3 16 O>D 3 18 O≥H 3 16 O
Effect of vibrational excitation on the dynamics of ion-molecule reactions
Anderson, S.L.
1981-11-01
A new experimental technique for the study of vibrational effects on ion-molecule reaction cross sections is described. Vibrational and collision energy dependent cross sections are presented for proton and H atom transfer, charge transfer and collision induced dissociation reactions in various isotopic H 2 + + H 2 systems. Charge and proton transfer cross sections are presented for the reactions of H 2 + and D 2 + with Ar, N 2 , CO, and O 2 . All the reactions are shown to be highly influenced by avoided crossings between the ground and first excited potential energy surfaces. Because of the nature of the crossings, vibrational motion of the systems can cause both adiabatic and non-adiabatic behavior of the system. This makes the vibrational dependences of the various cross sections a very sensitive probe of the dynamics of the collisions particularly, their behavior in the region of the crossings. Evidence is seen for charge transfer between reagents as they approach each other, transition to and in some cases reactions on excited potential energy surfaces, competition between different channels, and strong coupling of proton and charge transfer channels which occurs only for two of the systems studied (H 2 + + Ar, N 2 ). Oscillatory structure is observed in the collision energy dependence of the endoergic H 2 + (v = 0) + Ar charge transfer reaction for the first time, and a simple model which is commonly used for atom-atom charge transfer is used to fit the peaks. Finally a simple model is used to assess the importance of energy resonance and Franck-Condon effects on molecular charge transfer
Zapukhlyak, Myroslav
2008-12-05
The present thesis gives a theoretical contribution to the understanding of the many-particle dynamics in inelastic ion-atom collisions. Many-electron dynamics in ion-helium collisions and proton-sodium collisions was theoretically studied. The description is based on the semiclassical approximation with the straight orbit for the projectile motion. The ion-atom collision problem is by this reduced to a time-dependent many-electron problem and in the non-relativistic approximation described by the time-dependent Schroedinger equation. The solution of the many-electron problem pursues in the framework of the time-dependent density functional theory. The time-dependent Schroedinger equation for the interacting many-electron problem is transformed to the system of the time-dependent Kohn-Sham equations and solved by the two-center-basis generator method. The unknown time-dependent exchange-correlation one-particle potential forces different approximation in the time-dependent Kohn-Shan scheme. In this thesis the model of the independent electrons was applied as basis model, in which the electron-electron correlation is consistently neglected in all parts and in all steps. Differential cross sections for different one- and two-electron processes were calculated in the so-called eikonal approximation for the collisional systems p-He, He{sup 2+}-He, and Ar{sup q+}-He (q=15-18). [German] Die vorliegende Arbeit leistet einen theoretischen Beitrag zum Verstaendnis der Vielteilchendynamik in inelastischen Ion-Atom-Stoessen. Vielelektronendynamik in Ion-Helium-Stoessen und Proton-Natrium-Stoessen wurde theoretisch untersucht. Die Beschreibung basiert auf der semiklassischen Naeherung mit der geraden Bahn fuer die Projektilbewegung. Das Ion-Atom- Stossproblem wird damit auf ein zeitabhaengiges Vielelektronenproblem reduziert und in der nichtrelativistischen Naeherung mit der zeitabhaengigen Schroedinger-Gleichung beschrieben. Die Loesung des Vielelektronenproblems erfolgt im
Shimojo, Fuyuki; Hattori, Shinnosuke; Kalia, Rajiv K.; Kunaseth, Manaschai; Mou, Weiwei; Nakano, Aiichiro; Nomura, Ken-ichi; Ohmura, Satoshi; Rajak, Pankaj; Shimamura, Kohei; Vashishta, Priya
2014-05-01
We introduce an extension of the divide-and-conquer (DC) algorithmic paradigm called divide-conquer-recombine (DCR) to perform large quantum molecular dynamics (QMD) simulations on massively parallel supercomputers, in which interatomic forces are computed quantum mechanically in the framework of density functional theory (DFT). In DCR, the DC phase constructs globally informed, overlapping local-domain solutions, which in the recombine phase are synthesized into a global solution encompassing large spatiotemporal scales. For the DC phase, we design a lean divide-and-conquer (LDC) DFT algorithm, which significantly reduces the prefactor of the O(N) computational cost for N electrons by applying a density-adaptive boundary condition at the peripheries of the DC domains. Our globally scalable and locally efficient solver is based on a hybrid real-reciprocal space approach that combines: (1) a highly scalable real-space multigrid to represent the global charge density; and (2) a numerically efficient plane-wave basis for local electronic wave functions and charge density within each domain. Hybrid space-band decomposition is used to implement the LDC-DFT algorithm on parallel computers. A benchmark test on an IBM Blue Gene/Q computer exhibits an isogranular parallel efficiency of 0.984 on 786 432 cores for a 50.3 × 106-atom SiC system. As a test of production runs, LDC-DFT-based QMD simulation involving 16 661 atoms is performed on the Blue Gene/Q to study on-demand production of hydrogen gas from water using LiAl alloy particles. As an example of the recombine phase, LDC-DFT electronic structures are used as a basis set to describe global photoexcitation dynamics with nonadiabatic QMD (NAQMD) and kinetic Monte Carlo (KMC) methods. The NAQMD simulations are based on the linear response time-dependent density functional theory to describe electronic excited states and a surface-hopping approach to describe transitions between the excited states. A series of techniques
Shimojo, Fuyuki; Hattori, Shinnosuke; Kalia, Rajiv K.; Mou, Weiwei; Nakano, Aiichiro; Nomura, Ken-ichi; Rajak, Pankaj; Vashishta, Priya; Kunaseth, Manaschai; Ohmura, Satoshi; Shimamura, Kohei
2014-01-01
We introduce an extension of the divide-and-conquer (DC) algorithmic paradigm called divide-conquer-recombine (DCR) to perform large quantum molecular dynamics (QMD) simulations on massively parallel supercomputers, in which interatomic forces are computed quantum mechanically in the framework of density functional theory (DFT). In DCR, the DC phase constructs globally informed, overlapping local-domain solutions, which in the recombine phase are synthesized into a global solution encompassing large spatiotemporal scales. For the DC phase, we design a lean divide-and-conquer (LDC) DFT algorithm, which significantly reduces the prefactor of the O(N) computational cost for N electrons by applying a density-adaptive boundary condition at the peripheries of the DC domains. Our globally scalable and locally efficient solver is based on a hybrid real-reciprocal space approach that combines: (1) a highly scalable real-space multigrid to represent the global charge density; and (2) a numerically efficient plane-wave basis for local electronic wave functions and charge density within each domain. Hybrid space-band decomposition is used to implement the LDC-DFT algorithm on parallel computers. A benchmark test on an IBM Blue Gene/Q computer exhibits an isogranular parallel efficiency of 0.984 on 786 432 cores for a 50.3 × 10 6 -atom SiC system. As a test of production runs, LDC-DFT-based QMD simulation involving 16 661 atoms is performed on the Blue Gene/Q to study on-demand production of hydrogen gas from water using LiAl alloy particles. As an example of the recombine phase, LDC-DFT electronic structures are used as a basis set to describe global photoexcitation dynamics with nonadiabatic QMD (NAQMD) and kinetic Monte Carlo (KMC) methods. The NAQMD simulations are based on the linear response time-dependent density functional theory to describe electronic excited states and a surface-hopping approach to describe transitions between the excited states. A series of
Contopoulos, G.
1983-01-01
In this paper, three main areas of relativistic stellar dynamics are reviewed: (a) The dynamics of clusters, or nuclei of galaxies, of very high density; (b) The dynamics of systems containing a massive black hole; and (c) The dynamics of particles (and photons) in an expanding Universe. The emphasis is on the use of orbit perturbations. (Auth.)
Principles of magnetoplasma dynamics
Woods, L.C.
1987-01-01
A self-contained account is given of magnetoplasma dynamics covering fluid dynamics, thermodynamics, kinetic theory of gases, particle dynamics and electromagnetism. The six chapter headings are, basic concepts, magnetohydrodynamics, dynamics of charged particles, transport in a magnetoplasma, magnetoplasma shock waves, and transport in tokamaks. There are 231 references. (U.K.)
Ultraviolet relaxation dynamics of aniline, N, N-dimethylaniline and 3,5-dimethylaniline at 250 nm
Thompson, James O. F.; Saalbach, Lisa; Crane, Stuart W. [Institute of Photonics and Quantum Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Paterson, Martin J. [Institute of Chemical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Townsend, Dave, E-mail: D.Townsend@hw.ac.uk [Institute of Photonics and Quantum Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Institute of Chemical Sciences, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom)
2015-03-21
Time-resolved photoelectron imaging was used to investigate the electronic relaxation dynamics of gas-phase aniline, N, N-dimethylaniline, and 3,5-dimethylaniline following ultraviolet excitation at 250 nm. Our analysis was supported by ab initio coupled-cluster calculations evaluating excited state energies and (in aniline) the evolution of a range of excited state physical properties as a function of N–H bond extension. Due to a lack of consistency between several earlier studies undertaken in aniline, the specific aim of this present work was to gain new insight into the previously proposed non-adiabatic coupling interaction between the two lowest lying singlet excited states S{sub 1}(ππ{sup ∗}) and S{sub 2}(3s/πσ{sup ∗}). The methyl-substituted systems N, N-dimethylaniline and 3,5-dimethylaniline were included in order to obtain more detailed dynamical information about the key internal molecular coordinates that drive the S{sub 1}(ππ{sup ∗})/S{sub 2}(3s/πσ{sup ∗}) coupling mechanism. Our findings suggest that in all three systems, both electronic states are directly populated during the initial excitation, with the S{sub 2}(3s/πσ{sup ∗}) state then potentially decaying via either direct dissociation along the N–X stretching coordinate (X = H or CH{sub 3}) or internal conversion to the S{sub 1}(ππ{sup ∗}) state. In aniline and N, N-dimethylaniline, both pathways most likely compete in the depletion of S{sub 2}(3s/πσ{sup ∗}) state population. However, in 3,5-dimethylaniline, only the direct dissociation mechanism appears to be active. This is rationalized in terms of changes in the relative rates of the two decay pathways upon methylation of the aromatic ring system.
