Time-dependent density functional theory for strong-field ionization by circularly polarized pulses
Chirilă, Ciprian C.; Lein, Manfred
2017-03-01
By applying time-dependent density functional theory to a two-dimensional multielectron atom subject to strong circularly polarized light pulses, we confirm that the ionization of p orbitals with defined angular momentum depends on the sense of rotation of the applied field. A simple ad-hoc modification of the adiabatic local-density exchange-correlation functional is proposed to remedy its unphysical behavior under orbital depletion.
Indian Academy of Sciences (India)
Amita Wadehra; B M Deb
2007-09-01
A time-dependent generalized non-linear Schrödinger equation (GNLSE) of motion was earlier derived in our laboratory by combining density functional theory and quantum fluid dynamics in threedimensional space. In continuation of the work reported previously, the GNLSE is applied to provide additional knowledge on the femtosecond dynamics of the electron density in the hydrogen molecule interacting with high-intensity laser fields. For this purpose, the GNLSE is solved numerically for many time-steps over a total interaction time of 100 fs, by employing a finite-difference scheme. Various time-dependent (TD) quantities, namely, electron density, ground-state survival probability and dipole moment have been obtained for two laser wavelengths and four different intensities. The high-order harmonics generation (HHG) is also examined. The present approach goes beyond the linear response formalism and, in principle, calculates the TD electron density to all orders of change.
Linear-response time-dependent density-functional theory with pairing fields.
Peng, Degao; van Aggelen, Helen; Yang, Yang; Yang, Weitao
2014-05-14
Recent development in particle-particle random phase approximation (pp-RPA) broadens the perspective on ground state correlation energies [H. van Aggelen, Y. Yang, and W. Yang, Phys. Rev. A 88, 030501 (2013), Y. Yang, H. van Aggelen, S. N. Steinmann, D. Peng, and W. Yang, J. Chem. Phys. 139, 174110 (2013); D. Peng, S. N. Steinmann, H. van Aggelen, and W. Yang, J. Chem. Phys. 139, 104112 (2013)] and N ± 2 excitation energies [Y. Yang, H. van Aggelen, and W. Yang, J. Chem. Phys. 139, 224105 (2013)]. So far Hartree-Fock and approximated density-functional orbitals have been utilized to evaluate the pp-RPA equation. In this paper, to further explore the fundamentals and the potential use of pairing matrix dependent functionals, we present the linear-response time-dependent density-functional theory with pairing fields with both adiabatic and frequency-dependent kernels. This theory is related to the density-functional theory and time-dependent density-functional theory for superconductors, but is applied to normal non-superconducting systems for our purpose. Due to the lack of the proof of the one-to-one mapping between the pairing matrix and the pairing field for time-dependent systems, the linear-response theory is established based on the representability assumption of the pairing matrix. The linear response theory justifies the use of approximated density-functionals in the pp-RPA equation. This work sets the fundamentals for future density-functional development to enhance the description of ground state correlation energies and N ± 2 excitation energies.
Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J; Lopata, Kenneth
2016-09-07
Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.
Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J.; Lopata, Kenneth
2016-09-01
Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.
He 2++ molecular ion in a strong time-dependent magnetic field: a current-density functional study.
Vikas
2011-08-01
The He 2++ molecular ion exposed to a strong ultrashort time-dependent (TD) magnetic field of the order of 10(9) G is investigated through a quantum fluid dynamics (QFD) and current-density functional theory (CDFT) based approach using vector exchange-correlation (XC) potential and energy density functional that depend not only on the electronic charge-density but also on the current density. The TD-QFD-CDFT computations are performed in a parallel internuclear-axis and magnetic field-axis configuration at the field-free equilibrium internuclear separation R = 1.3 au with the field-strength varying between 0 and 10(11) G. The TD behavior of the exchange- and correlation energy of the He 2++ is analyzed and compared with that obtained using a [B-TD-QFD-density functional theory (DFT)] approach based on the conventional TD-DFT under similar computational constraints but using only scalar XC potential and energy density functional dependent on the electronic charge-density alone. The CDFT based approach yields TD exchange- and correlation energy and TD electronic charge-density significantly different from that obtained using the conventional TD-DFT based approach, particularly, at typical magnetic field strengths and during a typical time period of the TD field. This peculiar behavior of the CDFT-based approach is traced to the TD current-density dependent vector XC potential, which can induce nonadiabatic effects causing retardation of the oscillating electronic charge density. Such dissipative electron dynamics of the He 2++ molecular ion is elucidated by treating electronic charge density as an electron-"fluid" in the terminology of QFD.
Laser-assisted field evaporation of metal oxides: A time-dependent density functional theory study
Xia, Yu; Li, Zhibing
2016-11-01
To understand laser-assisted field evaporation of semiconductors and insulators at the microscopic level, we study the time evolution of the electronic and atomic structure of a MgO cluster in high electrostatic fields subjected to strong laser pulses. We find that the critical laser intensity for evaporation decreases linearly as the electrostatic field strength increases. The optical absorption enhancement in high electrostatic field is confirmed by the redshift of the optical absorption spectra, the reduction of the energy gap, and the increase of the absorption cross section.
Gao, Yi; Neuhauser, Daniel
2012-08-21
We develop an approach for dynamical (ω > 0) embedding of mixed quantum mechanical (QM)/classical (or more precisely QM/electrodynamics) systems with a quantum sub-region, described by time-dependent density functional theory (TDDFT), within a classical sub-region, modeled here by the recently proposed near-field (NF) method. Both sub-systems are propagated simultaneously and are coupled through a common Coulomb potential. As a first step we implement the method to study the plasmonic response of a metal film which is half jellium-like QM and half classical. The resulting response is in good agreement with both full-scale TDDFT and the purely classical NF method. The embedding method is able to describe the optical response of the whole system while capturing quantum mechanical effects, so it is a promising approach for studying electrodynamics in hybrid molecules-metals nanostructures.
Effective Maxwell Equations from Time-dependent Density Functional Theory
Institute of Scientific and Technical Information of China (English)
Weinan E; Jianfeng LU; Xu YANG
2011-01-01
The behavior of interacting electrons in a perfect crystal under macroscopic external electric and magnetic fields is studied. Effective Maxwell equations for the macroscopic electric and magnetic fields are derived starting from time-dependent density functional theory. Effective permittivity and permeability coefficients are obtained.
Vikas, Hash(0x125f4490)
2011-02-01
Evolution of the helium atom in a strong time-dependent (TD) magnetic field ( B) of strength up to 1011 G is investigated through a quantum fluid dynamics (QFD) based current-density functional theory (CDFT). The TD-QFD-CDFT computations are performed through numerical solution of a single generalized nonlinear Schrödinger equation employing vector exchange-correlation potentials and scalar exchange-correlation density functionals that depend both on the electronic charge-density and the current-density. The results are compared with that obtained from a B-TD-QFD-DFT approach (based on conventional TD-DFT) under similar numerical constraints but employing only scalar exchange-correlation potential dependent on electronic charge-density only. The B-TD-QFD-DFT approach, at a particular TD magnetic field-strength, yields electronic charge- and current-densities as well as exchange-correlation potential resembling with that obtained from the time-independent studies involving static (time-independent) magnetic fields. However, TD-QFD-CDFT electronic charge- and current-densities along with the exchange-correlation potential and energy differ significantly from that obtained using B-TD-QFD-DFT approach, particularly at field-strengths >109 G, representing dynamical effects of a TD field. The work concludes that when a helium atom is subjected to a strong TD magnetic field of order >109 G, the conventional TD-DFT based approach differs "dynamically" from the CDFT based approach under similar computational constraints.
Strubbe, David A.; Andrade, Xavier; Rubio, Angel; Louie, Steven G.
2010-03-01
Chloroform is often used as a solvent when measuring non-linear optical properties of organic molecules. We assess the influence of the solution environment on the molecular properties by calculating directly the non-linear susceptibilities of liquid chloroform at optical frequencies. We use the Sternheimer equation in time-dependent density-functional theory [J. Chem. Phys. 126, 184106 (2007)], on snapshots from ab initio molecular dynamics. We compare the results to those in the gas and solid phases, and to experimental values. We also calculate ab initio local-field factors, used to analyze electric-field-induced second-harmonic generation (EFISH) and hyper-Rayleigh scattering (HRS) experiments.
Studies of Spuriously Time-dependent Resonances in Time-dependent Density Functional Theory
Luo, Kai; Maitra, Neepa T
2016-01-01
Adiabatic approximations in time-dependent density functional theory (TDDFT) will in general yield unphysical time-dependent shifts in the resonance positions of a system driven far from its ground-state. This spurious time-dependence is rationalized in [J. I. Fuks, K. Luo, E. D. Sandoval and N. T. Maitra, Phys. Rev. Lett. {\\bf 114}, 183002 (2015)] in terms of the violation of an exact condition by the non-equilibrium exchange-correlation kernel of TDDFT. Here we give details on the derivation and discuss reformulations of the exact condition that apply in special cases. In its most general form, the condition states that when a system is left in an arbitrary state, in the absence of time-dependent external fields nor ionic motion, the TDDFT resonance position for a given transition is independent of the state. Special cases include the invariance of TDDFT resonances computed with respect to any reference interacting stationary state of a fixed potential, and with respect to any choice of appropriate stationa...
Energy Technology Data Exchange (ETDEWEB)
Vikas [Quantum Chemistry Group, Department of Chemistry and Centre of Advanced Studies in Chemistry, Panjab University, 160014 Chandigrah (India)
2011-02-15
Evolution of the helium atom in a strong time-dependent (TD) magnetic field (B) of strength up to 10{sup 11} G is investigated through a quantum fluid dynamics (QFD) based current-density functional theory (CDFT). The TD-QFD-CDFT computations are performed through numerical solution of a single generalized nonlinear Schroedinger equation employing vector exchange-correlation potentials and scalar exchange-correlation density functionals that depend both on the electronic charge-density and the current-density. The results are compared with that obtained from a B-TD-QFD-DFT approach (based on conventional TD-DFT) under similar numerical constraints but employing only scalar exchange-correlation potential dependent on electronic charge-density only. The B-TD-QFD-DFT approach, at a particular TD magnetic field-strength, yields electronic charge- and current-densities as well as exchange-correlation potential resembling with that obtained from the time-independent studies involving static (time-independent) magnetic fields. However, TD-QFD-CDFT electronic charge- and current-densities along with the exchange-correlation potential and energy differ significantly from that obtained using B-TD-QFD-DFT approach, particularly at field-strengths >10{sup 9} G, representing dynamical effects of a TD field. The work concludes that when a helium atom is subjected to a strong TD magnetic field of order >10{sup 9} G, the conventional TD-DFT based approach differs 'dynamically' from the CDFT based approach under similar computational constraints. (author)
Chu, Shih-I
2005-08-08
In this paper, we present a short account of some recent developments of self-interaction-free density-functional theory (DFT) and time-dependent density-functional theory (TDDFT) for accurate and efficient treatment of the electronic structure, and time-dependent quantum dynamics of many-electron atomic and molecular systems. The conventional DFT calculations using approximate and explicit exchange-correlation energy functional contain spurious self-interaction energy and improper long-range asymptotic potential, preventing reliable treatment of the excited, resonance, and continuum states. We survey some recent developments of DFT/TDDFT with optimized effective potential (OEP) and self-interaction correction (SIC) for both atomic and molecular systems for overcoming some of the above mentioned difficulties. These DFT (TDDFT)/OEP-SIC approaches allow the use of orbital-independent single-particle local potential which is self-interaction free. In addition we discuss several numerical techniques recently developed for efficient and high-precision treatment of the self-interaction-free DFT/TDDFT equations. The usefulness of these procedures is illustrated by a few case studies of atomic, molecular, and condensed matter processes of current interests, including (a) autoionizing resonances, (b) relativistic OEP-SIC treatment of atomic structure (Z=2-106), (c) shell-filling electronic structure in quantum dots, (d) atomic and molecular processes in intense laser fields, including multiphoton ionization, and very-high-order harmonic generation, etc. For the time-dependent processes, an alternative Floquet formulation of TDDFT is introduced for time-independent treatment of multiphoton processes in intense periodic or quasiperiodic fields. We conclude this paper with some open questions and perspectives of TDDFT.
Zheng, Xiao; Yam, ChiYung; Wang, Fan; Chen, GuanHua
2011-08-28
We present the time-dependent holographic electron density theorem (TD-HEDT), which lays the foundation of time-dependent density-functional theory (TDDFT) for open electronic systems. For any finite electronic system, the TD-HEDT formally establishes a one-to-one correspondence between the electron density inside any finite subsystem and the time-dependent external potential. As a result, any electronic property of an open system in principle can be determined uniquely by the electron density function inside the open region. Implications of the TD-HEDT on the practicality of TDDFT are also discussed.
Time dependent mean-field games
Gomes, Diogo A.
2014-01-06
We consider time dependent mean-field games (MFG) with a local power-like dependence on the measure and Hamiltonians satisfying both sub and superquadratic growth conditions. We establish existence of smooth solutions under a certain set of conditions depending both on the growth of the Hamiltonian as well as on the dimension. In the subquadratic case this is done by combining a Gagliardo-Nirenberg type of argument with a new class of polynomial estimates for solutions of the Fokker-Planck equation in terms of LrLp- norms of DpH. These techniques do not apply to the superquadratic case. In this setting we recur to a delicate argument that combines the non-linear adjoint method with polynomial estimates for solutions of the Fokker-Planck equation in terms of L1L1-norms of DpH. Concerning the subquadratic case, we substantially improve and extend the results previously obtained. Furthermore, to the best of our knowledge, the superquadratic case has not been addressed in the literature yet. In fact, it is likely that our estimates may also add to the current understanding of Hamilton-Jacobi equations with superquadratic Hamiltonians.
Yokogawa, D.
2016-09-01
Theoretical approach to design bright bio-imaging molecules is one of the most progressing ones. However, because of the system size and computational accuracy, the number of theoretical studies is limited to our knowledge. To overcome the difficulties, we developed a new method based on reference interaction site model self-consistent field explicitly including spatial electron density distribution and time-dependent density functional theory. We applied it to the calculation of indole and 5-cyanoindole at ground and excited states in gas and solution phases. The changes in the optimized geometries were clearly explained with resonance structures and the Stokes shift was correctly reproduced.
Multicomponent density-functional theory for time-dependent systems
Butriy, O.; Ebadi, H.; de Boeij, P. L.; van Leeuwen, R.; Gross, E. K. U.
2007-01-01
We derive the basic formalism of density functional theory for time-dependent electron-nuclear systems. The basic variables of this theory are the electron density in body-fixed frame coordinates and the diagonal of the nuclear N-body density matrix. The body-fixed frame transformation is carried ou
Invariant Hermitian Operator and Density Operator for the Adiabatically Time-Dependent System
Institute of Scientific and Technical Information of China (English)
YAN Feng-Li; YANG Lin-Guang
2001-01-01
The density operator is approximately expressed as a function of the invariant Hermitian operator for the adiabatically time-dependent system. Using this method, the calculation of the density operator for the Heisenberg spin system in a weakly time-dependent magnetic field is exemplified. By virtue of the density operator, we obtain equilibrium.``
Energy Technology Data Exchange (ETDEWEB)
Kapoor, Varun; Brics, Martins; Bauer, Dieter [Institut fuer Physik, Universitaet Rostock, 18051 Rostock (Germany)
2013-07-01
Autoionizing states are inaccessible to time-dependent density functional theory (TDDFT) using known, adiabatic Kohn-Sham (KS) potentials. We determine the exact KS potential for a numerically exactly solvable model Helium atom interacting with a laser field that is populating an autoionizing state. The exact single-particle density of the population in the autoionizing state corresponds to that of the energetically lowest quasi-stationary state in the exact KS potential. We describe how this exact potential controls the decay by a barrier whose height and width allows for the density to tunnel out and decay with the same rate as in the ab initio time-dependent Schroedinger calculation. However, devising a useful exchange-correlation potential that is capable of governing such a scenario in general and in more complex systems is hopeless. As an improvement over TDDFT, time-dependent reduced density matrix functional theory has been proposed. We are able to obtain for the above described autoionization process the exact time-dependent natural orbitals (i.e., the eigenfunctions of the exact, time-dependent one-body reduced density matrix) and study the potentials that appear in the equations of motion for the natural orbitals and the structure of the two-body density matrix expanded in them.
Eigenstates of the time-dependent density-matrix theory
Energy Technology Data Exchange (ETDEWEB)
Tohyama, M. [Kyorin University School of Medicine, 181-8611, Mitaka, Tokyo (Japan); Schuck, P. [Institut de Physique Nucleaire, IN2P3-CNRS, Universite Paris-Sud, F-91406, Orsay Cedex (France)
2004-02-01
An extended time-dependent Hartree-Fock theory, known as the time-dependent density-matrix theory (TDDM), is solved as a time-independent eigenvalue problem for low-lying 2{sup +} states in {sup 24}O to understand the foundation of the rather successful time-dependent approach. It is found that the calculated strength distribution of the 2{sup +} states has physically reasonable behavior and that the strength function is practically positive definite though the non-Hermitian Hamiltonian matrix obtained from TDDM does not guarantee it. A relation to an Extended RPA theory with hermiticity is also investigated. It is found that the density-matrix formalism is a good approximation to the Hermitian Extended RPA theory. (orig.)
Linear-response thermal time-dependent density functional theory
Pribram-Jones, Aurora; Burke, Kieron
2015-01-01
The van Leeuwen proof of linear-response time-dependent density functional theory (TDDFT) is generalized to thermal ensembles. This allows generalization to finite temperatures of the Gross-Kohn relation, the exchange-correlation kernel of TDDFT, and fluctuation dissipation theorem for DFT. This produces a natural method for generating new thermal exchange-correlation (XC) approximations.
Time dependent density functional calculation of plasmon response in clusters
Institute of Scientific and Technical Information of China (English)
Wang Feng(王锋); Zhang Feng-Shou(张丰收); Eric Suraud
2003-01-01
We have introduced a theoretical scheme for the efficient description of the optical response of a cluster based on the time-dependent density functional theory. The practical implementation is done by means of the fully fledged timedependent local density approximation scheme, which is solved directly in the time domain without any linearization.As an example we consider the simple Na2 cluster and compute its surface plasmon photoabsorption cross section, which is in good agreement with the experiments.
Time-dependent density functional theory for quantum transport.
Zheng, Xiao; Chen, GuanHua; Mo, Yan; Koo, SiuKong; Tian, Heng; Yam, ChiYung; Yan, YiJing
2010-09-21
Based on our earlier works [X. Zheng et al., Phys. Rev. B 75, 195127 (2007); J. S. Jin et al., J. Chem. Phys. 128, 234703 (2008)], we propose a rigorous and numerically convenient approach to simulate time-dependent quantum transport from first-principles. The proposed approach combines time-dependent density functional theory with quantum dissipation theory, and results in a useful tool for studying transient dynamics of electronic systems. Within the proposed exact theoretical framework, we construct a number of practical schemes for simulating realistic systems such as nanoscopic electronic devices. Computational cost of each scheme is analyzed, with the expected level of accuracy discussed. As a demonstration, a simulation based on the adiabatic wide-band limit approximation scheme is carried out to characterize the transient current response of a carbon nanotube based electronic device under time-dependent external voltages.
Time-dependent density-functional theory for extended systems
Energy Technology Data Exchange (ETDEWEB)
Botti, Silvana [European Theoretical Spectroscopy Facility (ETSF) (Country Unknown); Schindlmayr, Arno [European Theoretical Spectroscopy Facility (ETSF) (Country Unknown); Del Sole, Rodolfo [European Theoretical Spectroscopy Facility (ETSF) (Country Unknown); Reining, Lucia [European Theoretical Spectroscopy Facility (ETSF) (Country Unknown)
2007-03-15
For the calculation of neutral excitations, time-dependent density functional theory (TDDFT) is an exact reformulation of the many-body time-dependent Schroedinger equation, based on knowledge of the density instead of the many-body wavefunction. The density can be determined in an efficient scheme by solving one-particle non-interacting Schroedinger equations-the Kohn-Sham equations. The complication of the problem is hidden in the-unknown-time-dependent exchange and correlation potential that appears in the Kohn-Sham equations and for which it is essential to find good approximations. Many approximations have been suggested and tested for finite systems, where even the very simple adiabatic local-density approximation (ALDA) has often proved to be successful. In the case of solids, ALDA fails to reproduce optical absorption spectra, which are instead well described by solving the Bethe-Salpeter equation of many-body perturbation theory (MBPT). On the other hand, ALDA can lead to excellent results for loss functions (at vanishing and finite momentum transfer). In view of this and thanks to recent successful developments of improved linear-response kernels derived from MBPT, TDDFT is today considered a promising alternative to MBPT for the calculation of electronic spectra, even for solids. After reviewing the fundamentals of TDDFT within linear response, we discuss different approaches and a variety of applications to extended systems.
Density-functional perturbation theory goes time-dependent
Gebauer, Ralph; Rocca, Dario; Baroni, Stefano
2009-01-01
The scope of time-dependent density-functional theory (TDDFT) is limited to the lowest portion of the spectrum of rather small systems (a few tens of atoms at most). In the static regime, density-functional perturbation theory (DFPT) allows one to calculate response functions of systems as large as currently dealt with in ground-state simulations. In this paper we present an effective way of combining DFPT with TDDFT. The dynamical polarizability is first expressed as an off-diagonal matrix e...
Time-dependent density functional theory: Causality and other problems
Energy Technology Data Exchange (ETDEWEB)
Ruggenthaler, Michael; Bauer, Dieter [Max-Planck-Inst. fuer Kernphysik, Heidelberg (Germany)
2007-07-01
Time-dependent density functional theory (TDDFT) is a reformulation of the time dependent many-body problem in quantum mechanics which is capable of reducing the computational cost to calculate, e.g., strongly driven many-electron systems enormously. Recent developments were able to overcome fundamental problems associated with ionization processes. Still vital issues have to be clarified. Besides the construction of the underlying functionals we investigate the causality problem of TDDFT by general considerations and by studying a exactly solvable system of two correlated electrons in an intense laser-pulse. For the latter system, the two alternative approaches to the construction of the action functional or a constrained functional derivative by van Leeuwen and Gal, respectively, are explored.
Perspective: Fundamental aspects of time-dependent density functional theory
Maitra, Neepa T.
2016-06-01
In the thirty-two years since the birth of the foundational theorems, time-dependent density functional theory has had a tremendous impact on calculations of electronic spectra and dynamics in chemistry, biology, solid-state physics, and materials science. Alongside the wide-ranging applications, there has been much progress in understanding fundamental aspects of the functionals and the theory itself. This Perspective looks back to some of these developments, reports on some recent progress and current challenges for functionals, and speculates on future directions to improve the accuracy of approximations used in this relatively young theory.
Time-dependent density-functional theory concepts and applications
Ullrich, Carsten A
2011-01-01
Time-dependent density-functional theory (TDDFT) describes the quantum dynamics of interacting electronic many-body systems formally exactly and in a practical and efficient manner. TDDFT has become the leading method for calculating excitation energies and optical properties of large molecules, with accuracies that rival traditional wave-function based methods, but at a fraction of the computational cost.This book is the first graduate-level text on the concepts and applications of TDDFT, including many examples and exercises, and extensive coverage of the literature. The book begins with a s
Quantum mechanics in strong time dependent external fields
Energy Technology Data Exchange (ETDEWEB)
Pomeau, Y.
1986-01-01
In quantum mechanics, time dependent Hamiltonians are most often studied by perturbation methods, the amplitude of the unsteady force being assumed to be small. On two examples (two level system with a large time dependent coupling, and atoms in large external unsteady field). I show that the opposite limit (large time dependent field) can be analyzed in some details too. For a particle in a central potential and submitted to a large periodic external field, one is led to make a Kapitza averaging because the intrinsic frequency tends to zero when the external field diverges. In that way one has to introduce a steady effective potential with singular turning points.
Time-dependent density-functional description of nuclear dynamics
Nakatsukasa, Takashi; Matsuo, Masayuki; Yabana, Kazuhiro
2016-01-01
We present the basic concepts and recent developments in the time-dependent density functional theory (TDDFT) for describing nuclear dynamics at low energy. The symmetry breaking is inherent in nuclear energy density functionals (EDFs), which provides a practical description of important correlations at the ground state. Properties of elementary modes of excitation are strongly influenced by the symmetry breaking and can be studied with TDDFT. In particular, a number of recent developments in the linear response calculation have demonstrated their usefulness in description of collective modes of excitation in nuclei. Unrestricted real-time calculations have also become available in recent years, with new developments for quantitative description of nuclear collision phenomena. There are, however, limitations in the real-time approach; for instance, it cannot describe the many-body quantum tunneling. Thus, we treat the quantum fluctuations associated with slow collective motions assuming that time evolution of...
Stochastic Time-Dependent Current-Density Functional Theory
D'Agosta, Roberto
2008-03-01
Static and dynamical density functional methods have been applied with a certain degree of success to a variety of closed quantum mechanical systems, i.e., systems that can be described via a Hamiltonian dynamics. However, the relevance of open quantum systems - those coupled to external environments, e.g., baths or reservoirs - cannot be overestimated. To investigate open quantum systems with DFT methods we have introduced a new theory, we have named Stochastic Time-Dependent Current Density Functional theory (S-TDCDFT) [1]: starting from a suitable description of the system dynamics via a stochastic Schrödinger equation [2], we have proven that given an initial quantum state and the coupling between the system and the environment, there is a one-to-one correspondence between the ensemble-averaged current density and the external vector potential applied to the system.In this talk, I will introduce the stochastic formalism needed for the description of open quantum systems, discuss in details the theorem of Stochastic TD-CDFT, and provide few examples of its applicability like the dissipative dynamics of excited systems, quantum-measurement theory and other applications relevant to charge and energy transport in nanoscale systems.[1] M. Di Ventra and R. D'Agosta, Physical Review Letters 98, 226403 (2007)[2] N.G. van Kampen, Stochastic processes in Physics and Chemistry, (North Holland, 2001), 2nd ed.
Vacuum radiation induced by time dependent electric field
Directory of Open Access Journals (Sweden)
Bo Zhang
2017-04-01
Full Text Available Many predictions of new phenomena given by strong field quantum electrodynamics (SFQED will be tested on next generation multi-petawatt laser facilities in the near future. These new phenomena are basis to understand physics in extremely strong electromagnetic fields therefore have attracted wide research interest. Here we discuss a new SFQED phenomenon that is named as vacuum radiation. In vacuum radiation, a virtual electron loop obtain energy from time dependent external electric field and radiate an entangled photon pair. Features of vacuum radiation in a locally time dependent electric field including spectrum, characteristic temperature, production rate and power are given.
Vacuum radiation induced by time dependent electric field
Zhang, Bo; Zhang, Zhi-meng; Hong, Wei; He, Shu-Kai; Teng, Jian; Gu, Yu-qiu
2017-04-01
Many predictions of new phenomena given by strong field quantum electrodynamics (SFQED) will be tested on next generation multi-petawatt laser facilities in the near future. These new phenomena are basis to understand physics in extremely strong electromagnetic fields therefore have attracted wide research interest. Here we discuss a new SFQED phenomenon that is named as vacuum radiation. In vacuum radiation, a virtual electron loop obtain energy from time dependent external electric field and radiate an entangled photon pair. Features of vacuum radiation in a locally time dependent electric field including spectrum, characteristic temperature, production rate and power are given.