Quantum state-to-state dynamics for the quenching process of Br(2P1/2) + H2(v(i) = 0, 1, j(i) = 0).
Xie, Changjian; Jiang, Bin; Xie, Daiqian; Sun, Zhigang
2012-03-21
Quantum state-to-state dynamics for the quenching process Br((2)P(1/2)) + H(2)(v(i) = 0, 1, j(i) = 0) → Br((2)P(3/2)) + H(2)(v(f), j(f)) has been studied based on two-state model on the recent coupled potential energy surfaces. It was found that the quenching probabilities have some oscillatory structures due to the interference of reflected flux in the Br((2)P(1/2)) + H(2) and Br((2)P(3/2)) + H(2) channels by repulsive potential in the near-resonant electronic-to-vibrational energy transfer process. The final vibrational state resolved integral cross sections were found to be dominated by the quenching process Br((2)P(1/2)) + H(2)(v) → Br((2)P(3/2)) + H(2)(v+1) and the nonadiabatic reaction probabilities for Br((2)P(1/2)) + H(2)(v = 0, 1, j(i) = 0) are quite small, which are consistent with previous theoretical and experimental results. Our calculated total quenching rate constant for Br((2)P(1/2)) + H(2)(v(i) = 0, j(i) = 0) at room temperature is in good agreement with the available experimental data. © 2012 American Institute of Physics
Vanicek, Jiri
2014-03-01
Rigorous quantum-mechanical calculations of coherent ultrafast electronic spectra remain difficult. I will present several approaches developed in our group that increase the efficiency and accuracy of such calculations: First, we justified the feasibility of evaluating time-resolved spectra of large systems by proving that the number of trajectories needed for convergence of the semiclassical dephasing representation/phase averaging is independent of dimensionality. Recently, we further accelerated this approximation with a cellular scheme employing inverse Weierstrass transform and optimal scaling of the cell size. The accuracy of potential energy surfaces was increased by combining the dephasing representation with accurate on-the-fly ab initio electronic structure calculations, including nonadiabatic and spin-orbit couplings. Finally, the inherent semiclassical approximation was removed in the exact quantum Gaussian dephasing representation, in which semiclassical trajectories are replaced by communicating frozen Gaussian basis functions evolving classically with an average Hamiltonian. Among other examples I will present an on-the-fly ab initio semiclassical dynamics calculation of the dispersed time-resolved stimulated emission spectrum of the 54-dimensional azulene. This research was supported by EPFL and by the Swiss National Science Foundation NCCR MUST (Molecular Ultrafast Science and Technology) and Grant No. 200021124936/1.
Quantum Dynamical Behaviour in Complex Systems - A Semiclassical Approach
Ananth, Nandini [Univ. of California, Berkeley, CA (United States)
2008-01-01
systems is described. We proposed the use of a semiclassical correction term to a preliminary quantum calculation using, for instance, a variational approach. This allows us to increase the accuracy significantly. Modeling Nonadiabatic dynamics has always been a challenge to classical simulations because the multi-state nature of the dynamics cannot be described accurately by the time evolution on a single average surface, as is the classical approach. We show that using the Meyer-Miller-Stock-Thoss (MMST) representation of the exact vibronic Hamiltonian in combination with the IVR allows us to accurately describe dynamics where the non Born-Oppenheimer regime. One final problem that we address is that of extending this method to the long time regime. We propose the use of a time independent sampling function in the Monte Carlo integration over the phase space of initial trajectory conditions. This allows us to better choose the regions of importance at the various points in time; by using more trajectories in the important regions, we show that the integration can be converged much easier. An algorithm based loosely on the methods of Diffusion Monte Carlo is developed that allows us to carry out this time dependent sampling in a most efficient manner.
Fundamentals of structural dynamics
Craig, Roy R
2006-01-01
From theory and fundamentals to the latest advances in computational and experimental modal analysis, this is the definitive, updated reference on structural dynamics.This edition updates Professor Craig's classic introduction to structural dynamics, which has been an invaluable resource for practicing engineers and a textbook for undergraduate and graduate courses in vibrations and/or structural dynamics. Along with comprehensive coverage of structural dynamics fundamentals, finite-element-based computational methods, and dynamic testing methods, this Second Edition includes new and e
PREFACE: Dynamics of low-dimensional systems Dynamics of low-dimensional systems
Bernasconi, M.; Miret-Artés, S.; Toennies, J. P.
2012-03-01
With the development of techniques for high-resolution inelastic helium atom scattering (HAS), electron scattering (EELS) and neutron spin echo spectroscopy, it has become possible, within approximately the last thirty years, to measure the dispersion curves of surface phonons in insulators, semiconductors and metals. In recent years, the advent of new experimental techniques such as 3He spin-echo spectroscopy, scanning inelastic electron tunnel spectroscopy, inelastic x-ray scattering spectroscopy and inelastic photoemission have extended surface phonon spectroscopy to a variety of systems. These include ultra-thin metal films, adsorbates at surface and elementary processes where surface phonons play an important role. Other important directions have been actively pursued in the past decade: the dynamics of stepped surfaces and clusters grown on metal surfaces, due to their relevance in many dynamical and chemical processes at surfaces, including heterogeneous catalysis; clusters; diffusion etc. The role of surface effects in these processes has been conjectured since the early days of surface dynamics, although only now is the availability of ab initio approaches providing those conjectures with a microscopic basis. Last but not least, the investigation of non-adiabatic effects, originating for instance from the hybridization (avoided crossing) of the surface phonons branches with the quasi 1D electron-hole excitation branch, is also a challenging new direction. Furthermore, other elementary oscillations such as surface plasmons are being actively investigated. The aforementioned experimental breakthroughs have been accompanied by advances in the theoretical study of atom-surface interaction. In particular, in the past decade first principles calculations based on density functional perturbation theory have boosted the theoretical study of the dynamics of low-dimensional systems. Phonon dispersion relations of clean surfaces, the dynamics of adsorbates, and the
Dynamic light scattering. Observation of polymer dynamics
Hiroi, Takashi
2015-01-01
Dynamic light scattering is a technique to measure properties of polymer solutions such as size distribution. Principle of dynamic light scattering is briefly explained. Sometime dynamic light scattering is regarded as the observation of Doppler shift of scattered light. First, the difficulty for the direct observation of this Doppler shift is mentioned. Then the measurement by using a time correlation function is introduced. Measuring techniques for dynamic light scattering are also introduced. In addition to homodyne and heterodyne detection techniques, the technique called partial heterodyne method is also introduced. This technique is useful for the analysis of nonergodic medium such as polymer gels. Then the application of this technique to condensed suspension is briefly reviewed. As one of the examples, a dynamic light scattering microscope is introduced. By using this apparatus, we can measure the concentration dependence of the size distribution of polymer solutions. (author)
Uranga-Piña, L. [Facultad de Física, Universidad de la Habana, San Lázaro y L, Vedado, 10400 Havana (Cuba); Institute for Chemistry and Biochemistry, Freie Universität Berlin, Takustr. 3, D-14195 Berlin (Germany); Tremblay, J. C., E-mail: jean.c.tremblay@gmail.com [Institute for Chemistry and Biochemistry, Freie Universität Berlin, Takustr. 3, D-14195 Berlin (Germany)
2014-08-21
We investigate the effect of inter-mode coupling on the vibrational relaxation dynamics of molecules in weak dissipative environments. The simulations are performed within the reduced density matrix formalism in the Markovian regime, assuming a Lindblad form for the system-bath interaction. The prototypical two-dimensional model system representing two CO molecules approaching a Cu(100) surface is adapted from an ab initio potential, while the diatom-diatom vibrational coupling strength is systematically varied. In the weak system-bath coupling limit and at low temperatures, only first order non-adiabatic uni-modal coupling terms contribute to surface-mediated vibrational relaxation. Since dissipative dynamics is non-unitary, the choice of representation will affect the evolution of the reduced density matrix. Two alternative representations for computing the relaxation rates and the associated operators are thus compared: the fully coupled spectral basis, and a factorizable ansatz. The former is well-established and serves as a benchmark for the solution of Liouville-von Neumann equation. In the latter, a contracted grid basis of potential-optimized discrete variable representation is tailored to incorporate most of the inter-mode coupling, while the Lindblad operators are represented as tensor products of one-dimensional operators, for consistency. This procedure results in a marked reduction of the grid size and in a much more advantageous scaling of the computational cost with respect to the increase of the dimensionality of the system. The factorizable method is found to provide an accurate description of the dissipative quantum dynamics of the model system, specifically of the time evolution of the state populations and of the probability density distribution of the molecular wave packet. The influence of intra-molecular vibrational energy redistribution appears to be properly taken into account by the new model on the whole range of coupling strengths. It
Dynamics of H+ + CO at E(Lab) = 30 eV.