Density-functional perturbation theory goes time-dependent
Directory of Open Access Journals (Sweden)
Gebauer, Ralph
2008-05-01
Full Text Available The scope of time-dependent density-functional theory (TDDFT is limited to the lowest portion of the spectrum of rather small systems (a few tens of atoms at most. In the static regime, density-functional perturbation theory (DFPT allows one to calculate response functions of systems as large as currently dealt with in ground-state simulations. In this paper we present an effective way of combining DFPT with TDDFT. The dynamical polarizability is first expressed as an off-diagonal matrix element of the resolvent of the Kohn-Sham Liouvillian super-operator. A DFPT representation of response functions allows one to avoid the calculation of unoccupied Kohn-Sham orbitals. The resolvent of the Liouvillian is finally conveniently evaluated using a newly developed non-symmetric Lanczos technique, which allows for the calculation of the entire spectrum with a single Lanczos recursion chain. Each step of the chain essentially requires twice as many operations as a single step of the iterative diagonalization of the unperturbed Kohn-Sham Hamiltonian or, for that matter, as a single time step of a Car-Parrinello molecular dynamics run. The method will be illustrated with a few case molecular applications.
Charge transfer in time-dependent density functional theory
Maitra, Neepa T.
2017-10-01
Charge transfer plays a crucial role in many processes of interest in physics, chemistry, and bio-chemistry. In many applications the size of the systems involved calls for time-dependent density functional theory (TDDFT) to be used in their computational modeling, due to its unprecedented balance between accuracy and efficiency. However, although exact in principle, in practise approximations must be made for the exchange-correlation functional in this theory, and the standard functional approximations perform poorly for excitations which have a long-range charge-transfer component. Intense progress has been made in developing more sophisticated functionals for this problem, which we review. We point out an essential difference between the properties of the exchange-correlation kernel needed for an accurate description of charge-transfer between open-shell fragments and between closed-shell fragments. We then turn to charge-transfer dynamics, which, in contrast to the excitation problem, is a highly non-equilibrium, non-perturbative, process involving a transfer of one full electron in space. This turns out to be a much more challenging problem for TDDFT functionals. We describe dynamical step and peak features in the exact functional evolving over time, that are missing in the functionals currently used. The latter underestimate the amount of charge transferred and manifest a spurious shift in the charge transfer resonance position. We discuss some explicit examples.
Simple preconditioning for time-dependent density functional perturbation theory
Lehtovaara, Lauri; Marques, Miguel A. L.
2011-07-01
By far, the most common use of time-dependent density functional theory is in the linear-reponse regime, where it provides information about electronic excitations. Ideally, the linear-response equations should be solved by a method that avoids the use of the unoccupied Kohn-Sham states — such as the Sternheimer method — as this reduces the complexity and increases the precision of the calculation. However, the Sternheimer equation becomes ill-conditioned near and indefinite above the first resonant frequency, seriously hindering the use of efficient iterative solution methods. To overcome this serious limitation, and to improve the general convergence properties of the iterative techniques, we propose a simple preconditioning strategy. In our method, the Sternheimer equation is solved directly as a linear equation using an iterative Krylov subspace method, i.e., no self-consistent cycle is required. Furthermore, the preconditioner uses the information of just a few unoccupied states and requires simple and minimal modifications to existing implementations. In this way, convergence can be reached faster and in a considerably wider frequency range than the traditional approach.
Effective field theory in time-dependent settings
Collins, Hael; Ross, Andreas
2012-01-01
We use the in-in or Schwinger-Keldysh formalism to explore the construction and interpretation of effective field theories for time-dependent systems evolving out of equilibrium. Starting with a simple model consisting of a heavy and a light scalar field taken to be in their free vacuum states at a finite initial time, we study the effects from the heavy field on the dynamics of the light field by analyzing the equation of motion for the expectation value of the light background field. New terms appear which cannot arise from a local action of an effective field theory in terms of the light field, though they disappear in the adiabatic limit. We discuss the origins of these terms as well as their possible implications for time dependent situations such as inflation.
Quantum Drude friction for time-dependent density functional theory
Neuhauser, Daniel; Lopata, Kenneth
2008-10-01
way to very simple finite grid description of scattering and multistage conductance using time-dependent density functional theory away from the linear regime, just as absorbing potentials and self-energies are useful for noninteracting systems and leads.
Zahn, Jochen
2015-01-01
In the framework of quantum electrodynamics (QED) in external potentials, we introduce a method to compute the time-dependence of the expectation value of the current density for time-dependent homogeneous external electric fields. We apply it to the so-called Sauter pulse. For late times, our results agree with the asymptotic value due to electron-positron pair production. For sub-critical peak field strengths, or results agree very well with the general expression derived by Serber for the linearization in the external field. In particular, the expectation value of the current density at intermediate times can be much greater than at asymptotic times. We comment on consequences of these findings for recent proposals to test the Schwinger effect with high intensity lasers using processes at intermediate times.
Truncation scheme of time-dependent density-matrix approach
Energy Technology Data Exchange (ETDEWEB)
Tohyama, Mitsuru [Kyorin University School of Medicine, Mitaka, Tokyo (Japan); Schuck, Peter [Universite Paris-Sud, Institut de Physique Nucleaire, IN2P3-CNRS, Orsay Cedex (France); Laboratoire de Physique et de Modelisation des Milieux Condenses et Universite Joseph Fourier, Grenoble Cedex 9 (France)
2014-04-15
A truncation scheme of the Bogoliubov-Born-Green-Kirkwood-Yvon hierarchy for reduced density matrices, where a three-body density matrix is approximated by the antisymmetrized products of two-body density matrices, is proposed. This truncation scheme is tested for three model Hamiltonians. It is shown that the obtained results are in good agreement with the exact solutions. (orig.)
Energy Technology Data Exchange (ETDEWEB)
Seth, Michael, E-mail: mseth@ucalgary.ca [Department of Chemistry, University of Calgary, University Drive 2500, Calgary, AB T2N-1N4 (Canada); Ziegler, Tom, E-mail: ziegler@ucalgary.ca [Department of Chemistry, University of Calgary, University Drive 2500, Calgary, AB T2N-1N4 (Canada)
2012-02-20
The theory of calculating magnetic circular dichroism in the presence of zero-field splitting is presented and illustrated with applications to small and medium-sized systems. Highlights: Black-Right-Pointing-Pointer ZFS and MCD calculated with DFT are combined. Black-Right-Pointing-Pointer Influence of ZFS on the MCD spectra of group 15 hydrides analyzed. Black-Right-Pointing-Pointer Absorption and MCD spectra of Fe-EDTA-peroxide complex calculated. Black-Right-Pointing-Pointer ZFS does not appear to influence MCD spectra qualitatively. Black-Right-Pointing-Pointer Quantitative effects are present and difficult to model. - Abstract: An implementation into the ADF program of a method for calculating zero-field splitting (ZFS) of molecules with spin degenerate ground states and S > 1/2 is reported. ZFS can influence temperature-dependent magnetic circular dichroism (MCD) intensity. Previously published equations for the calculation of MCD with time-dependent density functional theory are modified to take zero-field splitting into account. The MCD spectra of the group 15 hydrides and the complex formed from iron (III), ethylenediaminetetraacetate and peroxide, [Fe(III)(EDTA)O{sub 2}]{sup 3-} are simulated. These spectra are analyzed with particular reference to the influence of ZFS on the MCD intensity.
Time-Dependent Mean-Field Games with Logarithmic Nonlinearities
Gomes, Diogo A.
2015-10-06
In this paper, we prove the existence of classical solutions for time-dependent mean-field games with a logarithmic nonlinearity and subquadratic Hamiltonians. Because the logarithm is unbounded from below, this nonlinearity poses substantial mathematical challenges that have not been addressed in the literature. Our result is proven by recurring to a delicate argument which combines Lipschitz regularity for the Hamilton-Jacobi equation with estimates for the nonlinearity in suitable Lebesgue spaces. Lipschitz estimates follow from an application of the nonlinear adjoint method. These are then combined with a priori bounds for solutions of the Fokker-Planck equation and a concavity argument for the nonlinearity.
Time-Dependent Neutron and Photon Dose-Field Analysis
Energy Technology Data Exchange (ETDEWEB)
Wooten, Hasani Omar [Georgia Inst. of Technology, Atlanta, GA (United States)
2005-08-01
A unique tool is developed that allows the user to model physical representations of complicated glovebox facilities in two dimensions and determine neutral-particle flux and ambient dose-equivalent fields throughout that geometry. The Pandemonium code, originally designed to determine flux and dose-rates only, is improved to include realistic glovebox geometries, time-dependent source and detector positions, time-dependent shielding thickness calculations, time-integrated doses, a representative criticality accident scenario based on time-dependent reactor kinetics, and more rigorous photon treatment. A primary benefit of this work has been an extensive analysis and improvement of the photon model that is not limited to the application described in this thesis. The photon model has been extended in energy range to 10 MeV to include photons from fission and new photon buildup factors have been included that account for the effects of photon buildup at slant-path thicknesses as a function of angle, where the mean free path thickness has been preserved. The overall system of codes is user-friendly and it is directly applicable to facilities such as the plutonium facility at Los Alamos National Laboratory, where high-intensity neutron and photon emitters are regularly used. The codes may be used to determine a priori doses for given work scenarios in an effort to supply dose information to process models which will in turn assist decision makers on ensuring as low as reasonably achievable (ALARA) compliance. In addition, coupling the computational results of these tools with the process model visualization tools will help to increase worker safety and radiological safety awareness.
Numerical density-to-potential inversions in time-dependent density functional theory.
Jensen, Daniel S; Wasserman, Adam
2016-08-01
We treat the density-to-potential inverse problem of time-dependent density functional theory as an optimization problem with a partial differential equation constraint. The unknown potential is recovered from a target density by applying a multilevel optimization method controlled by error estimates. We employ a classical optimization routine using gradients efficiently computed by the discrete adjoint method. The inverted potential has both a real and imaginary part to reduce reflections at the boundaries and other numerical artifacts. We demonstrate this method on model one-dimensional systems. The method can be straightforwardly extended to a variety of numerical solvers of the time-dependent Kohn-Sham equations and to systems in higher dimensions.
Pernal, Katarzyna
2012-05-14
Time-dependent density functional theory (TD-DFT) in the adiabatic formulation exhibits known failures when applied to predicting excitation energies. One of them is the lack of the doubly excited configurations. On the other hand, the time-dependent theory based on a one-electron reduced density matrix functional (time-dependent density matrix functional theory, TD-DMFT) has proven accurate in determining single and double excitations of H(2) molecule if the exact functional is employed in the adiabatic approximation. We propose a new approach for computing excited state energies that relies on functionals of electron density and one-electron reduced density matrix, where the latter is applied in the long-range region of electron-electron interactions. A similar approach has been recently successfully employed in predicting ground state potential energy curves of diatomic molecules even in the dissociation limit, where static correlation effects are dominating. In the paper, a time-dependent functional theory based on the range-separation of electronic interaction operator is rigorously formulated. To turn the approach into a practical scheme the adiabatic approximation is proposed for the short- and long-range components of the coupling matrix present in the linear response equations. In the end, the problem of finding excitation energies is turned into an eigenproblem for a symmetric matrix. Assignment of obtained excitations is discussed and it is shown how to identify double excitations from the analysis of approximate transition density matrix elements. The proposed method used with the short-range local density approximation (srLDA) and the long-range Buijse-Baerends density matrix functional (lrBB) is applied to H(2) molecule (at equilibrium geometry and in the dissociation limit) and to Be atom. The method accounts for double excitations in the investigated systems but, unfortunately, the accuracy of some of them is poor. The quality of the other
Time-dependent density-functional theory for open electronic systems
Institute of Scientific and Technical Information of China (English)
ZHENG Xiao; WANG RuLin
2014-01-01
Time-dependent density-functional theory（TDDFT）has been successfully applied to predict excited-state properties of isolated and periodic systems.However,it cannot address a system coupled to an environment or whose number of electrons is not conserved.To tackle these problems,TDDFT needs to be extended to accommodate open systems.This paper provides a comprehensive account of the recent developments of TDDFT for open systems（TDDFT-OS）,including both theoretical and practical aspects.The practicality and accuracy of a latest TDDFT-OS method is demonstrated with two numerical examples：the time-dependent electron transport through a series of quasi-one-dimensional atomic chains,and the real-time electronic dynamics on a two-dimensional graphene surface.The advancement of TDDFT-OS may lead to promising applications in various fields of chemistry,including energy conversion and heterogeneous catalysis.
Accurate high-harmonic spectra from time-dependent two-particle reduced density matrix theory
Lackner, Fabian; Sato, Takeshi; Ishikawa, Kenichi L; Burgdörfer, Joachim
2016-01-01
The accurate description of the non-linear response of many-electron systems to strong-laser fields remains a major challenge. Methods that bypass the unfavorable exponential scaling with particle number are required to address larger systems. In this paper we present a fully three-dimensional implementation of the time-dependent two-particle reduced density matrix (TD-2RDM) method for many-electron atoms. We benchmark this approach by a comparison with multi-configurational time-dependent Hartree-Fock (MCTDHF) results for the harmonic spectra of beryllium and neon. We show that the TD-2RDM is very well-suited to describe the non-linear atomic response and to reveal the influence of electron-correlation effects.
van Duijnen, Piet Th; Greene, Shannon N; Richards, Nigel G J
2007-07-28
We report the calculated visible spectrum of [FeIII(PyPepS)2]- in aqueous solution. From all-classical molecular dynamics simulations on the solute and 200 water molecules with a polarizable force field, 25 solute/solvent configurations were chosen at random from a 50 ps production run and subjected the systems to calculations using time-dependent density functional theory (TD-DFT) for the solute, combined with a solvation model in which the water molecules carry charges and polarizabilities. In each calculation the first 60 excited states were collected in order to span the experimental spectrum. Since the solute has a doublet ground state several excitations to states are of type "three electrons in three orbitals," each of which gives rise to a manifold of a quartet and two doublet states which cannot properly be represented by single Slater determinants. We applied a tentative scheme to analyze this type of spin contamination in terms of Delta and Delta transitions between the same orbital pairs. Assuming the associated states as pure single determinants obtained from restricted calculations, we construct conformation state functions (CFSs), i.e., eigenfunctions of the Hamiltonian Sz and S2, for the two doublets and the quartet for each Delta,Delta pair, the necessary parameters coming from regular and spin-flip calculations. It appears that the lower final states remain where they were originally calculated, while the higher states move up by some tenths of an eV. In this case filtering out these higher states gives a spectrum that compares very well with experiment, but nevertheless we suggest investigating a possible (re)formulation of TD-DFT in terms of CFSs rather than determinants.
Multi-configuration time-dependent density-functional theory based on range separation
DEFF Research Database (Denmark)
Fromager, E.; Knecht, S.; Jensen, Hans Jørgen Aagaard
2013-01-01
Multi-configuration range-separated density-functional theory is extended to the time-dependent regime. An exact variational formulation is derived. The approximation, which consists in combining a long-range Multi-Configuration- Self-Consistent Field (MCSCF) treatment with an adiabatic short...... in Be and the 11u+ state in the stretched H molecule are improved, although the latter is still significantly underestimated. Exploratory TD-MC-srDFT/GGA calculations for ferrocene yield in general excitation energies at least as good as TD-DFT using the Coulomb attenuated method based on the three-parameter Becke...
The development of the time dependence of the nuclear EMP electric field
Energy Technology Data Exchange (ETDEWEB)
Eng, C
2009-10-30
The nuclear electromagnetic pulse (EMP) electric field calculated with the legacy code CHAP is compared with the field given by an integral solution of Maxwell's equations, also known as the Jefimenko equation, to aid our current understanding on the factors that affect the time dependence of the EMP. For a fair comparison the CHAP current density is used as a source in the Jefimenko equation. At first, the comparison is simplified by neglecting the conduction current and replacing the standard atmosphere with a constant density air slab. The simplicity of the resultant current density aids in determining the factors that affect the rise, peak and tail of the EMP electric field versus time. The three dimensional nature of the radiating source, i.e. sources off the line-of-sight, and the time dependence of the derivative of the current density with respect to time are found to play significant roles in shaping the EMP electric field time dependence. These results are found to hold even when the conduction current and the standard atmosphere are properly accounted for. Comparison of the CHAP electric field with the Jefimenko electric field offers a direct validation of the high-frequency/outgoing wave approximation.
Analyzing Density Operator in Thermal State for Complicated Time-Dependent Optical Systems
Directory of Open Access Journals (Sweden)
Jeong Ryeol Choi
2014-01-01
Full Text Available Density operator of oscillatory optical systems with time-dependent parameters is analyzed. In this case, a system is described by a time-dependent Hamiltonian. Invariant operator theory is introduced in order to describe time-varying behavior of the system. Due to the time dependence of parameters, the frequency of oscillation, so-called a modified frequency of the system, is somewhat different from the natural frequency. In general, density operator of a time-dependent optical system is represented in terms of the modified frequency. We showed how to determine density operator of complicated time-dependent optical systems in thermal state. Usually, density operator description of quantum states is more general than the one described in terms of the state vector.
Correlated electron dynamics and memory in time-dependent density functional theory
Energy Technology Data Exchange (ETDEWEB)
Thiele, Mark
2009-07-28
Time-dependent density functional theory (TDDFT) is an exact reformulation of the time-dependent many-electron Schroedinger equation, where the problem of many interacting electrons is mapped onto the Kohn-Sham system of noninteracting particles which reproduces the exact electronic density. In the Kohn-Sham system all non-classical many-body effects are incorporated in the exchange-correlation potential which is in general unknown and needs to be approximated. It is the goal of this thesis to investigate the connection between memory effects and correlated electron dynamics in strong and weak fields. To this end one-dimensional two-electron singlet systems are studied. At the same time these systems include the onedimensional helium atom model, which is an established system to investigate the crucial effects of correlated electron dynamics in external fields. The studies presented in this thesis show that memory effects are negligible for typical strong field processes. Here the approximation of the spatial nonlocality is of primary importance. For the photoabsorption spectra on the other hand the neglect of memory effects leads to qualitative and quantitative errors, which are shown to be connected to transitions of double excitation character. To develop a better understanding of the conditions under which memory effects become important quantum fluid dynamics has been found to be especially suitable. It represents a further exact reformulation of the quantum mechanic many-body problem which is based on hydrodynamic quantities such as density and velocity. Memory effects are shown to be important whenever the velocity field develops strong gradients and dissipative effects contribute. (orig.)
Time-dependent second Born calculations for model atoms and molecules in strong laser fields
Balzer, K; Bonitz, M
2010-01-01
Using the finite-element discrete variable representation of the nonequilibrium Green's function (NEGF) we extend previous work [K.~Balzer et al., Phys. Rev. A \\textbf{81}, 022510 (2010)] to nonequilibrium situations and compute---from the two-time Schwinger-Keldysh-Kadanoff-Baym equations---the response of the helium atom and the heteronuclear molecule lithium hydride to laser fields in the uv and xuv regime. In particular, by comparing the one-electron density and the dipole moment to time-dependent Hartree-Fock results on one hand and the full solution of the time-dependent Schr\\"odinger equation on the other hand, we demonstrate that the time-dependent second Born approximation carries valuable information about electron-electron correlation effects. Also, we outline an efficient distributed memory concept which enables a parallel and well scalable algorithm for computing the NEGF in the two-time domain.
2007 Time_Dependent Density-Functional Therory (July 15-20, 2007 Colby College, Maine)
Energy Technology Data Exchange (ETDEWEB)
Ullrich Carsten
2008-09-19
Time-dependent density-functional theory (TDDFT) provides an efficient, elegant, and formally exact way of describing the dynamics of interacting many-body quantum systems, circumventing the need for solving the full time-dependent Schroedinger equation. In the 20 years since it was first rigorously established in 1984, the field of TDDFT has made rapid and significant advances both formally as well as in terms of successful applications in chemistry, physics and materials science. Today, TDDFT has become the method of choice for calculating excitation energies of complex molecules, and is becoming increasingly popular for describing optical and spectroscopic properties of a variety of materials such as bulk solids, clusters and nanostructures. Other growing areas of applications of TDDFT are nonlinear dynamics of strongly excited electronic systems and molecular electronics. The purpose and scope of this Gordon Research Conference is to provide a platform for discussing the current state of the art of the rapidly progressing, highly interdisciplinary field of TDDFT, to identify and debate open questions, and to point out new promising research directions. The conference will bring together experts with a diverse background in chemistry, physics, and materials science.
Second Quantized Scalar QED in Homogeneous Time-Dependent Electromagnetic Fields
Kim, Sang Pyo
2014-01-01
We formulate the second quantized scalar quantum electrodynamics in homogeneous, time-dependent electromagnetic fields, in which the Hamiltonian for a charged scalar field is an infinite system of decoupled time-dependent oscillators for electric fields but of coupled time-dependent oscillators for magnetic fields. We then employ the quantum invariant method to find various quantum states for the charged field. For time-dependent electric fields, a pair of quantum invariant operators for each oscillator plays the role of the time-dependent annihilation and creation operators, constructs the exact quantum states, and gives the vacuum persistence amplitude as well as the pair-production rate. We also find the quantum invariants for the coupled oscillators for the charged field in time-dependent magnetic fields and advance a perturbation method when the magnetic fields change adiabatically. Finally the quantum state and pair production is discussed when a time-dependent electric field is present in parallel to t...
Krykunov, Mykhaylo; Autschbach, Jochen
2007-01-14
We report implementations and results of time-dependent density functional calculations (i) of the frequency-dependent magnetic dipole-magnetic dipole polarizability, (ii) of the (observable) translationally invariant linear magnetic response, and (iii) of a linear intensity differential (LID) which includes the dynamic dipole magnetizability. The density functional calculations utilized density fitting. For achieving gauge-origin independence we have employed time-periodic magnetic-field-dependent basis functions as well as the dipole velocity gauge, and have included explicit density-fit related derivatives of the Coulomb potential. We present the results of calculations of static and dynamic magnetic dipole-magnetic dipole polarizabilities for a set of small molecules, the LID for the SF6 molecule, and dispersion curves for M-hexahelicene of the origin invariant linear magnetic response as well as of three dynamic polarizabilities: magnetic dipole-magnetic dipole, electric dipole-electric dipole, and electric dipole-magnetic dipole. We have also performed comparison of the linear magnetic response and magnetic dipole-magnetic dipole polarizability over a wide range of frequencies for H2O and SF6.
Farzanehpour, M.; Tokatly, I. V.
2016-05-01
We use analytic (current) density-potential maps of time-dependent (current) density-functional theory [TD(C)DFT] to inverse engineer analytically solvable time-dependent quantum problems. In this approach the driving potential (the control signal) and the corresponding solution of the Schrödinger equation are parametrized analytically in terms of the basic TD(C)DFT observables. We describe the general reconstruction strategy and illustrate it with a number of explicit examples. First we consider the real space one-particle dynamics driven by a time-dependent electromagnetic field and recover, from the general TDDFT reconstruction formulas, the known exact solution for a driven oscillator with a time-dependent frequency. Then we use analytic maps of the lattice TD(C)DFT to control quantum dynamics in a discrete space. As a first example we construct a time-dependent potential which generates prescribed dynamics on a tight-binding chain. Then our method is applied to the dynamics of spin-1/2 driven by a time-dependent magnetic field. We design an analytic control pulse that transfers the system from the ground to excited state and vice versa. This pulse generates the spin flip thus operating as a quantum not gate.
Developments in deep brain stimulation using time dependent magnetic fields
Energy Technology Data Exchange (ETDEWEB)
Crowther, L.J.; Nlebedim, I.C.; Jiles, D.C.
2012-03-07
The effect of head model complexity upon the strength of field in different brain regions for transcranial magnetic stimulation (TMS) has been investigated. Experimental measurements were used to verify the validity of magnetic field calculations and induced electric field calculations for three 3D human head models of varying complexity. Results show the inability for simplified head models to accurately determine the site of high fields that lead to neuronal stimulation and highlight the necessity for realistic head modeling for TMS applications.
A trapped ion with time-dependent frequency interaction with a laser field
Energy Technology Data Exchange (ETDEWEB)
MartInez, J M Vargas; Moya-Cessa, H [INAOE, Apartado Postal 51 y 216, 72000 Puebla (Mexico)
2004-06-01
We analyse the problem of a trapped ion with time-dependent frequency interacting with a laser field. By using a set of unitary time-dependent transformations we show that this system is equivalent to the interaction between a quantized field and a double level with time-dependent interaction parameters. In passing, we show that in the on-resonance case different vibrational transitions may be achieved by using time-dependent parameters.
Liao, Sheng-Lun; Ho, Tak-San; Rabitz, Herschel; Chu, Shih-I.
2017-06-01
A long-standing challenge in the time-dependent density functional theory is to efficiently solve the exact time-dependent optimized effective potential (TDOEP) integral equation derived from orbital-dependent functionals, especially for the study of nonadiabatic dynamics in time-dependent external fields. In this Letter, we formulate a completely equivalent time-local TDOEP equation that admits a unique real-time solution in terms of time-dependent Kohn-Sham and effective memory orbitals. The time-local formulation is numerically implemented, with the incorporation of exponential memory loss to address the unaccounted for correlation component in the exact-exchange-only functional, to enable the study of the many-electron dynamics of a one-dimensional hydrogen chain. It is shown that the long time behavior of the electric dipole converges correctly and the zero-force theorem is fulfilled in the current implementation.
Phase-Space Explorations in Time-Dependent Density Functional Theory
Rajam, Arun K.; Hessler, Paul; Gaun, Christian; Maitra, Neepa T.
2009-01-01
We discuss two problems which are particularly challenging for approximations in time-dependent density functional theory (TDDFT) to capture: momentum-distributions in ionization processes, and memory-dependence in real-time dynamics. We propose an extension of TDDFT to phase-space densities, discuss some formal aspects of such a "phase-space density functional theory" and explain why it could ameliorate the problems in both cases. For each problem, a two-electron model system is exactly nume...
Rüger, Robert; van Lenthe, Erik; Heine, Thomas; Visscher, Lucas
2016-01-01
We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the harmonic approximation. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner's group, excellent agreement with TD-DFT calculations using local functionals was achieved.
Rüger, Robert; Niehaus, Thomas; van Lenthe, Erik; Heine, Thomas; Visscher, Lucas
2016-01-01
We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon (AH|FC) method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) ...
Time dependent electromagnetic fields and 4-dimensional Stokes' theorem
Andosca, Ryan
2016-01-01
Stokes' theorem is central to many aspects of physics -- electromagnetism, the Aharonov-Bohm effect, and Wilson loops to name a few. However, the pedagogical examples and research work almost exclusively focus on situations where the fields are time-independent so that one need only deal with purely spatial line integrals ({\\it e.g.} $\\oint {\\bf A} \\cdot d{\\bf x}$) and purely spatial area integrals ({\\it e.g.} $\\int (\
Time-dependent density functional theory of open quantum systems in the linear-response regime.