Stopera, Christopher; Maiti, Buddhadev; Grimes, Thomas V; McLaurin, Patrick M; Morales, Jorge A
2012-02-07
The astrophysically relevant system H(+) + CO (v(i) = 0) → H(+) + CO (v(f)) at E(Lab) = 30 eV is studied with the simplest-level electron nuclear dynamics (SLEND) method. This investigation follows previous successful SLEND studies of H(+) + H(2) and H(+) + N(2) at E(Lab) = 30 eV [J. Morales, A. Diz, E. Deumens, and Y. Öhrn, J. Chem. Phys. 103(23), 9968 (1995); C. Stopera, B. Maiti, T. V. Grimes, P. M. McLaurin, and J. A. Morales, J. Chem. Phys. 134(22), 224308 (2011)]. SLEND is a direct, time-dependent, variational, and non-adiabatic method that adopts a classical-mechanics description for the nuclei and a single-determinantal wavefunction for the electrons. A canonical coherent-states (CS) procedure associated with SLEND reconstructs quantum vibrational properties from the SLEND classical dynamics. Present SLEND results include reactivity predictions, snapshots of the electron density evolution, average vibrational energy transfers, rainbow angle predictions, total and vibrationally resolved differential cross sections (DCS), and average vibrational excitation probabilities. SLEND results are compared with available data from experiments and vibrational close-coupling rotational infinite-order sudden (VCC-RIOS) approximation calculations. Present simulations employ four basis sets: STO-3G, 6-31G, 6-31G**, and cc-pVDZ to determine their effect on the results. SLEND simulations predict non-charge-transfer scattering and CO collision-induced dissociation as the main reactions. SLEND/6-31G, /6-31G**, and /cc-pVDZ predict rainbow angles and total DCS in excellent agreement with experiments and more accurate than their VCC-RIOS counterparts. SLEND/6-31G** and /cc-pVDZ predict vibrationally resolved DCS for v(f) = 0-2 in satisfactory experimental agreement, but less accurate than their comparable H(+) + CO VCC-RIOS and H(+) + H(2) and H(+) + N(2) SLEND results. SLEND∕6-31G** and ∕cc-pVDZ predict qualitatively correct average vibrational excitation probabilities
Dynamic statistical information theory
无
2006-01-01
In recent years we extended Shannon static statistical information theory to dynamic processes and established a Shannon dynamic statistical information theory, whose core is the evolution law of dynamic entropy and dynamic information. We also proposed a corresponding Boltzmman dynamic statistical information theory. Based on the fact that the state variable evolution equation of respective dynamic systems, i.e. Fokker-Planck equation and Liouville diffusion equation can be regarded as their information symbol evolution equation, we derived the nonlinear evolution equations of Shannon dynamic entropy density and dynamic information density and the nonlinear evolution equations of Boltzmann dynamic entropy density and dynamic information density, that describe respectively the evolution law of dynamic entropy and dynamic information. The evolution equations of these two kinds of dynamic entropies and dynamic informations show in unison that the time rate of change of dynamic entropy densities is caused by their drift, diffusion and production in state variable space inside the systems and coordinate space in the transmission processes; and that the time rate of change of dynamic information densities originates from their drift, diffusion and dissipation in state variable space inside the systems and coordinate space in the transmission processes. Entropy and information have been combined with the state and its law of motion of the systems. Furthermore we presented the formulas of two kinds of entropy production rates and information dissipation rates, the expressions of two kinds of drift information flows and diffusion information flows. We proved that two kinds of information dissipation rates (or the decrease rates of the total information) were equal to their corresponding entropy production rates (or the increase rates of the total entropy) in the same dynamic system. We obtained the formulas of two kinds of dynamic mutual informations and dynamic channel
Structure, Reactivity and Dynamics
Understanding structure, reactivity and dynamics is the core issue in chemical ... functional theory (DFT) calculations, molecular dynamics (MD) simulations, light- ... between water and protein oxygen atoms, the superionic conductors which ...
Ghanem, Bernard; Ahuja, Narendra
2013-01-01
This paper proposes the problem of modeling video sequences of dynamic swarms (DSs). We define a DS as a large layout of stochastically repetitive spatial configurations of dynamic objects (swarm elements) whose motions exhibit local spatiotemporal
Pilyugin, Sergei Yu
2012-01-01
Dynamical systems are abundant in theoretical physics and engineering. Their understanding, with sufficient mathematical rigor, is vital to solving many problems. This work conveys the modern theory of dynamical systems in a didactically developed fashion.In addition to topological dynamics, structural stability and chaotic dynamics, also generic properties and pseudotrajectories are covered, as well as nonlinearity. The author is an experienced book writer and his work is based on years of teaching.
Traag, V.A.; Reinanda, R.; Hicks, J.; van Klinken, G.; Aziz-Alaoui, M.A.; Bertelle, C.; Liu, X.; Olivier, D.
2014-01-01
Studies of human attention dynamics analyses how attention is focused on specific topics, issues or people. In online social media, there are clear signs of exogenous shocks, bursty dynamics, and an exponential or powerlaw lifetime distribution. We here analyse the attention dynamics of traditional
Intramolecular and nonlinear dynamics
Davis, M.J. [Argonne National Laboratory, IL (United States)
1993-12-01
Research in this program focuses on three interconnected areas. The first involves the study of intramolecular dynamics, particularly of highly excited systems. The second area involves the use of nonlinear dynamics as a tool for the study of molecular dynamics and complex kinetics. The third area is the study of the classical/quantum correspondence for highly excited systems, particularly systems exhibiting classical chaos.
PREFACE: Dynamics of wetting Dynamics of wetting
Grest, Gary S.; Oshanin, Gleb; Webb, Edmund B., III
2009-11-01
Capillary phenomena associated with fluids wetting other condensed matter phases have drawn great scientific interest for hundreds of years; consider the recent bicentennial celebration of Thomas Young's paper on equilibrium contact angles, describing the geometric shape assumed near a three phase contact line in terms of the relevant surface energies of the constituent phases [1]. Indeed, nearly a century has passed since the seminal papers of Lucas and Washburn, describing dynamics of capillary imbibition [2, 3]. While it is generally appreciated that dynamics of fluid wetting processes are determined by the degree to which a system is out of capillary equilibrium, myriad complications exist that challenge the fundamental understanding of dynamic capillary phenomena. The topic has gathered much interest from recent Nobel laureate Pierre-Gilles de Gennes, who provided a seminal review of relevant dissipation mechanisms for fluid droplets spreading on solid surfaces [4] Although much about the dynamics of wetting has been revealed, much remains to be learned and intrinsic technological and fundamental interest in the topic drives continuing high levels of research activity. This is enabled partly by improved experimental capabilities for resolving wetting processes at increasingly finer temporal, spatial, and chemical resolution. Additionally, dynamic wetting research advances via higher fidelity computational modeling capabilities, which drive more highly refined theory development. The significance of this topic both fundamentally and technologically has resulted in a number of reviews of research activity in wetting dynamics. One recent example addresses the evaluation of existing wetting dynamics theories from an experimentalist's perspective [5]. A Current Opinion issue was recently dedicated to high temperature capillarity, including dynamics of high temperature spreading [6]. New educational tools have recently emerged for providing instruction in wetting
Harada, Hiroo; Asai, Kiyoshi; Kihara, Kazuhisa.
1981-09-01
The purpose of dynamic link facility is to link a load module dynamically only when it is used in execution time. The facility is very useful for development, execution and maintenance of a large scale computer program which is too big to be saved as one load module in main memory, or it is poor economy to save it due to many unused subroutines depending on an input. It is also useful for standardization and common utilization of programs. Standard usage of dynamic link facility of FACOM M-200 computer system, a software tool which analyzes the effect of dynamic link facility and application of dynamic link to nuclear codes are described. (author)
PREFACE: Domain wall dynamics in nanostructures Domain wall dynamics in nanostructures
Marrows, C. H.; Meier, G.
2012-01-01
spin-transfer torque threshold current density in coupled vortex domain wallsS Lepadatu, A P Mihai, J S Claydon, F Maccherozzi, S S Dhesi, C J Kinane, S Langridge and C H Marrows Large RF susceptibility of transverse domain wallsO Rousseau, S Petit-Watelot and M Viret Expansion and relaxation of magnetic mirror domains in a Pt/Co/Pt/Co/Pt multilayer with antiferromagnetic interlayer couplingP J Metaxas, R L Stamps, J-P Jamet, J Ferré, V Baltz and B Rodmacq Current-induced domain wall motion and magnetization dynamics in CoFeB/Cu/Co nanostripesV Uhlíř, J Vogel, N Rougemaille, O Fruchart, Z Ishaque, V Cros, J Camarero, J C Cezar, F Sirotti and S Pizzini Roles of the magnetic field and electric current in thermally activated domain wall motion in a submicrometer magnetic strip with perpendicular magnetic anisotropySatoru Emori and Geoffrey S D Beach Electrical domain morphologies in compositionally graded ferroelectric filmsM B Okatan, A L Roytburd, V Nagarajan and S P Alpay Domain-wall pinning by local control of anisotropy in Pt/Co/Pt strips J H Franken, M Hoeijmakers, R Lavrijsen and H J M Swagten Experimental detection of domain wall propagation above the Walker field Kouta Kondou, Norikazu Ohshima, Daichi Chiba, Shinya Kasai, Kensuke Kobayashi and Teruo Ono Enhanced functionality in magnonics by domain walls and inhomogeneous spin configurationsG Duerr, R Huber and D Grundler Domain wall motion in perpendicular anisotropy nanowires with edge roughness Maximilian Albert, Matteo Franchin, Thomas Fischbacher, Guido Meier and Hans Fangohr Determination of the spin torque non-adiabaticity in perpendicularly magnetized nanowiresJ Heinen, D Hinzke, O Boulle, G Malinowski, H J M Swagten, B Koopmans, C Ulysse, G Faini, B Ocker, J Wrona and M Kläui Domain wall dynamics driven by spin transfer torque and the spin-orbit field Masamitsu Hayashi, Yoshinobu Nakatani, Shunsuke Fukami, Michihiko Yamanouchi, Seiji Mitani and Hideo Ohno Dynamic propagation and nucleation in domain
Nonadiabatic corrections to a quantum dot quantum computer ...
2014-07-02
Jul 2, 2014 ... corrections in it. If the decoherence times of a quantum dot computer are ∼100 ns [J M Kikkawa and D D Awschalom, Phys. Rev. Lett. 80, 4313 (1998)] then the predicted number of one qubit gate (primitive) operations of the Loss–DiVincenzo quantum computer in such an interval of time must be >1010.
Adiabatic temperature change from non-adiabatic measurements
Carvalho, A.M.G.; Mejía, C.S.; Ponte, C.A.; Silva, L.E.L.; Kaštil, Jiří; Kamarád, Jiří; Gomes, A.M.
2016-01-01
Roč. 122, č. 3 (2016), s. 1-5, č. článku 246. ISSN 0947-8396 Institutional support: RVO:68378271 Keywords : magnetocaloric effect * adiabatic temperature change * calorimetric device * gadolinium Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.455, year: 2016
Field-free molecular orientation of nonadiabatically aligned OCS
Sonoda, Kotaro; Iwasaki, Atsushi; Yamanouchi, Kaoru; Hasegawa, Hirokazu
2018-02-01
We investigate an enhancement of the orientation of OCS molecules by irradiating them with a near IR (ω) ultrashort laser pulse for alignment followed by another ultrashort laser pulse for orientation, which is synthesized by a phase-locked coherent superposition of the near IR laser pulse and its second harmonic (2ω). On the basis of the asymmetry in the ejection direction of S3+ fragment ions generated by the Coulomb explosion of multiply charged OCS, we show that the extent of the orientation of OCS is significantly enhanced when the delay between the alignment pulse and the orientation pulse is a quarter or three quarters of the rotational period. The recorded enhanced orientation was interpreted well by a numerical simulation of the temporal evolution of a rotational wave packet prepared by the alignment and orientation pulses.
Lagrangian Description of Nonadiabatic Particle Motion in Spherical Tori
R.B. White; Yu.V. Yakovenko; Ya.I. Kolesnichenko
2002-06-21
The ability of a device to provide adiabatic motion of charged particles is crucial for magnetic confinement. As the magnetic field in the present-day spherical tori, e.g., MAST and NSTX, is much lower than in the conventional tokamaks, effects of the finite Larmor radius (FLR) on the motion of fast ions are of importance in these devices, affecting the stochasticity threshold for the interaction of the ions with electromagnetic perturbations. In addition, FLR by itself may result in non-conservation (jumps) of the magnetic moment of particles [4]. In this work we propose a Lagrangian approach to description of the resonant collisionless motion of charged particles under a perturbation, allowing for FLR. The work generalizes results of Ref. [1], where only time-independent perturbations were considered. The approach is used to find the stochasticity thresholds for the Goldston-White-Boozer (GWB) diffusion [2] and the cyclotron-resonance-induced (CRI) diffusion (for the case of the firs t cyclotron resonance, the latter was discovered in Ref. [3]). In addition, a new expression for the magnetic moment variation caused by FLR is found.
Non-adiabatic pumping in an oscillating-piston model
Chuchem, Maya; Dittrich, Thomas; Cohen, Doron
2012-05-01
We consider the prototypical "piston pump" operating on a ring, where a circulating current is induced by means of an AC driving. This can be regarded as a generalized Fermi-Ulam model, incorporating a finite-height moving wall (piston) and non-trivial topology (ring). The amount of particles transported per cycle is determined by a layered structure of phase space. Each layer is characterized by a different drift velocity. We discuss the differences compared with the adiabatic and Boltzmann pictures, and highlight the significance of the "diabatic" contribution that might lead to a counter-stirring effect.
A nonlinear wave equation in nonadiabatic flame propagation
Booty, M.R.; Matalon, M.; Matkowsky, B.J.
1988-01-01
The authors derive a nonlinear wave equation from the diffusional thermal model of gaseous combustion to describe the evolution of a flame front. The equation arises as a long wave theory, for values of the volumeric heat loss in a neighborhood of the extinction point (beyond which planar uniformly propagating flames cease to exist), and for Lewis numbers near the critical value beyond which uniformly propagating planar flames lose stability via a degenerate Hopf bifurcation. Analysis of the equation suggests the possibility of a singularity developing in finite time
Adiabatic and Nonadiabatic Charge Transport in Li-S Batteries
Park, Haesun; Kumar, Nitin; Melander, Marko
2018-01-01
The insulating nature of the redox end members in Li-S batteries, -S and Li2S, has the potential to limit the capacity and efficiency of this emerging energy storage system. Nevertheless, the mechanisms responsible for ionic and electronic transport in these materials remain a matter of debate...... studies, we conclude that low equilibrium carrier concentrations are responsible for sluggish charge transport in -S and Li2S. Thus, a potential strategy for improving the performance of Li-S batteries is to increase the concentrations of holes in these redox end members....
Lagrangian Description of Nonadiabatic Particle Motion in Spherical Tori
White, R.B.; Yakovenko, Yu.V.; Kolesnichenko, Ya.I.
2002-01-01
The ability of a device to provide adiabatic motion of charged particles is crucial for magnetic confinement. As the magnetic field in the present-day spherical tori, e.g., MAST and NSTX, is much lower than in the conventional tokamaks, effects of the finite Larmor radius (FLR) on the motion of fast ions are of importance in these devices, affecting the stochasticity threshold for the interaction of the ions with electromagnetic perturbations. In addition, FLR by itself may result in non-conservation (jumps) of the magnetic moment of particles [4]. In this work we propose a Lagrangian approach to description of the resonant collisionless motion of charged particles under a perturbation, allowing for FLR. The work generalizes results of Ref. [1], where only time-independent perturbations were considered. The approach is used to find the stochasticity thresholds for the Goldston-White-Boozer (GWB) diffusion [2] and the cyclotron-resonance-induced (CRI) diffusion (for the case of the first cyclotron resonance, the latter was discovered in Ref. [3]). In addition, a new expression for the magnetic moment variation caused by FLR is found
Lattice-induced nonadiabatic frequency shifts in optical lattice clocks
Beloy, K.
2010-01-01
We consider the frequency shift in optical lattice clocks which arises from the coupling of the electronic motion to the atomic motion within the lattice. For the simplest of three-dimensional lattice geometries this coupling is shown to affect only clocks based on blue-detuned lattices. We have estimated the size of this shift for the prospective strontium lattice clock operating at the 390-nm blue-detuned magic wavelength. The resulting fractional frequency shift is found to be on the order of 10 -18 and is largely overshadowed by the electric quadrupole shift. For lattice clocks based on more complex geometries or other atomic systems, this shift could potentially be a limiting factor in clock accuracy.
Critical quench dynamics in confined systems.
Collura, Mario; Karevski, Dragi
2010-05-21
We analyze the coherent quantum evolution of a many-particle system after slowly sweeping a power-law confining potential. The amplitude of the confining potential is varied in time along a power-law ramp such that the many-particle system finally reaches or crosses a critical point. Under this protocol we derive general scaling laws for the density of excitations created during the nonadiabatic sweep of the confining potential. It is found that the mean excitation density follows an algebraic law as a function of the sweeping rate with an exponent that depends on the space-time properties of the potential. We confirm our scaling laws by first order adiabatic calculation and exact results on the Ising quantum chain with a varying transverse field.
Complexity and Dynamical Depth
Terrence Deacon
2014-07-01
Full Text Available We argue that a critical difference distinguishing machines from organisms and computers from brains is not complexity in a structural sense, but a difference in dynamical organization that is not well accounted for by current complexity measures. We propose a measure of the complexity of a system that is largely orthogonal to computational, information theoretic, or thermodynamic conceptions of structural complexity. What we call a system’s dynamical depth is a separate dimension of system complexity that measures the degree to which it exhibits discrete levels of nonlinear dynamical organization in which successive levels are distinguished by local entropy reduction and constraint generation. A system with greater dynamical depth than another consists of a greater number of such nested dynamical levels. Thus, a mechanical or linear thermodynamic system has less dynamical depth than an inorganic self-organized system, which has less dynamical depth than a living system. Including an assessment of dynamical depth can provide a more precise and systematic account of the fundamental difference between inorganic systems (low dynamical depth and living systems (high dynamical depth, irrespective of the number of their parts and the causal relations between them.
Dynamic and quasi-dynamic multileaf collimation
Bortfeld, T.
1995-01-01
Several recent investigations deal with the problem of how to produce arbitrary two-dimensional x-ray fluence distributions by means of a multileaf collimator (MLC), an approach, which could be called multileaf modulation. The goal of this approach is to facilitate the delivery of compensated or intensity-modulated fields. The present work gives an overview of these developments. The hardware requirements on MLCs for this special application are specified. Most commercially available MLCs fulfill these requirement sufficiently, however, the MLC control software is generally not capable of controlling an MLC dynamically. There is also the question of how to verify the dynamic movement of the leaves. Some minimum requirements on a control software suitable for application in clinical practice are therefore specified. An alternative, the stepwise or 'quasi-dynamic' movement of the MLC-leaves, is also discussed with respect to practicality. In this case the control is easier, but the demands on the stability of the accelerator for small dose deliveries are higher. Nevertheless, it can be expected that, for reasons of ease of control and verification, the quasi-dynamic technique will become the method of choice in the near future, while the slightly more effective fully dynamic technique will become available later in the future. In any case, multileaf modulation is an interesting and important alternative to the tomotherapy-concept
Synchronization dynamics of two different dynamical systems
Luo, Albert C.J.; Min Fuhong
2011-01-01
Highlights: → Synchronization dynamics of two distinct dynamical systems. → Synchronization, de-synchronization and instantaneous synchronization. → A controlled pendulum synchronizing with the Duffing oscillator. → Synchronization invariant set. → Synchronization parameter map. - Abstract: In this paper, synchronization dynamics of two different dynamical systems is investigated through the theory of discontinuous dynamical systems. The necessary and sufficient conditions for the synchronization, de-synchronization and instantaneous synchronization (penetration or grazing) are presented. Using such a synchronization theory, the synchronization of a controlled pendulum with the Duffing oscillator is systematically discussed as a sampled problem, and the corresponding analytical conditions for the synchronization are presented. The synchronization parameter study is carried out for a better understanding of synchronization characteristics of the controlled pendulum and the Duffing oscillator. Finally, the partial and full synchronizations of the controlled pendulum with periodic and chaotic motions are presented to illustrate the analytical conditions. The synchronization of the Duffing oscillator and pendulum are investigated in order to show the usefulness and efficiency of the methodology in this paper. The synchronization invariant domain is obtained. The technique presented in this paper should have a wide spectrum of applications in engineering. For example, this technique can be applied to the maneuvering target tracking, and the others.