Tempel, David G; Watson, Mark A; Olivares-Amaya, Roberto; Aspuru-Guzik, Alán
2011-02-21
Time-dependent density functional theory (TDDFT) has recently been extended to describe many-body open quantum systems evolving under nonunitary dynamics according to a quantum master equation. In the master equation approach, electronic excitation spectra are broadened and shifted due to relaxation and dephasing of the electronic degrees of freedom by the surrounding environment. In this paper, we develop a formulation of TDDFT linear-response theory (LR-TDDFT) for many-body electronic systems evolving under a master equation, yielding broadened excitation spectra. This is done by mapping an interacting open quantum system onto a noninteracting open Kohn-Sham system yielding the correct nonequilibrium density evolution. A pseudoeigenvalue equation analogous to the Casida equations of the usual LR-TDDFT is derived for the Redfield master equation, yielding complex energies and Lamb shifts. As a simple demonstration, we calculate the spectrum of a C(2 +) atom including natural linewidths, by treating the electromagnetic field vacuum as a photon bath. The performance of an adiabatic exchange-correlation kernel is analyzed and a first-order frequency-dependent correction to the bare Kohn-Sham linewidth based on the Görling-Levy perturbation theory is calculated.
Time-dependent current-density-functional theory for the metallic response of solids
Romaniello, P; de Boeij, PL
2005-01-01
We extend the formulation of time-dependent current-density-functional theory for the linear response properties of dielectric and semi-metallic solids [Kootstra , J. Chem. Phys. 112, 6517 (2000)] to treat metals as well. To achieve this, the Kohn-Sham response functions have to include both interba
Time-dependent current-density-functional theory for the metallic response of solids
Romaniello, P; de Boeij, PL
We extend the formulation of time-dependent current-density-functional theory for the linear response properties of dielectric and semi-metallic solids [Kootstra , J. Chem. Phys. 112, 6517 (2000)] to treat metals as well. To achieve this, the Kohn-Sham response functions have to include both
Time-dependent density-functional theory in the projector augmented-wave method
DEFF Research Database (Denmark)
Walter, Michael; Häkkinen, Hannu; Lehtovaara, Lauri
2008-01-01
We present the implementation of the time-dependent density-functional theory both in linear-response and in time-propagation formalisms using the projector augmented-wave method in real-space grids. The two technically very different methods are compared in the linear-response regime where we...
The Keldysh formalism applied to time-dependent current-density-functional theory
Gidopoulos, NI; Wilson, S
2003-01-01
In this work we demonstrate how to derive the Kohn-Sham equations of time-dependent current-density functional theory from a generating action functional defined on a Keldysh time contour. These Kohn-Sham equations contain an exchange-correlation contribution to the vector potential. For this
Time Dependent Influence of Rotating Magnetic Field on Bacterial Cellulose
Directory of Open Access Journals (Sweden)
Karol Fijałkowski
2016-01-01
Full Text Available The aim of the study was to assess the influence of rotating magnetic field (RMF on the morphology, physicochemical properties, and the water holding capacity of bacterial cellulose (BC synthetized by Gluconacetobacter xylinus. The cultures of G. xylinus were exposed to RMF of frequency that equals 50 Hz and magnetic induction 34 mT for 3, 5, and 7 days during cultivation at 28°C in the customized RMF exposure system. It was revealed that BC exposed for 3 days to RMF exhibited the highest water retention capacity as compared to the samples exposed for 5 and 7 days. The observation was confirmed for both the control and RMF exposed BC. It was proved that the BC exposed samples showed up to 26% higher water retention capacity as compared to the control samples. These samples also required the highest temperature to release the water molecules. Such findings agreed with the observation via SEM examination which revealed that the structure of BC synthesized for 7 days was more compacted than the sample exposed to RMF for 3 days. Furthermore, the analysis of 2D correlation of Fourier transform infrared spectra demonstrated the impact of RMF exposure on the dynamics of BC microfibers crystallinity formation.
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.
Extended gyrokinetic field theory for time-dependent magnetic confinement fields
Energy Technology Data Exchange (ETDEWEB)
Sugama, H.; Watanabe, T.-H.; Nunami, M. [National Institute for Fusion Science, Toki 509-5292 (Japan)
2014-01-15
A gyrokinetic system of equations for turbulent toroidal plasmas in time-dependent axisymmetric background magnetic fields is derived from the variational principle. Besides governing equations for gyrocenter distribution functions and turbulent electromagnetic fields, the conditions which self-consistently determine the background magnetic fields varying on a transport time scale are obtained by using the Lagrangian, which includes the constraint on the background fields. Conservation laws for energy and toroidal angular momentum of the whole system in the time-dependent background magnetic fields are naturally derived by applying Noether's theorem. It is shown that the ensemble-averaged transport equations of particles, energy, and toroidal momentum given in the present work agree with the results from the conventional recursive formulation with the WKB representation except that collisional effects are disregarded here.
DEFF Research Database (Denmark)
Gavnholt, Jeppe; Rubio, Angel; Olsen, Thomas;
2009-01-01
Using time-evolution time-dependent density functional theory (TDDFT) within the adiabatic local-density approximation, we study the interactions between single electrons and molecular resonances at surfaces. Our system is a nitrogen molecule adsorbed on a ruthenium surface. The surface is modeled...... resonance and the lowering of the resonance energy due to an image charge effect. Finally we apply the TDDFT procedure to only consider the decay of molecular excitations and find that it agrees quite well with the width of the projected density of Kohn-Sham states....
Real time propagation of the exact two component time-dependent density functional theory
Goings, Joshua J.; Kasper, Joseph M.; Egidi, Franco; Sun, Shichao; Li, Xiaosong
2016-09-01
We report the development of a real time propagation method for solving the time-dependent relativistic exact two-component density functional theory equations (RT-X2C-TDDFT). The method is fundamentally non-perturbative and may be employed to study nonlinear responses for heavy elements which require a relativistic Hamiltonian. We apply the method to several group 12 atoms as well as heavy-element hydrides, comparing with the extensive theoretical and experimental studies on this system, which demonstrates the correctness of our approach. Because the exact two-component Hamiltonian contains spin-orbit operators, the method is able to describe the non-zero transition moment of otherwise spin-forbidden processes in non-relativistic theory. Furthermore, the two-component approach is more cost effective than the full four-component approach, with similar accuracy. The RT-X2C-TDDFT will be useful in future studies of systems containing heavy elements interacting with strong external fields.
Non-Markovian Brownian motion in a magnetic field and time-dependent force fields
Hidalgo-Gonzalez, J. C.; Jiménez-Aquino, J. I.; Romero-Bastida, M.
2016-11-01
This work focuses on the derivation of the velocity and phase-space generalized Fokker-Planck equations for a Brownian charged particle embedded in a memory thermal bath and under the action of force fields: a constant magnetic field and arbitrary time-dependent force fields. To achieve the aforementioned goal we use a Gaussian but non-Markovian generalized Langevin equation with an arbitrary friction memory kernel. In a similar way, the generalized diffusion equation in the zero inertia limit is also derived. Additionally we show, in the absence of the time-dependent external forces, that, if the fluctuation-dissipation relation of the second kind is valid, then the generalized Langevin dynamics associated with the charged particle reaches a stationary state in the large-time limit. The consistency of our theoretical results is also verified when they are compared with those derived in the absence of the force fields and in the Markovian case.
Second quantized scalar QED in homogeneous time-dependent electromagnetic fields
Kim, Sang Pyo
2014-12-01
We formulate the second quantization of a charged scalar field in homogeneous, time-dependent electromagnetic fields, in which the Hamiltonian is an infinite system of decoupled, time-dependent oscillators for electric fields, but it is another infinite system of coupled, time-dependent oscillators for magnetic fields. We then employ the quantum invariant method to find various quantum states for the charged field. For time-dependent electric fields, a pair of quantum invariant operators for each oscillator with the given momentum plays the role of the time-dependent annihilation and the creation operators, constructs the exact quantum states, and gives the vacuum persistence amplitude as well as the pair-production rate. We also find the quantum invariants for the coupled oscillators for the charged field in time-dependent magnetic fields and advance a perturbation method when the magnetic fields change adiabatically. Finally, the quantum state and the pair production are discussed when a time-dependent electric field is present in parallel to the magnetic field.
Rüger, Robert; Niehaus, Thomas; van Lenthe, Erik; Heine, Thomas; Visscher, Lucas
2016-11-01
We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner's group, very good agreement with TD-DFT calculations using local functionals was achieved.
Rüger, Robert; Niehaus, Thomas; van Lenthe, Erik; Heine, Thomas; Visscher, Lucas
2016-11-14
We report a time-dependent density functional based tight-binding (TD-DFTB) scheme for the calculation of UV/Vis spectra, explicitly taking into account the excitation of nuclear vibrations via the adiabatic Hessian Franck-Condon method with a harmonic approximation for the nuclear wavefunction. The theory of vibrationally resolved UV/Vis spectroscopy is first summarized from the viewpoint of TD-DFTB. The method is benchmarked against time-dependent density functional theory (TD-DFT) calculations for strongly dipole allowed excitations in various aromatic and polar molecules. Using the recent 3ob:freq parameter set of Elstner's group, very good agreement with TD-DFT calculations using local functionals was achieved.
Time-dependent density functional theory quantum transport simulation in non-orthogonal basis.
Kwok, Yan Ho; Xie, Hang; Yam, Chi Yung; Zheng, Xiao; Chen, Guan Hua
2013-12-14
Basing on the earlier works on the hierarchical equations of motion for quantum transport, we present in this paper a first principles scheme for time-dependent quantum transport by combining time-dependent density functional theory (TDDFT) and Keldysh's non-equilibrium Green's function formalism. This scheme is beyond the wide band limit approximation and is directly applicable to the case of non-orthogonal basis without the need of basis transformation. The overlap between the basis in the lead and the device region is treated properly by including it in the self-energy and it can be shown that this approach is equivalent to a lead-device orthogonalization. This scheme has been implemented at both TDDFT and density functional tight-binding level. Simulation results are presented to demonstrate our method and comparison with wide band limit approximation is made. Finally, the sparsity of the matrices and computational complexity of this method are analyzed.
DEFF Research Database (Denmark)
Lacevic, N.; Starr, F. W.; Schrøder, Thomas
2003-01-01
two-point time-dependent density correlation functions, while providing information about the transient "caging" of particles on cooling, are unable to provide sufficiently detailed information about correlated motion and dynamical heterogeneity. Here, we study a four-point, time-dependent density...... simulations of a binary Lennard-Jones mixture approaching the mode coupling temperature from above. We find that the correlations between particles measured by g4(r,t) and S4(q,t) become increasingly pronounced on cooling. The corresponding dynamical correlation length xi4(t) extracted from the small......-q behavior of S4(q,t) provides an estimate of the range of correlated particle motion. We find that xi4(t) has a maximum as a function of time t, and that the value of the maximum of xi4(t) increases steadily from less than one particle diameter to a value exceeding nine particle diameters in the temperature...
Magnetic circular dichroism in real-time time-dependent density functional theory
Lee, K -M; Bertsch, G F
2010-01-01
We apply the adiabatic time-dependent density functional theory to magnetic ci the real-space, real-time computational method. The standard formulas for the MCD response and its A and B terms are derived from the observables in the time-dependent wave function. We find the real time method is well suited for calculating the overall spectrum, particularly at higher excitation energies where individual excited states are numerous and overlapping. The MCD sum rules are derived and interpreted in the real-time formalism; we find that they are very useful for normalization purposes and assessing the accuracy of the theory. The method is applied to MCD spectrum of C-60 using the adiabatic energy functional from the local density approximation. The theory correctly predicts the signs of the A and B terms for the lowest allowed excitations. However, the magnitudes of the terms only show qualitative agreement with experiment.
Institute of Scientific and Technical Information of China (English)
HE Xiang; WANG Fan
2006-01-01
@@ Thioaldehydes and thioketones are candidates of new photoluminescence materials. The time-dependent density functional theory is applied to calculate the absorption and emission wavelengths of ten thiocarbonyl compounds using both B3LYP and PBE0 functionals. The theoretical results are in agreement with the measurable ones.Furthermore, it is found that the maximum absorption and emission wavelengths are linearly correlated to the C-S bond lengths.
Optical Absorption in Molecular Crystals from Time-Dependent Density Functional Theory
2017-04-23
quantitatively and non-empirically within the framework of time-dependent density functional theory (TDDFT), using the recently-developed optimally-tuned...showing that fundamental gaps and optical spectra of molecular solids can be predicted quantitatively and non-empirically within the framework of...II. THEORETICAL AND COMPUTATIONAL APPROACH A. Optimally-tuned range-separated hybrid functionals In the range-separated hybrid (RSH) method, the
Time-dependent relativistic density functional study of Yb and YbO
Institute of Scientific and Technical Information of China (English)
XU WenHua; ZHANG Yong; LIU WenJian
2009-01-01
The low-lying electronic states of Yb and YbO are investigated by using time-dependent relativistic density functional theory,which is based on the newly developed exact two-component Hamiltonian resulting from symmetrized elimination of the small component.The nature of the excited states is analyzed by using the full molecular symmetry.The calculated results support the previous experimental assignment of the ground and excited states of YbO.
Optical properties of Al nanostructures from time dependent density functional theory
Mokkath, Junais Habeeb
2016-04-05
The optical properties of Al nanostructures are investigated by means of time dependent density functional theory, considering chains of varying length and ladders/stripes of varying aspect ratio. The absorption spectra show redshifting for increasing length and aspect ratio. For the chains the absorption is dominated by HOMO → LUMO transitions, whereas ladders and stripes reveal more complex spectra of plasmonic nature above a specific aspect ratio.
Towards time-dependent current-density-functional theory in the non-linear regime.
Escartín, J M; Vincendon, M; Romaniello, P; Dinh, P M; Reinhard, P-G; Suraud, E
2015-02-28
Time-Dependent Density-Functional Theory (TDDFT) is a well-established theoretical approach to describe and understand irradiation processes in clusters and molecules. However, within the so-called adiabatic local density approximation (ALDA) to the exchange-correlation (xc) potential, TDDFT can show insufficiencies, particularly in violently dynamical processes. This is because within ALDA the xc potential is instantaneous and is a local functional of the density, which means that this approximation neglects memory effects and long-range effects. A way to go beyond ALDA is to use Time-Dependent Current-Density-Functional Theory (TDCDFT), in which the basic quantity is the current density rather than the density as in TDDFT. This has been shown to offer an adequate account of dissipation in the linear domain when the Vignale-Kohn (VK) functional is used. Here, we go beyond the linear regime and we explore this formulation in the time domain. In this case, the equations become very involved making the computation out of reach; we hence propose an approximation to the VK functional which allows us to calculate the dynamics in real time and at the same time to keep most of the physics described by the VK functional. We apply this formulation to the calculation of the time-dependent dipole moment of Ca, Mg and Na2. Our results show trends similar to what was previously observed in model systems or within linear response. In the non-linear domain, our results show that relaxation times do not decrease with increasing deposited excitation energy, which sets some limitations to the practical use of TDCDFT in such a domain of excitations.
Time-dependent renormalized Redfield theory II for off-diagonal transition in reduced density matrix
Kimura, Akihiro
2016-09-01
In our previous letter (Kimura, 2016), we constructed time-dependent renormalized Redfield theory (TRRT) only for diagonal transition in a reduced density matrix. In this letter, we formulate the general expression for off-diagonal transition in the reduced density matrix. We discuss the applicability of TRRT by numerically comparing the dependencies on the energy gap of the exciton relaxation rate by using the TRRT and the modified Redfield theory (MRT). In particular, we roughly show that TRRT improves MRT for the detailed balance about the excitation energy transfer reaction.
Application of Time-Dependent Density-Functional Theory to C6
Institute of Scientific and Technical Information of China (English)
ZHOU Xiao-Lin; BAI Yu-Lin; CHEN Xiang-Rong; YANG Xiang-Dong
2004-01-01
@@ We employ a real-space pseudopotential method to determine the ground state structure of the carbon cluster C6 via simulated annealing and the corresponding optical absorption spectra from the adiabatic time-dependent density-functional theory (TDDFT) and the local density approximation (TDLDA). It is found that the ground state structure of the carbon cluster C6 belongs to a monocyclic D3h structure and the calculated spectra exhibit a variety of features that can be used for comparison against future experimental investigations.
Irani, E.; Sadighi-Bonabi, R.; Anvari, A.
2014-06-01
Three dimensional calculations of electronic dynamics of CH4 in a strong laser field are presented with time-dependent density-functional theory. Time evolution of dipole moment and electron localization function is presented. The dependence of dissociation rate on the laser characters is shown and optimal effective parameters are evaluated. The optimum field leads to 76% dissociation probability for GAUSSIAN envelope and 40 fs (FWHM) at 1016 W cm-2. The dissociation probability is calculated by optimum convolution of dual short pulses. By combining of field assisted dissociation process and Ehrenfest molecular dynamics, time variation of bond length, velocity and orientation effect are investigated.
Energy Technology Data Exchange (ETDEWEB)
Brics, Martins; Kapoor, Varun; Bauer, Dieter [Institut fuer Physik, Universitaet Rostock, 18051 Rostock (Germany)
2013-07-01
Time-dependent density functional theory (TDDFT) with known and practicable exchange-correlation potentials does not capture highly correlated electron dynamics such as single-photon double ionization, autoionization, or nonsequential ionization. Time-dependent reduced density matrix functional theory (TDRDMFT) may remedy these problems. The key ingredients in TDRDMFT are the natural orbitals (NOs), i.e., the eigenfunctions of the one-body reduced density matrix (1-RDM), and the occupation numbers (OCs), i.e., the respective eigenvalues. The two-body reduced density matrix (2-RDM) is then expanded in NOs, and equations of motion for the NOs can be derived. If the expansion coefficients of the 2-RDM were known exactly, the problem at hand would be solved. In practice, approximations have to be made. We study the prospects of TDRDMFT following a top-down approach. We solve the exact two-electron time-dependent Schroedinger equation for a model Helium atom in intense laser fields in order to study highly correlated phenomena such as the population of autoionizing states or single-photon double ionization. From the exact wave function we calculate the exact NOs, OCs, the exact expansion coefficients of the 2-RDM, and the exact potentials in the equations of motion. In that way we can identify how many NOs and which level of approximations are necessary to capture such phenomena.
D'Angelo, E; Milic-Emili, J; Marazzini, L
1996-11-01
It has been shown that in normal subjects and chronic obstructive pulmonary disease (COPD) patients the maximal expiratory flows and FEV1 are significantly higher if the FVC maneuver is preceded by a rapid inspiration without an end-inspiratory pause (maneuver 1) compared with a slow inspiration with an end-inspiratory pause of approximately 5 s (maneuver 2). This time dependency of FVC was attributed primarily to loss of lung recoil (stress relaxation) during breath-holding at TLC, in association with time constant inequality within the lungs, and changes in bronchomotor tone. To examine the role of bronchomotor tone on time dependency of FVC, 11 COPD and 10 asthmatic patients performed FVC maneuvers 1 and 2 before and after administration of a bronchodilator drug (salbutamol). In addition, using the same approach, the effects of changing airway resistance per se were assessed in another group of 10 COPD patients and 10 normal subjects, while breathing air and after equilibration with 80% helium in oxygen. Main findings were: peak expiratory flow (PEF), FEV1, and maximal midexpiratory flow rate (MMF) were significantly larger with maneuver 1 than 2; after salbutamol administration and during helium-oxygen breathing, all indices increased significantly with both maneuvers but the relative differences between maneuvers 1 and 2 were unchanged. We conclude that time dependency of maximal expiratory flow-volume (MEFV) curves, as indexed by PEF, FEV1, and MMF, is largely independent of bronchomotor tone and gas density, and probably reflects mainly stress relaxation of the respiratory tissues. The relevance of time dependency of FVC maneuver in the assessment of bronchodilator response and density dependence is discussed.
Pernal, Katarzyna; Giesbertz, Klaas J H
2016-01-01
Recent advances in reduced density matrix functional theory (RDMFT) and linear response time-dependent reduced density matrix functional theory (TD-RDMFT) are reviewed. In particular, we present various approaches to develop approximate density matrix functionals which have been employed in RDMFT. We discuss the properties and performance of most available density matrix functionals. Progress in the development of functionals has been paralleled by formulation of novel RDMFT-based methods for predicting properties of molecular systems and solids. We give an overview of these methods. The time-dependent extension, TD-RDMFT, is a relatively new theory still awaiting practical and generally useful functionals which would work within the adiabatic approximation. In this chapter we concentrate on the formulation of TD-RDMFT response equations and various adiabatic approximations. None of the adiabatic approximations is fully satisfactory, so we also discuss a phase-dependent extension to TD-RDMFT employing the concept of phase-including-natural-spinorbitals (PINOs). We focus on applications of the linear response formulations to two-electron systems, for which the (almost) exact functional is known.
Energy Technology Data Exchange (ETDEWEB)
Kullie, Ossama, E-mail: kullie@uni-kassel.de [Institute de Chimie de Strasbourg, CNRS et Université de Strasbourg, Laboratoire de Chimie Quantique, 4 rue Blaise Pascal, 67070 Strasbourg (France); Theoretical Physics, Institute for Physics, Department of Mathematics and Natural Science, University of Kassel (Germany)
2013-03-29
Highlights: ► The achievement of CAMB3LYP functional for excited states in framework of TD-DFT. ► Relativistic 4-components calculations for the excited states of the Cd{sub 2} dimer. ► Relativistic Spin-Free calculations for the excited states of Cd{sub 2} dimer. ► A comparison of the achievements of different types of DFT approximations upon Cd{sub 2}. - Abstract: In this paper we present a time-dependent density functional study for the ground-state as well the 20-lowest laying excited states of the cadmium dimer Cd{sub 2}, we analyze its spectrum obtained from all electrons calculations performed with time-depended density functional for the relativistic Dirac-Coulomb- and relativistic spin-free-Hamiltonian as implemented in DIRAC-PACKAGE. The calculations were obtained with different density functional approximations, and a comparison with the literature is given as far as available. Our result is very encouraging, especially for the lowest excited states of this dimer, and is expected to be enlightened for similar systems. The result shows that only long-range corrected functionals such as CAMB3LYP, gives the correct asymptotic behavior for the higher states. A comparable but less satisfactory results were obtained with B3LYP and PBE0 functionals. Spin-free-Hamiltonian is shown to be very efficient for systems containing heavy elements such as Cd{sub 2} in frameworks of (time-dependent) density functional without introducing large errors.
Wong, Bryan M
2009-01-01
The electronic structure and size-scaling of optoelectronic properties in cycloparaphenylene carbon nanorings are investigated using time-dependent density functional theory (TDDFT). The TDDFT calculations on these molecular nanostructures indicate that the lowest excitation energy surprisingly becomes larger as the carbon nanoring size is increased, in contradiction with typical quantum confinement effects. In order to understand their unusual electronic properties, I performed an extensive investigation of excitonic effects by analyzing electron-hole transition density matrices and exciton binding energies as a function of size in these nanoring systems. The transition density matrices allow a global view of electronic coherence during an electronic excitation, and the exciton binding energies give a quantitative measure of electron-hole interaction energies in the nanorings. Based on overall trends in exciton binding energies and their spatial delocalization, I find that excitonic effects play a vital role...
Two-component hybrid time-dependent density functional theory within the Tamm-Dancoff approximation
Energy Technology Data Exchange (ETDEWEB)
Kühn, Michael [Institut für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstraße 12, 76131 Karlsruhe (Germany); Weigend, Florian, E-mail: florian.weigend@kit.edu [Institut für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstraße 12, 76131 Karlsruhe (Germany); Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, 76021 Karlsruhe (Germany)
2015-01-21
We report the implementation of a two-component variant of time-dependent density functional theory (TDDFT) for hybrid functionals that accounts for spin-orbit effects within the Tamm-Dancoff approximation (TDA) for closed-shell systems. The influence of the admixture of Hartree-Fock exchange on excitation energies is investigated for several atoms and diatomic molecules by comparison to numbers for pure density functionals obtained previously [M. Kühn and F. Weigend, J. Chem. Theory Comput. 9, 5341 (2013)]. It is further related to changes upon switching to the local density approximation or using the full TDDFT formalism instead of TDA. Efficiency is demonstrated for a comparably large system, Ir(ppy){sub 3} (61 atoms, 1501 basis functions, lowest 10 excited states), which is a prototype molecule for organic light-emitting diodes, due to its “spin-forbidden” triplet-singlet transition.
Remarks on time-dependent [current]-density functional theory for open quantum systems.
Yuen-Zhou, Joel; Aspuru-Guzik, Alán
2013-08-14
Time-dependent [current]-density functional theory for open quantum systems (OQS) has emerged as a formalism that can incorporate dissipative effects in the dynamics of many-body quantum systems. Here, we review and clarify some formal aspects of these theories that have been recently questioned in the literature. In particular, we provide theoretical support for the following conclusions: (1) contrary to what we and others had stated before, within the master equation framework, there is in fact a one-to-one mapping between vector potentials and current densities for fixed initial state, particle-particle interaction, and memory kernel; (2) regardless of the first conclusion, all of our recently suggested Kohn-Sham (KS) schemes to reproduce the current and particle densities of the original OQS, and in particular, the use of a KS closed driven system, remains formally valid; (3) the Lindblad master equation maintains the positivity of the density matrix regardless of the time-dependence of the Hamiltonian or the dissipation operators; (4) within the stochastic Schrödinger equation picture, a one-to-one mapping from stochastic vector potential to stochastic current density for individual trajectories has not been proven so far, except in the case where the vector potential is the same for every member of the ensemble, in which case, it reduces to the Lindblad master equation picture; (5) master equations may violate certain desired properties of the density matrix, such as positivity, but they remain as one of the most useful constructs to study OQS when the environment is not easily incorporated explicitly in the calculation. The conclusions support our previous work as formally rigorous, offer new insights into it, and provide a common ground to discuss related theories.
Energy Technology Data Exchange (ETDEWEB)
Quijada, M. [Departamento de Fisica de Materiales, Facultad de Quimicas UPV/EHU, Apartado 1072, 20080 San Sebastian (Spain); Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastian (Spain); Borisov, A.G. [Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastian (Spain); Universite Paris-Sud, Laboratoire des Collisions Atomiques et Moleculaires (France); CNRS, UMR 8625, Laboratoire des Collisions Atomiques et Moleculaires, LCAM, Batiment 351, UPS-11, Orsay, 91405 Orsay Cedex (France); Muino, R.D. [Donostia International Physics Center DIPC, P. Manuel de Lardizabal 4, 20018 San Sebastian (Spain); Centro de Fisica de Materiales, Centro Mixto CSIC-UPV/EHU, Edificio Korta, Avenida de Tolosa 72, 20018 San Sebastian (Spain)
2008-06-15
Time-dependent density functional theory is used to study the interaction between antiprotons and metallic nanoshells. The ground state electronic properties of the nanoshell are obtained in the jellium approximation. The energy lost by the antiproton during the collision is calculated and compared to that suffered by antiprotons traveling in metal clusters. The resulting energy loss per unit path length of material in thin nanoshells is larger than the corresponding quantity for clusters. It is shown that the collision process can be interpreted as the antiproton crossing of two nearly bi-dimensional independent metallic systems. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)
Excitons in solids with non-empirical hybrid time-dependent density-functional theory
Ullrich, Carsten; Yang, Zeng-Hui; Sottile, Francesco
2015-03-01
The Bethe-Salpeter equation (BSE) accurately describes the optical properties of solids, but is computationally expensive. Time-dependent density-functional theory (TDDFT) is more efficient, but standard functionals do not produce excitons in extended systems. We present a new, non-empirical hybrid TDDFT approach whose computational cost is much less than BSE, while the accuracy for both bound excitons and the continuum spectra is comparable to that of the BSE. Good performance is observed for both small-gap semiconductors and large-gap insulators. Work supported by NSF Grant DMR-1408904.