Sørensen, Kim
Traditionally, boilers have been designed mainly focussing on the static operation of the plant. The dynamic capability has been given lower priority and the analysis has typically been limited to assuring that the plant was not over-stressed due to large temperature gradients. New possibilities...... developed. Analyzing boilers for dynamic operation gives rise to a number of opposing aims: shrinking and swelling, steam quality, stress levels, control system/philosophy, pressurization etc. Common for these opposing aims is that an optimum can be found for selected operation conditions. The framework has...... for buying and selling energy has increased the focus on the dynamic operation capability, efciency, emissions etc. For optimizing the design of boilers for dynamic operation a quantication of the dynamic capability is needed. A framework for optimizing design of boilers for dynamic operation has been...
Nonlinear dynamics and astrophysics
Vallejo, J. C.; Sanjuan, M. A. F.
2000-01-01
Concepts and techniques from Nonlinear Dynamics, also known as Chaos Theory, have been applied successfully to several astrophysical fields such as orbital motion, time series analysis or galactic dynamics, providing answers to old questions but also opening a few new ones. Some of these topics are described in this review article, showing the basis of Nonlinear Dynamics, and how it is applied in Astrophysics. (Author)
Record Statistics and Dynamics
Sibani, Paolo; Jensen, Henrik J.
2009-01-01
with independent random increments. The term record dynamics covers the rather new idea that records may, in special situations, have measurable dynamical consequences. The approach applies to the aging dynamics of glasses and other systems with multiple metastable states. The basic idea is that record sizes...... fluctuations of e. g. the energy are able to push the system past some sort of ‘edge of stability’, inducing irreversible configurational changes, whose statistics then closely follows the statistics of record fluctuations....
Posch, H.A.; Narnhofer, H.; Thirring, W.
1990-01-01
We study the dynamics of classical particles interacting with attractive Gaussian potentials. This system is thermodynamically not stable and exhibits negative specific heat. The results of the computer simulation of the dynamics are discussed in comparison with various theories. In particular, we find that the condensed phase is a stationary solution of the Vlasov equation, but the Vlasov dynamics cannot describe the collapse. 14 refs., 1 tab., 11 figs. (Authors)
Dynamical principles in neuroscience
Rabinovich, Mikhail I.; Varona, Pablo; Selverston, Allen I.; Abarbanel, Henry D. I.
2006-01-01
Dynamical modeling of neural systems and brain functions has a history of success over the last half century. This includes, for example, the explanation and prediction of some features of neural rhythmic behaviors. Many interesting dynamical models of learning and memory based on physiological experiments have been suggested over the last two decades. Dynamical models even of consciousness now exist. Usually these models and results are based on traditional approaches and paradigms of nonlinear dynamics including dynamical chaos. Neural systems are, however, an unusual subject for nonlinear dynamics for several reasons: (i) Even the simplest neural network, with only a few neurons and synaptic connections, has an enormous number of variables and control parameters. These make neural systems adaptive and flexible, and are critical to their biological function. (ii) In contrast to traditional physical systems described by well-known basic principles, first principles governing the dynamics of neural systems are unknown. (iii) Many different neural systems exhibit similar dynamics despite having different architectures and different levels of complexity. (iv) The network architecture and connection strengths are usually not known in detail and therefore the dynamical analysis must, in some sense, be probabilistic. (v) Since nervous systems are able to organize behavior based on sensory inputs, the dynamical modeling of these systems has to explain the transformation of temporal information into combinatorial or combinatorial-temporal codes, and vice versa, for memory and recognition. In this review these problems are discussed in the context of addressing the stimulating questions: What can neuroscience learn from nonlinear dynamics, and what can nonlinear dynamics learn from neuroscience?
Dynamical principles in neuroscience
Rabinovich, Mikhail I.; Varona, Pablo; Selverston, Allen I.; Abarbanel, Henry D. I.
2006-10-01
Dynamical modeling of neural systems and brain functions has a history of success over the last half century. This includes, for example, the explanation and prediction of some features of neural rhythmic behaviors. Many interesting dynamical models of learning and memory based on physiological experiments have been suggested over the last two decades. Dynamical models even of consciousness now exist. Usually these models and results are based on traditional approaches and paradigms of nonlinear dynamics including dynamical chaos. Neural systems are, however, an unusual subject for nonlinear dynamics for several reasons: (i) Even the simplest neural network, with only a few neurons and synaptic connections, has an enormous number of variables and control parameters. These make neural systems adaptive and flexible, and are critical to their biological function. (ii) In contrast to traditional physical systems described by well-known basic principles, first principles governing the dynamics of neural systems are unknown. (iii) Many different neural systems exhibit similar dynamics despite having different architectures and different levels of complexity. (iv) The network architecture and connection strengths are usually not known in detail and therefore the dynamical analysis must, in some sense, be probabilistic. (v) Since nervous systems are able to organize behavior based on sensory inputs, the dynamical modeling of these systems has to explain the transformation of temporal information into combinatorial or combinatorial-temporal codes, and vice versa, for memory and recognition. In this review these problems are discussed in the context of addressing the stimulating questions: What can neuroscience learn from nonlinear dynamics, and what can nonlinear dynamics learn from neuroscience?
Myeong, Hyeon Guk
1999-06-01
This book deals with computational fluid dynamics with basic and history of numerical fluid dynamics, introduction of finite volume method using one-dimensional heat conduction equation, solution of two-dimensional heat conduction equation, solution of Navier-Stokes equation, fluid with heat transport, turbulent flow and turbulent model, Navier-Stokes solution by generalized coordinate system such as coordinate conversion, conversion of basic equation, program and example of calculation, application of abnormal problem and high speed solution of numerical fluid dynamics.
Double dynamic scaling in human communication dynamics
Wang, Shengfeng; Feng, Xin; Wu, Ye; Xiao, Jinhua
2017-05-01
In the last decades, human behavior has been deeply understanding owing to the huge quantities data of human behavior available for study. The main finding in human dynamics shows that temporal processes consist of high-activity bursty intervals alternating with long low-activity periods. A model, assuming the initiator of bursty follow a Poisson process, is widely used in the modeling of human behavior. Here, we provide further evidence for the hypothesis that different bursty intervals are independent. Furthermore, we introduce a special threshold to quantitatively distinguish the time scales of complex dynamics based on the hypothesis. Our results suggest that human communication behavior is a composite process of double dynamics with midrange memory length. The method for calculating memory length would enhance the performance of many sequence-dependent systems, such as server operation and topic identification.
Introduction to dynamic programming
Cooper, Leon; Rodin, E Y
1981-01-01
Introduction to Dynamic Programming provides information pertinent to the fundamental aspects of dynamic programming. This book considers problems that can be quantitatively formulated and deals with mathematical models of situations or phenomena that exists in the real world.Organized into 10 chapters, this book begins with an overview of the fundamental components of any mathematical optimization model. This text then presents the details of the application of dynamic programming to variational problems. Other chapters consider the application of dynamic programming to inventory theory, Mark
Essential dynamics and relativity
O'Donnell, Peter J
2014-01-01
Essential Dynamics & Relativity provides students with an introduction to the core aspects of dynamics and special relativity. The author reiterates important ideas and terms throughout and covers concepts that are often missing from other textbooks at this level. He also places each topic within the wider constructs of the theory, without jumping from topic to topic to illustrate a point.The first section of the book focuses on dynamics, discussing the basic aspects of single particle motion and analyzing the motion of multi-particle systems. The book also explains the dynamical behavior of b
Gils, S; Hoveijn, I; Takens, F; Nonlinear Dynamical Systems and Chaos
1996-01-01
Symmetries in dynamical systems, "KAM theory and other perturbation theories", "Infinite dimensional systems", "Time series analysis" and "Numerical continuation and bifurcation analysis" were the main topics of the December 1995 Dynamical Systems Conference held in Groningen in honour of Johann Bernoulli. They now form the core of this work which seeks to present the state of the art in various branches of the theory of dynamical systems. A number of articles have a survey character whereas others deal with recent results in current research. It contains interesting material for all members of the dynamical systems community, ranging from geometric and analytic aspects from a mathematical point of view to applications in various sciences.
Lloyd, Seth; Viola, Lorenza
2002-01-01
The ability to perform measurements on a quantum system, combined with the ability to feed back the measurement results via coherent control, allows one to control the system to follow any desired coherent or incoherent quantum dynamics. Such universal dynamical control can be achieved, in principle, through the repeated application of only two coherent control operations and a simple 'Yes-No' measurement. As a consequence, a quantum computer can simulate an arbitrary open-system dynamics using just one qubit more than required to simulate closed-system dynamics
Kleinstreuer, Clement
2018-01-01
Modern Fluid Dynamics, Second Edition provides up-to-date coverage of intermediate and advanced fluids topics. The text emphasizes fundamentals and applications, supported by worked examples and case studies. Scale analysis, non-Newtonian fluid flow, surface coating, convection heat transfer, lubrication, fluid-particle dynamics, microfluidics, entropy generation, and fluid-structure interactions are among the topics covered. Part A presents fluids principles, and prepares readers for the applications of fluid dynamics covered in Part B, which includes computer simulations and project writing. A review of the engineering math needed for fluid dynamics is included in an appendix.