Excitons in solids with time-dependent density-functional theory: the bootstrap kernel and beyond
Byun, Young-Moo; Yang, Zeng-Hui; Ullrich, Carsten
Time-dependent density-functional theory (TDDFT) is an efficient method to describe the optical properties of solids. Lately, a series of bootstrap-type exchange-correlation (xc) kernels have been reported to produce accurate excitons in solids, but different bootstrap-type kernels exist in the literature, with mixed results. In this presentation, we reveal the origin of the confusion and show a new empirical TDDFT xc kernel to compute excitonic properties of semiconductors and insulators efficiently and accurately. Our method can be used for high-throughput screening calculations and large unit cell calculations. Work supported by NSF Grant DMR-1408904.
Energy Technology Data Exchange (ETDEWEB)
Magyar, R.J.; Shulenburger, L.; Baczewski, A.D. [Sandia National Laboratories - Multi-scale Physics 1444 MS 1322, Albuquerque, NM (United States)
2016-06-15
In these proceedings, we show that time-dependent density functional theory is capable of stopping calculations at the extreme conditions of temperature and pressure seen in warm dense matter. The accuracy of the stopping curves tends to be up to about 20% lower than empirical models that are in use. However, TDDFT calculations are free from fitting parameters and assumptions about the model form of the dielectric function. This work allows the simulation of ion stopping in many materials that are difficult to study experimentally. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)
Time-dependent density functional theory for open quantum systems with unitary propagation.
Yuen-Zhou, Joel; Tempel, David G; Rodríguez-Rosario, César A; Aspuru-Guzik, Alán
2010-01-29
We extend the Runge-Gross theorem for a very general class of open quantum systems under weak assumptions about the nature of the bath and its coupling to the system. We show that for Kohn-Sham (KS) time-dependent density functional theory, it is possible to rigorously include the effects of the environment within a bath functional in the KS potential. A Markovian bath functional inspired by the theory of nonlinear Schrödinger equations is suggested, which can be readily implemented in currently existing real-time codes. Finally, calculations on a helium model system are presented.
On the effect of time-dependent inhomogeneous magnetic fields in electron–positron pair production
Directory of Open Access Journals (Sweden)
Christian Kohlfürst
2016-05-01
Full Text Available Electron–positron pair production in space- and time-dependent electromagnetic fields is investigated. Especially, the influence of a time-dependent, inhomogeneous magnetic field on the particle momenta and the total particle yield is analyzed for the first time. The role of the Lorentz invariant E2−B2, including its sign and local values, in the pair creation process is emphasized.
Adiabatic approximation of time-dependent density matrix functional response theory.
Pernal, Katarzyna; Giesbertz, Klaas; Gritsenko, Oleg; Baerends, Evert Jan
2007-12-07
Time-dependent density matrix functional theory can be formulated in terms of coupled-perturbed response equations, in which a coupling matrix K(omega) features, analogous to the well-known time-dependent density functional theory (TDDFT) case. An adiabatic approximation is needed to solve these equations, but the adiabatic approximation is much more critical since there is not a good "zero order" as in TDDFT, in which the virtual-occupied Kohn-Sham orbital energy differences serve this purpose. We discuss a simple approximation proposed earlier which uses only results from static calculations, called the static approximation (SA), and show that it is deficient, since it leads to zero response of the natural orbital occupation numbers. This leads to wrong behavior in the omega-->0 limit. An improved adiabatic approximation (AA) is formulated. The two-electron system affords a derivation of exact coupled-perturbed equations for the density matrix response, permitting analytical comparison of the adiabatic approximation with the exact equations. For the two-electron system also, the exact density matrix functional (2-matrix in terms of 1-matrix) is known, enabling testing of the static and adiabatic approximations unobscured by approximations in the functional. The two-electron HeH(+) molecule shows that at the equilibrium distance, SA consistently underestimates the frequency-dependent polarizability alpha(omega), the adiabatic TDDFT overestimates alpha(omega), while AA improves upon SA and, indeed, AA produces the correct alpha(0). For stretched HeH(+), adiabatic density matrix functional theory corrects the too low first excitation energy and overpolarization of adiabatic TDDFT methods and exhibits excellent agreement with high-quality CCSD ("exact") results over a large omega range.
Time-Dependent 2-D Vector Field Topology: An Approach Inspired by Lagrangian Coherent Structures
Sadlo, Filip; Weiskopf, Daniel
2011-01-01
This paper presents an approach to a time-dependent variant of the concept of vector field topology for 2-D vector fields. Vector field topology is defined for steady vector fields and aims at discriminating the domain of a vector field into regions of qualitatively different behaviour. The presented approach represents a generalization for saddle-type critical points and their separatrices to unsteady vector fields based on generalized streak lines, with the classical vector field topology a...
Real-time, real-space implementation of the linear response time-dependent density-functional theory
Yabana, K.; Nakatsukasa, T.; Iwata, J.-I.; Bertsch, G. F.
We review our methods to calculate optical response of molecules in the linear response time-dependent density-functional theory. Three distinct formalisms which are implemented in the three-dimensional grid representation are explained in detail. They are the real-time method solving the time-dependent Kohn-Sham equation in the time domain, the modified Sternheimer method which calculates the response to an external field of fixed frequency, and the matrix eigenvalue approach. We also illustrate treatments of the scattering boundary condition, needed to accurately describe photoionization processes. Finally, we show how the real-time formalism for molecules can be used to determine the response of infinite periodic systems.
Real-time, real-space implementation of the linear response time-dependent density-functional theory
Energy Technology Data Exchange (ETDEWEB)
Yabana, K.; Nakatsukasa, T. [Center for Computational Sciences, University of Tsukuba, Tsukuba 305-8571 (Japan); Institute of Physics, University of Tsukuba, Tsukuba 305-8571 (Japan); Iwata, J.I. [Center for Computational Sciences, University of Tsukuba, Tsukuba 305-8571 (Japan); Bertsch, G.F. [Department of Physics and Institute for Nuclear Theory, University of Washington, Seattle 98195 (United States)
2006-04-15
We review our methods to calculate optical response of molecules in the linear response time-dependent density-functional theory. Three distinct formalisms which are implemented in the three-dimensional grid representation are explained in detail. They are the real-time method solving the time-dependent Kohn-Sham equation in the time domain, the modified Sternheimer method which calculates the response to an external field of fixed frequency, and the matrix eigenvalue approach. We also illustrate treatments of the scattering boundary condition, needed to accurately describe photoionization processes. Finally, we show how the real-time formalism for molecules can be used to determine the response of infinite periodic systems. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)
Giesbertz, K J H; Pernal, K; Gritsenko, O V; Baerends, E J
2009-03-21
Time-dependent density functional theory in its current adiabatic implementations exhibits three striking failures: (a) Totally wrong behavior of the excited state surface along a bond-breaking coordinate, (b) lack of doubly excited configurations, affecting again excited state surfaces, and (c) much too low charge transfer excitation energies. We address these problems with time-dependent density matrix functional theory (TDDMFT). For two-electron systems the exact exchange-correlation functional is known in DMFT, hence exact response equations can be formulated. This affords a study of the performance of TDDMFT in the TDDFT failure cases mentioned (which are all strikingly exhibited by prototype two-electron systems such as dissociating H(2) and HeH(+)). At the same time, adiabatic approximations, which will eventually be necessary, can be tested without being obscured by approximations in the functional. We find the following: (a) In the fully nonadiabatic (omega-dependent, exact) formulation of linear response TDDMFT, it can be shown that linear response (LR)-TDDMFT is able to provide exact excitation energies, in particular, the first order (linear response) formulation does not prohibit the correct representation of doubly excited states; (b) within previously formulated simple adiabatic approximations the bonding-to-antibonding excited state surface as well as charge transfer excitations are described without problems, but not the double excitations; (c) an adiabatic approximation is formulated in which also the double excitations are fully accounted for.
Nagesh, Jayashree; Brumer, Paul; Izmaylov, Artur F
2016-01-01
We extend the localized operator partitioning method (LOPM) [J. Nagesh, A.F. Izmaylov, and P. Brumer, J. Chem. Phys. 142, 084114 (2015)] to the time-dependent density functional theory (TD-DFT) framework to partition molecular electronic energies of excited states in a rigorous manner. A molecular fragment is defined as a collection of atoms using Stratman-Scuseria-Frisch atomic partitioning. A numerically efficient scheme for evaluating the fragment excitation energy is derived employing a resolution of the identity to preserve standard one- and two-electron integrals in the final expressions. The utility of this partitioning approach is demonstrated by examining several excited states of two bichromophoric compounds: 9-((1-naphthyl)-methyl)-anthracene and 4-((2-naphthyl)-methyl)-benzaldehyde. The LOPM is found to provide nontrivial insights into the nature of electronic energy localization that are not accessible using simple density difference analysis.
Verdict: Time-Dependent Density Functional Theory "Not Guilty" of Large Errors for Cyanines.
Jacquemin, Denis; Zhao, Yan; Valero, Rosendo; Adamo, Carlo; Ciofini, Ilaria; Truhlar, Donald G
2012-04-10
We assess the accuracy of eight Minnesota density functionals (M05 through M08-SO) and two others (PBE and PBE0) for the prediction of electronic excitation energies of a family of four cyanine dyes. We find that time-dependent density functional theory (TDDFT) with the five most recent of these functionals (from M06-HF through M08-SO) is able to predict excitation energies for cyanine dyes within 0.10-0.36 eV accuracy with respect to the most accurate available Quantum Monte Carlo calculations, providing a comparable accuracy to the latest generation of CASPT2 calculations, which have errors of 0.16-0.34 eV. Therefore previous conclusions that TDDFT cannot treat cyanine dyes reasonably accurately must be revised.
Time-dependent current-density functional theory for generalized open quantum systems.
Yuen-Zhou, Joel; Rodríguez-Rosario, César; Aspuru-Guzik, Alán
2009-06-14
In this article, we prove the one-to-one correspondence between vector potentials and particle and current densities in the context of master equations with arbitrary memory kernels, therefore extending time-dependent current-density functional theory (TD-CDFT) to the domain of generalized many-body open quantum systems (OQS). We also analyse the issue of A-representability for the Kohn-Sham (KS) scheme proposed by D'Agosta and Di Ventra for Markovian OQS [Phys. Rev. Lett. 2007, 98, 226403] and discuss its domain of validity. We suggest ways to expand their scheme, but also propose a novel KS scheme where the auxiliary system is both closed and non-interacting. This scheme is tested numerically with a model system, and several considerations for the future development of functionals are indicated. Our results formalize the possibility of practising TD-CDFT in OQS, hence expanding the applicability of the theory to non-Hamiltonian evolutions.
Guido, Ciro A.; Cortona, Pietro; Adamo, Carlo
2014-03-01
We extend our previous definition of the metric Δr for electronic excitations in the framework of the time-dependent density functional theory [C. A. Guido, P. Cortona, B. Mennucci, and C. Adamo, J. Chem. Theory Comput. 9, 3118 (2013)], by including a measure of the difference of electronic position variances in passing from occupied to virtual orbitals. This new definition, called Γ, permits applications in those situations where the Δr-index is not helpful: transitions in centrosymmetric systems and Rydberg excitations. The Γ-metric is then extended by using the Natural Transition Orbitals, thus providing an intuitive picture of how locally the electron density changes during the electronic transitions. Furthermore, the Γ values give insight about the functional performances in reproducing different type of transitions, and allow one to define a "confidence radius" for GGA and hybrid functionals.
van Duijnen, Piet Th.; Greene, Shannon N.; Richards, Nigel G. J.
2007-01-01
We report the calculated visible spectrum of [Fe-III(PyPepS)(2)](-) in aqueous solution. From all-classical molecular dynamics simulations on the solute and 200 water molecules with a polarizable force field, 25 solute/solvent configurations were chosen at random from a 50 ps production run and subj
Ruggenthaler, Michael; Penz, Markus; van Leeuwen, Robert
2015-05-27
In this work we review the mapping from densities to potentials in quantum mechanics, which is the basic building block of time-dependent density-functional theory and the Kohn-Sham construction. We first present detailed conditions such that a mapping from potentials to densities is defined by solving the time-dependent Schrödinger equation. We specifically discuss intricacies connected with the unboundedness of the Hamiltonian and derive the local-force equation. This equation is then used to set up an iterative sequence that determines a potential that generates a specified density via time propagation of an initial state. This fixed-point procedure needs the invertibility of a certain Sturm-Liouville problem, which we discuss for different situations. Based on these considerations we then present a discussion of the famous Runge-Gross theorem which provides a density-potential mapping for time-analytic potentials. Further we give conditions such that the general fixed-point approach is well-defined and converges under certain assumptions. Then the application of such a fixed-point procedure to lattice Hamiltonians is discussed and the numerical realization of the density-potential mapping is shown. We conclude by presenting an extension of the density-potential mapping to include vector-potentials and photons.
Energy Technology Data Exchange (ETDEWEB)
Appel, H.