Control of dynamical localization
Gong Jiangbin; Woerner, Hans Jakob; Brumer, Paul
2003-01-01
Control over the quantum dynamics of chaotic kicked rotor systems is demonstrated. Specifically, control over a number of quantum coherent phenomena is achieved by a simple modification of the kicking field. These include the enhancement of the dynamical localization length, the introduction of classical anomalous diffusion assisted control for systems far from the semiclassical regime, and the observation of a variety of strongly nonexponential line shapes for dynamical localization. The results provide excellent examples of controlled quantum dynamics in a system that is classically chaotic and offer opportunities to explore quantum fluctuations and correlations in quantum chaos
Nonlinear dynamics and complexity
Luo, Albert; Fu, Xilin
2014-01-01
This important collection presents recent advances in nonlinear dynamics including analytical solutions, chaos in Hamiltonian systems, time-delay, uncertainty, and bio-network dynamics. Nonlinear Dynamics and Complexity equips readers to appreciate this increasingly main-stream approach to understanding complex phenomena in nonlinear systems as they are examined in a broad array of disciplines. The book facilitates a better understanding of the mechanisms and phenomena in nonlinear dynamics and develops the corresponding mathematical theory to apply nonlinear design to practical engineering.
Structural Dynamics Laboratory (SDL)
Federal Laboratory Consortium — Structural dynamic testing is performed to verify the survivability of a component or assembly when exposed to vibration stress screening, or a controlled simulation...
How electronic dynamics with Pauli exclusion produces Fermi-Dirac statistics.
Nguyen, Triet S; Nanguneri, Ravindra; Parkhill, John
2015-04-07
It is important that any dynamics method approaches the correct population distribution at long times. In this paper, we derive a one-body reduced density matrix dynamics for electrons in energetic contact with a bath. We obtain a remarkable equation of motion which shows that in order to reach equilibrium properly, rates of electron transitions depend on the density matrix. Even though the bath drives the electrons towards a Boltzmann distribution, hole blocking factors in our equation of motion cause the electronic populations to relax to a Fermi-Dirac distribution. These factors are an old concept, but we show how they can be derived with a combination of time-dependent perturbation theory and the extended normal ordering of Mukherjee and Kutzelnigg for a general electronic state. The resulting non-equilibrium kinetic equations generalize the usual Redfield theory to many-electron systems, while ensuring that the orbital occupations remain between zero and one. In numerical applications of our equations, we show that relaxation rates of molecules are not constant because of the blocking effect. Other applications to model atomic chains are also presented which highlight the importance of treating both dephasing and relaxation. Finally, we show how the bath localizes the electron density matrix.
How electronic dynamics with Pauli exclusion produces Fermi-Dirac statistics
Nguyen, Triet S.; Nanguneri, Ravindra; Parkhill, John
2015-01-01
It is important that any dynamics method approaches the correct population distribution at long times. In this paper, we derive a one-body reduced density matrix dynamics for electrons in energetic contact with a bath. We obtain a remarkable equation of motion which shows that in order to reach equilibrium properly, rates of electron transitions depend on the density matrix. Even though the bath drives the electrons towards a Boltzmann distribution, hole blocking factors in our equation of motion cause the electronic populations to relax to a Fermi-Dirac distribution. These factors are an old concept, but we show how they can be derived with a combination of time-dependent perturbation theory and the extended normal ordering of Mukherjee and Kutzelnigg for a general electronic state. The resulting non-equilibrium kinetic equations generalize the usual Redfield theory to many-electron systems, while ensuring that the orbital occupations remain between zero and one. In numerical applications of our equations, we show that relaxation rates of molecules are not constant because of the blocking effect. Other applications to model atomic chains are also presented which highlight the importance of treating both dephasing and relaxation. Finally, we show how the bath localizes the electron density matrix
Vegetation dynamics and dynamic vegetation science
Van der Maarel, E
1996-01-01
his contribution presents a review of the development of the study of vegetation dynamics since 1979, in the framework of a jubilee meeting on progress in the study of vegetation. However, an exhaustive review is both impossible and unnecessary. It is impossible within the few pages available
Crosby, Sean Michael; Doak, Justin E.; Haas, Jason Juedes.; Helinski, Ryan; Lamb, Christopher C.
2013-02-01
On September 5th and 6th, 2012, the Dynamic Defense Workshop: From Research to Practice brought together researchers from academia, industry, and Sandia with the goals of increasing collaboration between Sandia National Laboratories and external organizations, de ning and un- derstanding dynamic, or moving target, defense concepts and directions, and gaining a greater understanding of the state of the art for dynamic defense. Through the workshop, we broadened and re ned our de nition and understanding, identi ed new approaches to inherent challenges, and de ned principles of dynamic defense. Half of the workshop was devoted to presentations of current state-of-the-art work. Presentation topics included areas such as the failure of current defenses, threats, techniques, goals of dynamic defense, theory, foundations of dynamic defense, future directions and open research questions related to dynamic defense. The remainder of the workshop was discussion, which was broken down into sessions on de ning challenges, applications to host or mobile environments, applications to enterprise network environments, exploring research and operational taxonomies, and determining how to apply scienti c rigor to and investigating the eld of dynamic defense.
Nielsen, Søren R.K.
This book has been prepared for the course on Computational Dynamics given at the 8th semester at the structural program in civil engineering at Aalborg University.......This book has been prepared for the course on Computational Dynamics given at the 8th semester at the structural program in civil engineering at Aalborg University....
Nonlinear dynamics in Nuclotron
Dinev, D.
1997-01-01
The paper represents an extensive study of the nonlinear beam dynamics in the Nuclotron. Chromatic effects, including the dependence of the betatron tunes on the amplitude, and chromatic perturbations have been investigated taking into account the measured field imperfections. Beam distortion, smear, dynamic aperture and nonlinear acceptance have been calculated for different particle energies and betatron tunes
Gagie, Travis
2005-01-01
We present a new algorithm for dynamic prefix-free coding, based on Shannon coding. We give a simple analysis and prove a better upper bound on the length of the encoding produced than the corresponding bound for dynamic Huffman coding. We show how our algorithm can be modified for efficient length-restricted coding, alphabetic coding and coding with unequal letter costs.
Dynamic paradigm of turbulence
Mukhamedov, Alfred M.
2006-01-01
In this paper a dynamic paradigm of turbulence is proposed. The basic idea consists in the novel definition of chaotic structure given with the help of Pfaff system of PDE associated with the turbulent dynamics. A methodological analysis of the new and the former paradigm is produced
Dynamic Capabilities and Performance
Wilden, Ralf; Gudergan, Siegfried P.; Nielsen, Bo Bernhard
2013-01-01
are contingent on the competitive intensity faced by firms. Our findings demonstrate the performance effects of internal alignment between organizational structure and dynamic capabilities, as well as the external fit of dynamic capabilities with competitive intensity. We outline the advantages of PLS...
2009-04-01
GAMING PLATFORM (DGP) Lockheed Martin Corporation...YYYY) APR 09 2. REPORT TYPE Final 3. DATES COVERED (From - To) Jul 07 – Mar 09 4. TITLE AND SUBTITLE DYNAMIC GAMING PLATFORM (DGP) 5a...CMU Carnegie Mellon University DGP Dynamic Gaming Platform GA Genetic Algorithm IARPA Intelligence Advanced Research Projects Activity LM ATL Lockheed Martin Advanced Technology Laboratories PAINT ProActive INTelligence
Minkenberg, C.B.
2012-01-01
In this thesis the development of surfactant aggregates with fast exchange dynamics between the aggregated and non-aggregated state is described. Dynamic surfactant exchange plays an important role in natural systems, for instance in cell signaling, cell division, and uptake and release of cargo.
Home; Journals; Resonance – Journal of Science Education; Volume 8; Issue 11. Dynamics on the Circle - Interval Dynamics and Rotation Number. Siddhartha Gadgil. General Article Volume 8 Issue 11 November 2003 pp 25-36. Fulltext. Click here to view fulltext PDF. Permanent link:
Hill, Kent; Sabet, Mehran
2009-01-01
This article describes an attempt to adopt dynamic assessment (DA) methods in classroom speaking assessments. The study reported in this article focused on four particular applications of dynamic speaking assessment (DSA). The first, "mediated assistance" (MA), involves interaction between an assistor and a learner to reveal problems in…
Dynamical supersymmetry breaking
Affleck, I.
1985-03-01
Supersymmetry, and in particular, dynamical supersymmetry breaking, offers the hope of a natural solution of the gauge hierarchy problem in grand unification. I briefly review recent work on dynamical supersymmetry breaking in four-dimensional Higgs theories and its application to grand unified model building
Dynamic Latent Classification Model
Zhong, Shengtong; Martínez, Ana M.; Nielsen, Thomas Dyhre
as possible. Motivated by this problem setting, we propose a generative model for dynamic classification in continuous domains. At each time point the model can be seen as combining a naive Bayes model with a mixture of factor analyzers (FA). The latent variables of the FA are used to capture the dynamics...
Dynamic combinatorial chemistry
Otto, Sijbren; Furlan, Ricardo L.E.; Sanders, Jeremy K.M.
2002-01-01
A combinatorial library that responds to its target by increasing the concentration of strong binders at the expense of weak binders sounds ideal. Dynamic combinatorial chemistry has the potential to achieve exactly this. In this review, we will highlight the unique features that distinguish dynamic
Karsai, Márton; Kaski, Kimmo
2018-01-01
This book provides a comprehensive overview on emergent bursty patterns in the dynamics of human behaviour. It presents common and alternative understanding of the investigated phenomena, and points out open questions worthy of further investigations. The book is structured as follows. In the introduction the authors discuss the motivation of the field, describe bursty phenomena in case of human behaviour, and relate it to other disciplines. The second chapter addresses the measures commonly used to characterise heterogeneous signals, bursty human dynamics, temporal paths, and correlated behaviour. These definitions are first introduced to set the basis for the discussion of the third chapter about the observations of bursty human patterns in the dynamics of individuals, dyadic interactions, and collective behaviour. The subsequent fourth chapter discusses the models of bursty human dynamics. Various mechanisms have been proposed about the source of the heterogeneities in human dynamics, which leads to the in...
Nonlinear dynamics of structures
Oller, Sergio
2014-01-01
This book lays the foundation of knowledge that will allow a better understanding of nonlinear phenomena that occur in structural dynamics. This work is intended for graduate engineering students who want to expand their knowledge on the dynamic behavior of structures, specifically in the nonlinear field, by presenting the basis of dynamic balance in non‐linear behavior structures due to the material and kinematics mechanical effects. Particularly, this publication shows the solution of the equation of dynamic equilibrium for structure with nonlinear time‐independent materials (plasticity, damage and frequencies evolution), as well as those time dependent non‐linear behavior materials (viscoelasticity and viscoplasticity). The convergence conditions for the non‐linear dynamic structure solution are studied, and the theoretical concepts and its programming algorithms are presented.
Rajamani, Rajesh
2012-01-01
Vehicle Dynamics and Control provides a comprehensive coverage of vehicle control systems and the dynamic models used in the development of these control systems. The control system applications covered in the book include cruise control, adaptive cruise control, ABS, automated lane keeping, automated highway systems, yaw stability control, engine control, passive, active and semi-active suspensions, tire-road friction coefficient estimation, rollover prevention, and hybrid electric vehicle. In developing the dynamic model for each application, an effort is made to both keep the model simple enough for control system design but at the same time rich enough to capture the essential features of the dynamics. A special effort has been made to explain the several different tire models commonly used in literature and to interpret them physically. In the second edition of the book, chapters on roll dynamics, rollover prevention and hybrid electric vehicles have been added, and the chapter on electronic stability co...
Long, Run; Prezhdo, Oleg V
2015-07-08
Hybrid organic/inorganic polymer/quantum dot (QD) solar cells are an attractive alternative to the traditional cells. The original, simple models postulate that one-dimensional polymers have continuous energy levels, while zero-dimensional QDs exhibit atom-like electronic structure. A realistic, atomistic viewpoint provides an alternative description. Electronic states in polymers are molecule-like: finite in size and discrete in energy. QDs are composed of many atoms and have high, bulk-like densities of states. We employ ab initio time-domain simulation to model the experimentally observed ultrafast photoinduced dynamics in a QD/polymer hybrid and show that an atomistic description is essential for understanding the time-resolved experimental data. Both electron and hole transfers across the interface exhibit subpicosecond time scales. The interfacial processes are fast due to strong electronic donor-acceptor, as evidenced by the densities of the photoexcited states which are delocalized between the donor and the acceptor. The nonadiabatic charge-phonon coupling is also strong, especially in the polymer, resulting in rapid energy losses. The electron transfer from the polymer is notably faster than the hole transfer from the QD, due to a significantly higher density of acceptor states. The stronger molecule-like electronic and charge-phonon coupling in the polymer rationalizes why the electron-hole recombination inside the polymer is several orders of magnitude faster than in the QD. As a result, experiments exhibit multiple transfer times for the long-lived hole inside the QD, ranging from subpicoseconds to nanoseconds. In contrast, transfer of the short-lived electron inside the polymer does not occur beyond the first picosecond. The energy lost by the hole on its transit into the polymer is accommodated by polymer's high-frequency vibrations. The energy lost by the electron injected into the QD is accommodated primarily by much lower-frequency collective and
Bayesian dynamic mediation analysis.
Huang, Jing; Yuan, Ying
2017-12-01
Most existing methods for mediation analysis assume that mediation is a stationary, time-invariant process, which overlooks the inherently dynamic nature of many human psychological processes and behavioral activities. In this article, we consider mediation as a dynamic process that continuously changes over time. We propose Bayesian multilevel time-varying coefficient models to describe and estimate such dynamic mediation effects. By taking the nonparametric penalized spline approach, the proposed method is flexible and able to accommodate any shape of the relationship between time and mediation effects. Simulation studies show that the proposed method works well and faithfully reflects the true nature of the mediation process. By modeling mediation effect nonparametrically as a continuous function of time, our method provides a valuable tool to help researchers obtain a more complete understanding of the dynamic nature of the mediation process underlying psychological and behavioral phenomena. We also briefly discuss an alternative approach of using dynamic autoregressive mediation model to estimate the dynamic mediation effect. The computer code is provided to implement the proposed Bayesian dynamic mediation analysis. (PsycINFO Database Record (c) 2017 APA, all rights reserved).
Dynamics of aesthetic appreciation
Carbon, Claus-Christian
2012-03-01
Aesthetic appreciation is a complex cognitive processing with inherent aspects of cold as well as hot cognition. Research from the last decades of empirical has shown that evaluations of aesthetic appreciation are highly reliable. Most frequently, facial attractiveness was used as the corner case for investigating aesthetic appreciation. Evaluating facial attractiveness shows indeed high internal consistencies and impressively high inter-rater reliabilities, even across cultures. Although this indicates general and stable mechanisms underlying aesthetic appreciation, it is also obvious that our taste for specific objects changes dynamically. Aesthetic appreciation on artificial object categories, such as fashion, design or art is inherently very dynamic. Gaining insights into the cognitive mechanisms that trigger and enable corresponding changes of aesthetic appreciation is of particular interest for research as this will provide possibilities to modeling aesthetic appreciation for longer durations and from a dynamic perspective. The present paper refers to a recent two-step model ("the dynamical two-step-model of aesthetic appreciation"), dynamically adapting itself, which accounts for typical dynamics of aesthetic appreciation found in different research areas such as art history, philosophy and psychology. The first step assumes singular creative sources creating and establishing innovative material towards which, in a second step, people adapt by integrating it into their visual habits. This inherently leads to dynamic changes of the beholders' aesthetic appreciation.
Perspectives of nonlinear dynamics
Jackson, E.A.
1985-03-01
Four lectures were given weekly in October and November, 1984, and some of the ideas presented here will be of use in the future. First, a brief survey of the historical development of nonlinear dynamics since about 1890 was given, and then, a few topics were discussed in detail. The objective was to introduce some of many concepts and methods which are presently used for describing nonlinear dynamics. The symbiotic relationship between sciences of all types and mathematics, two main categories of the models describing nature, the method for describing the dynamics of a system, the idea of control parameters and topological dimension, the asymptotic properties of dynamics, abstract dynamics, the concept of embedding, singular perturbation theory, strange attractor, Fermi-Pasta-Ulam phenomena, an example of computer heuristics, the idea of elementary catastrophe theory and so on were explained. The logistic map is the simplest introduction to complex dynamics. The complicated dynamics is referred to as strange attractors. Two-dimensional maps are the highest dimensional maps commonly studied. These were discussed in detail. (Kako, I.)
Operational Dynamic Configuration Analysis
Lai, Chok Fung; Zelinski, Shannon
2010-01-01
Sectors may combine or split within areas of specialization in response to changing traffic patterns. This method of managing capacity and controller workload could be made more flexible by dynamically modifying sector boundaries. Much work has been done on methods for dynamically creating new sector boundaries [1-5]. Many assessments of dynamic configuration methods assume the current day baseline configuration remains fixed [6-7]. A challenging question is how to select a dynamic configuration baseline to assess potential benefits of proposed dynamic configuration concepts. Bloem used operational sector reconfigurations as a baseline [8]. The main difficulty is that operational reconfiguration data is noisy. Reconfigurations often occur frequently to accommodate staff training or breaks, or to complete a more complicated reconfiguration through a rapid sequence of simpler reconfigurations. Gupta quantified a few aspects of airspace boundary changes from this data [9]. Most of these metrics are unique to sector combining operations and not applicable to more flexible dynamic configuration concepts. To better understand what sort of reconfigurations are acceptable or beneficial, more configuration change metrics should be developed and their distribution in current practice should be computed. This paper proposes a method to select a simple sequence of configurations among operational configurations to serve as a dynamic configuration baseline for future dynamic configuration concept assessments. New configuration change metrics are applied to the operational data to establish current day thresholds for these metrics. These thresholds are then corroborated, refined, or dismissed based on airspace practitioner feedback. The dynamic configuration baseline selection method uses a k-means clustering algorithm to select the sequence of configurations and trigger times from a given day of operational sector combination data. The clustering algorithm selects a simplified
Dynamic training algorithm for dynamic neural networks
Tan, Y.; Van Cauwenberghe, A.; Liu, Z.
1996-01-01
The widely used backpropagation algorithm for training neural networks based on the gradient descent has a significant drawback of slow convergence. A Gauss-Newton method based recursive least squares (RLS) type algorithm with dynamic error backpropagation is presented to speed-up the learning procedure of neural networks with local recurrent terms. Finally, simulation examples concerning the applications of the RLS type algorithm to identification of nonlinear processes using a local recurrent neural network are also included in this paper
Living with Dynamic Concepts in Dynamic Environments
Rehm, Matthias
2003-01-01
a dynamic perspective, concepts depend on different factors like the learning process, the environment, i.e. the situational setting. It is indispensable for an agent to create individual concepts that adhere to restrictions imposed by the environment and the society it is living in. It is shown...... that changes in the environment lead to changes in existing concepts and to establishing new ones with only a small irritation in the use of the old ones....
Fiszdon, W
1965-01-01
Fluid Dynamics Transactions, Volume 2 compiles 46 papers on fluid dynamics, a subdiscipline of fluid mechanics that deals with fluid flow. The topics discussed in this book include developments in interference theory for aeronautical applications; diffusion from sources in a turbulent boundary layer; unsteady motion of a finite wing span in a compressible medium; and wall pressure covariance and comparison with experiment. The certain classes of non-stationary axially symmetric flows in magneto-gas-dynamics; description of the phenomenon of secondary flows in curved channels by means of co
Breton, Michele
2011-01-01
This book focuses on various aspects of dynamic game theory, presenting state-of-the-art research and serving as a testament to the vitality and growth of the field of dynamic games and their applications. The selected contributions, written by experts in their respective disciplines, are outgrowths of presentations originally given at the 13th International Symposium of Dynamic Games and Applications held in WrocACaw. The book covers a variety of topics, ranging from theoretical developments in game theory and algorithmic methods to applications, examples, and analysis in fields as varied as
Anderson, James C
2012-01-01
A concise introduction to structural dynamics and earthquake engineering Basic Structural Dynamics serves as a fundamental introduction to the topic of structural dynamics. Covering single and multiple-degree-of-freedom systems while providing an introduction to earthquake engineering, the book keeps the coverage succinct and on topic at a level that is appropriate for undergraduate and graduate students. Through dozens of worked examples based on actual structures, it also introduces readers to MATLAB, a powerful software for solving both simple and complex structural d
Rathakrishnan, Ethirajan
2014-01-01
This is an introductory level textbook which explains the elements of high temperature and high-speed gas dynamics. written in a clear and easy to follow style, the author covers all the latest developments in the field including basic thermodynamic principles, compressible flow regimes and waves propagation in one volume covers theoretical modeling of High Enthalpy Flows, with particular focus on problems in internal and external gas-dynamic flows, of interest in the fields of rockets propulsion and hypersonic aerodynamics High enthalpy gas dynamics is a compulsory course for aerospace engine
Shadowing in dynamical systems
Pilyugin, Sergei Yu
1999-01-01
This book is an introduction to the theory of shadowing of approximate trajectories in dynamical systems by exact ones. This is the first book completely devoted to the theory of shadowing. It shows the importance of shadowing theory for both the qualitative theory of dynamical systems and the theory of numerical methods. Shadowing Methods allow us to estimate differences between exact and approximate solutions on infinite time intervals and to understand the influence of error terms. The book is intended for specialists in dynamical systems, for researchers and graduate students in the theory of numerical methods.
Goodwin, Andrew L.; Tucker, Matthew G.; Cope, Elizabeth R.; Dove, Martin T.; Keen, David A.
2006-01-01
We explore the possibility that detailed dynamical information might be extracted from powder diffraction data. Our focus is a recently reported technique that employs statistical analysis of atomistic configurations to calculate dynamical properties from neutron total scattering data. We show that it is possible to access the phonon dispersion of low-frequency modes using such an approach, without constraining the results in terms of some pre-defined dynamical model. The high-frequency regions of the phonon spectrum are found to be less well preserved in the diffraction data
Babu, V
2014-01-01
Fundamentals of Gas Dynamics, Second Edition isa comprehensively updated new edition and now includes a chapter on the gas dynamics of steam. It covers the fundamental concepts and governing equations of different flows, and includes end of chapter exercises based on the practical applications. A number of useful tables on the thermodynamic properties of steam are also included.Fundamentals of Gas Dynamics, Second Edition begins with an introduction to compressible and incompressible flows before covering the fundamentals of one dimensional flows and normal shock wav
Stability of dynamical systems
Liao, Xiaoxin; Yu, P 0
2007-01-01
The main purpose of developing stability theory is to examine dynamic responses of a system to disturbances as the time approaches infinity. It has been and still is the object of intense investigations due to its intrinsic interest and its relevance to all practical systems in engineering, finance, natural science and social science. This monograph provides some state-of-the-art expositions of major advances in fundamental stability theories and methods for dynamic systems of ODE and DDE types and in limit cycle, normal form and Hopf bifurcation control of nonlinear dynamic systems.ʺ Presents
Stoneham, A.M.; Gavartin, J.L.
2007-01-01
However fascinating structures may be at the nanoscale, time-dependent behaviour at the nanoscale has far greater importance. Some of the dynamics is random, with fluctuations controlling rate processes and making thermal ratchets possible. Some of the dynamics causes the transfer of energy, of signals, or of charge. Such transfers are especially efficiently controlled in biological systems. Other dynamical processes occur when we wish to control the nanoscale, e.g., to avoid local failures of gate dielectrics, or to manipulate structures by electronic excitation, to use spin manipulation in quantum information processing. Our prime purpose is to make clear the enormous range and variety of time-dependent nanoscale phenomena
Shivamoggi, Bhimsen K
1998-01-01
"Although there are many texts and monographs on fluid dynamics, I do not know of any which is as comprehensive as the present book. It surveys nearly the entire field of classical fluid dynamics in an advanced, compact, and clear manner, and discusses the various conceptual and analytical models of fluid flow." - Foundations of Physics on the first edition. Theoretical Fluid Dynamics functions equally well as a graduate-level text and a professional reference. Steering a middle course between the empiricism of engineering and the abstractions of pure mathematics, the author focuses
Wuensche, Andrew
DDLab is interactive graphics software for creating, visualizing, and analyzing many aspects of Cellular Automata, Random Boolean Networks, and Discrete Dynamical Networks in general and studying their behavior, both from the time-series perspective — space-time patterns, and from the state-space perspective — attractor basins. DDLab is relevant to research, applications, and education in the fields of complexity, self-organization, emergent phenomena, chaos, collision-based computing, neural networks, content addressable memory, genetic regulatory networks, dynamical encryption, generative art and music, and the study of the abstract mathematical/physical/dynamical phenomena in their own right.
Dynamic Systems and Control Engineering
Kim, Jong Seok
1994-02-01
This book deals with introduction of dynamic system and control engineering, frequency domain modeling of dynamic system, temporal modeling of dynamic system, typical dynamic system and automatic control device, performance and stability of control system, root locus analysis, analysis of frequency domain dynamic system, design of frequency domain dynamic system, design and analysis of space, space of control system and digital control system such as control system design of direct digital and digitalization of consecutive control system.
Dynamic Systems and Control Engineering
Kim, Jong Seok
1994-02-15
This book deals with introduction of dynamic system and control engineering, frequency domain modeling of dynamic system, temporal modeling of dynamic system, typical dynamic system and automatic control device, performance and stability of control system, root locus analysis, analysis of frequency domain dynamic system, design of frequency domain dynamic system, design and analysis of space, space of control system and digital control system such as control system design of direct digital and digitalization of consecutive control system.
Ibrahim, Raouf A.
2005-06-01
The problem of liquid sloshing in moving or stationary containers remains of great concern to aerospace, civil, and nuclear engineers; physicists; designers of road tankers and ship tankers; and mathematicians. Beginning with the fundamentals of liquid sloshing theory, this book takes the reader systematically from basic theory to advanced analytical and experimental results in a self-contained and coherent format. The book is divided into four sections. Part I deals with the theory of linear liquid sloshing dynamics; Part II addresses the nonlinear theory of liquid sloshing dynamics, Faraday waves, and sloshing impacts; Part III presents the problem of linear and nonlinear interaction of liquid sloshing dynamics with elastic containers and supported structures; and Part IV considers the fluid dynamics in spinning containers and microgravity sloshing. This book will be invaluable to researchers and graduate students in mechanical and aeronautical engineering, designers of liquid containers, and applied mathematicians.
Ansatz for dynamical hierarchies
Rasmussen, S.; Baas, N.A.; Mayer, B.
2001-01-01
Complex, robust functionalities can be generated naturally in at least two ways: by the assembly of structures and by the evolution of structures. This work is concerned with spontaneous formation of structures. We define the notion of dynamical hierarchies in natural systems and show...... the importance of this particular kind of organization for living systems. We then define a framework that enables us to formulate, investigate, and manipulate such dynamical hierarchies. This framework allows us to simultaneously investigate different levels of description together with them interrelationship...... three. Formulating this system as a simple two-dimensional molecular dynamics (MD) lattice gas allows us within one dynamical system to demonstrate the successive emergence of two higher levels (three levels all together) of robust structures with associated properties. Second, we demonstrate how...
Tecker, F
2014-01-01
The course gives a summary of longitudinal beam dynamics for both linear and circular accelerators. After discussing different types of acceleration methods and synchronism conditions, it focuses on the particle motion in synchrotrons
Stochastic dynamics and irreversibility
Tomé, Tânia
2015-01-01
This textbook presents an exposition of stochastic dynamics and irreversibility. It comprises the principles of probability theory and the stochastic dynamics in continuous spaces, described by Langevin and Fokker-Planck equations, and in discrete spaces, described by Markov chains and master equations. Special concern is given to the study of irreversibility, both in systems that evolve to equilibrium and in nonequilibrium stationary states. Attention is also given to the study of models displaying phase transitions and critical phenomema both in thermodynamic equilibrium and out of equilibrium. These models include the linear Glauber model, the Glauber-Ising model, lattice models with absorbing states such as the contact process and those used in population dynamic and spreading of epidemic, probabilistic cellular automata, reaction-diffusion processes, random sequential adsorption and dynamic percolation. A stochastic approach to chemical reaction is also presented.The textbook is intended for students of ...