2007-05-15
In part I of this work we present a double-pole approximation (DPA) to the response equations of time-dependent density functional theory (TDDFT). The double-pole approximation provides an exact description of systems with two strongly coupled excitations which are isolated from the rest of the spectrum. In contrast to the traditional single-pole approximation of TDDFT the DPA also yields corrections to the Kohn-Sham oscillator strengths. We also demonstrate how to invert the double-pole solution which allows us to predict matrix elements of the exchange-correlation kernel f{sub xc} from experimental input. We attempt some first steps towards a time-dependent generalization of reduced density matrix functional theory (RDMFT). In part II we derive equations of motion for natural orbitals and occupation numbers. Using the equation of motion for the occupation numbers we show that an adiabatic extension of presently known ground-state functionals of static RDMFT always leads to occupation numbers which are constant in time. From the stationary conditions of the equations of motion for the N-body correlations (correlated parts of the N-body matrices) we derive a new class of ground-state functionals which can be used in static RDMFT. Applications are presented for a one-dimensional model system where the time-dependent many-body Schroedinger equation can be propagated numerically. We use optimal control theory to find optimized laser pulses for transitions in a model for atomic Helium. From the numerically exact correlated wavefunction we extract the exact time evolution of natural orbitals and occupation numbers for (i) laser-driven Helium and (ii) electron-ion scattering. Part III of this work considers time-dependent quantum transport within TDDFT. We present an algorithm for the calculation of extended eigenstates of single-particle Hamiltonians which is especially tailored to a finite-difference discretization of the Schroedinger equation. We consider the
DEFF Research Database (Denmark)
Hedegård, Erik D.; Jensen, Hans Jørgen Aagaard; Knecht, Stefan;
2013-01-01
formulation of multi-determinantal TD-DFT schemes where excitation classes, which are absent in conventional TD-DFT spectra (like for example double excitations), can be addressed. This paper investigates the combination of both the long-range Multi-Configuration Self-Consistent Field (MCSCF) and Second Order...... TD-MC-srDFT and performs slightly better against the reference data for this small subset. Beyond the proof-of-principle calculations comprising the first part of this contribution, we additionally studied the low-lying singlet excited states (S1 and S2) of the retinal chromophore. The chromophore...... displays multireference character in the ground state and both excited states exhibit considerable double excitation character, which in turn cannot be described within standard TD-DFT, due to the adiabatic approximation. However, a TD-MC-srDFT approach can account for the multireference character...
Evolution of Arbitrary States under Fock-Darwin Hamiltonian and a Time-Dependent Electric Field
Institute of Scientific and Technical Information of China (English)
徐晓飞; 杨涛; 翟智远; 潘孝胤
2012-01-01
The method of path integral is employed to calculate the time evolution of the eigenstates of a charged particle under the Fock-Darwin （FD） Hamiltonian subjected to a time-dependent electric field in the plane of the system. An exact analytical expression is established for the evolution of the eigenstates. This result then provides a general solution to the time-dependent Schrodinger equation.
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).
Andrade, Xavier; Alberdi-Rodriguez, Joseba; Strubbe, David A.; Oliveira, Micael J. T.; Nogueira, Fernando; Castro, Alberto; Muguerza, Javier; Arruabarrena, Agustin; Louie, Steven G.; Aspuru-Guzik, Alán; Rubio, Angel; Marques, Miguel A. L.
2012-06-01
Octopus is a general-purpose density-functional theory (DFT) code, with a particular emphasis on the time-dependent version of DFT (TDDFT). In this paper we present the ongoing efforts to achieve the parallelization of octopus. We focus on the real-time variant of TDDFT, where the time-dependent Kohn-Sham equations are directly propagated in time. This approach has great potential for execution in massively parallel systems such as modern supercomputers with thousands of processors and graphics processing units (GPUs). For harvesting the potential of conventional supercomputers, the main strategy is a multi-level parallelization scheme that combines the inherent scalability of real-time TDDFT with a real-space grid domain-partitioning approach. A scalable Poisson solver is critical for the efficiency of this scheme. For GPUs, we show how using blocks of Kohn-Sham states provides the required level of data parallelism and that this strategy is also applicable for code optimization on standard processors. Our results show that real-time TDDFT, as implemented in octopus, can be the method of choice for studying the excited states of large molecular systems in modern parallel architectures.
Criteria for the determination of time dependent scalings in the Fock quantization of scalar fields
Cortez, Jerónimo; Olmedo, Javier; Velhinho, José M
2012-01-01
The quantization of scalar fields in nonstationary spacetimes is plagued with ambiguities that undermine the significance of physical predictions. A context in which this kind of ambiguities arises and prevents the derivation of robust results is, e.g., in the quantum analysis of cosmological perturbations. In these situations, typically, a suitable scaling of the field by a time dependent function leads to a description in an auxiliary static background, though the nonstationarity still shows up in a time dependent mass. For such a field description, and assuming the compactness of the spatial sections, we recently proved in three or less spatial dimensions that the criteria of a natural implementation of the spatial isometries and of a unitary time evolution are able to select a unique class of unitarily equivalent vacua, and hence of Fock representations. In this work, we extend our uniqueness result to the consideration of all possible field descriptions that can be reached by a time dependent canonical t...
Time-dependent density functional theory with twist-averaged boundary conditions
Schuetrumpf, B; Reinhard, P -G
2016-01-01
Time-dependent density functional theory is widely used to describe excitations of many-fermion systems. In its many applications, 3D coordinate-space representation is used, and infinite-domain calculations are limited to a finite volume represented by a box. For finite quantum systems (atoms, molecules, nuclei), the commonly used periodic or reflecting boundary conditions introduce spurious quantization of the continuum states and artificial reflections from boundary; hence, an incorrect treatment of evaporated particles. These artifacts can be practically cured by introducing absorbing boundary conditions (ABC) through an absorbing potential in a certain boundary region sufficiently far from the described system. But also the calculations of infinite matter (crystal electrons, quantum fluids, neutron star crust) suffer artifacts from a finite computational box. In this regime, twist- averaged boundary conditions (TABC) have been used successfully to diminish the finite-volume effects. In this work, we exte...
Self-consistent RPA and the time-dependent density matrix approach
Energy Technology Data Exchange (ETDEWEB)
Schuck, P. [Institut de Physique Nucleaire, Orsay (France); CNRS et Universite Joseph Fourier, Laboratoire de Physique et Modelisation des Milieux Condenses, Grenoble (France); Tohyama, M. [Kyorin University School of Medicine, Mitaka, Tokyo (Japan)
2016-10-15
The time-dependent density matrix (TDDM) or BBGKY (Bogoliubov, Born, Green, Kirkwood, Yvon) approach is decoupled and closed at the three-body level in finding a natural representation of the latter in terms of a quadratic form of two-body correlation functions. In the small amplitude limit an extended RPA coupled to an also extended second RPA is obtained. Since including two-body correlations means that the ground state cannot be a Hartree-Fock state, naturally the corresponding RPA is upgraded to Self-Consistent RPA (SCRPA) which was introduced independently earlier and which is built on a correlated ground state. SCRPA conserves all the properties of standard RPA. Applications to the exactly solvable Lipkin and the 1D Hubbard models show good performances of SCRPA and TDDM. (orig.)
Time-dependent density functional studies of nuclear quantum dynamics in large amplitudes
Wen, Kai; Fang, Ni; Nakatsukasa, Takashi
2015-01-01
The time-dependent density functional theory (TDDFT) provides a unified description of the structure and reaction. The linear approximation leads to the random-phase approximation (RPA) which is capable of describing a variety of collective motion in a harmonic regime. Beyond the linear regime, we present applications of the TDDFT to nuclear fusion and fission reaction. In particular, the extraction of the internuclear potential and the inertial mass parameter is performed using two different methods. A fusion hindrance mechanism for heavy systems is investigated from the microscopic point of view. The canonical collective variables are determined by the adiabatic self-consistent collective coordinate method. Preliminary results of the spontaneous fission path, the potential, and the collective mass parameter are shown for 8Be --> alpha+alpha.
Time-dependent density functional study on the photoisomerization mechanism of azobenzene
Oyama, Norihisa; Tateyama, Yoshitaka; Miyamoto, Yoshiyuki; Ohno, Takahisa
2004-03-01
Photochemical reactions in organic molecules have attracted considerable attention in semiconductor physics and also in bioscience. Azobenzene is a simple molecule which shows the reversible photoisomerization at high quantum yields, and can be used as a light-driven molecular switch and so on. However, the photoisomerization process of azobenzene is still an open question because of its femtosecond ultra-fast reaction. In this talk, we present time-dependent density functional calculations for the azobenzene molecule, and discuss the mechanism of photoisomerization induced by S1 and S2 excitations. This research is partially supported by ACT-JST, and also by FSIS and Special Coordination Funds of MEXT of Japanese Government. The calculations were carried out partly using the Numerical Materials Simulator in National Institute for Materials Science, and partly using the NEC-SX5 at Cybermedia Center of Osaka University.
DEFF Research Database (Denmark)
Bast, Radovan; Jensen, Hans Jørgen Aagaard; Saue, Trond
2009-01-01
We report an implementation of adiabatic time-dependent density functional theory based on the 4-component relativistic Dirac-Coulomb Hamiltonian and a closed-shell reference. The implementation includes noncollinear spin magnetization and full derivatives of functionals, including hybrid...... and time reversal symmetry on trial vectors to obtain even better reductions in terms of memory and run time, and without invoking approximations. Further reductions are obtained by exploiting point group symmetries for D2h and subgroups in a symmetry scheme where symmetry reductions translate...... into reduction of algebra from quaternion to complex or real. For hybrid GGAs with noncollinear spin magnetization we derive a new computationally advantageous equation for the full second variational derivatives of such exchange-correlation functionals. We apply our implementation to calculations on the ns2...
Hübener, Hannes; Giustino, Feliciano
2014-02-01
We present the implementation of linear-response time-dependent density functional theory based on the self-consistent Sternheimer equation and employing a basis set of numerical pseudo-atomic orbitals. We demonstrate this method by presenting test calculations on systems of increasing size ranging from benzene to chlorophyll a, and by comparing our results with those obtained within Casida's formalism and with previous calculations. We provide a detailed assessment of the accuracy of this method, both in relation to the use of local orbitals for describing electronic excitations and to the handling of the frequency response using Padé approximants. We establish a simple criterion for estimating a priori the accuracy of the basis set in the calculation of optical spectra. We show that the computational cost of this method scales quadratically with the system size.
Andrade, Xavier; Botti, Silvana; Marques, Miguel A. L.; Rubio, Angel
2007-05-01
The authors present an efficient perturbative method to obtain both static and dynamic polarizabilities and hyperpolarizabilities of complex electronic systems. This approach is based on the solution of a frequency-dependent Sternheimer equation, within the formalism of time-dependent density functional theory, and allows the calculation of the response both in resonance and out of resonance. Furthermore, the excellent scaling with the number of atoms opens the way to the investigation of response properties of very large molecular systems. To demonstrate the capabilities of this method, they implemented it in a real-space (basis-set-free) code and applied it to benchmark molecules, namely, CO, H2O, and para-nitroaniline. Their results are in agreement with experimental and previous theoretical studies and fully validate their approach.
The role of exchange and correlation in time-dependent density-functional theory for photoionization
Stener, M.; Decleva, P.; Görling, A.
2001-05-01
Atomic photoionization cross sections are calculated by time-dependent density-functional (TDDF) methods using different exchange-correlation potentials including the exact one. The exchange-correlation kernel is treated in the adiabatic local density approximation (ALDA). Results for the exact full and the exact exchange-only Kohn-Sham (KS) potential are very similar, the calculated photo cross section agree very well with experimental data. Thus the exact correlation potential seems to have no influence on photoionization and the ALDA for the exchange-correlation kernel seems to be sufficient for most features of the cross sections. The TDDF method employing the exact exchange-only KS potential in combination with the ALDA exchange-correlation kernel therefore is a promising approach to describe photoionization. Deviations from experiment are observed for the widths and shape of the autoionization resonances and have to be attributed to deficiencies of the ALDA exchange-correlation kernel. The calculation of widths and shapes of autoionization resonances therefore may serve as a severe test for new approximate exchange-correlation density-functionals. The asymptotically exact exchange-correlation potential of van Leeuwen and Baerends also leads to quite good photo cross section, which, however, shows deficiencies close to the ionization threshold and in the energetic position of the autoionization resonances. Supplementation of the exact exchange potential with the LDA correlation potential leads to a worsening of the photo cross section because the LDA correlation potential is too attractive.
Wavelet-Based Linear-Response Time-Dependent Density-Functional Theory
Natarajan, Bhaarathi; Casida, Mark E; Deutsch, Thierry; Burchak, Olga N; Philouze, Christian; Balakirev, Maxim Y
2011-01-01
Linear-response time-dependent (TD) density-functional theory (DFT) has been implemented in the pseudopotential wavelet-based electronic structure program BigDFT and results are compared against those obtained with the all-electron Gaussian-type orbital program deMon2k for the calculation of electronic absorption spectra of N2 using the TD local density approximation (LDA). The two programs give comparable excitation energies and absorption spectra once suitably extensive basis sets are used. Convergence of LDA density orbitals and orbital energies to the basis-set limit is significantly faster for BigDFT than for deMon2k. However the number of virtual orbitals used in TD-DFT calculations is a parameter in BigDFT, while all virtual orbitals are included in TD-DFT calculations in deMon2k. As a reality check, we report the x-ray crystal structure and the measured and calculated absorption spectrum (excitation energies and oscillator strengths) of the small organic molecule N-cyclohexyl-2-(4-methoxyphenyl)imidaz...
Mixing of photons with light pseudoscalars in time-dependent magnetic fields
Energy Technology Data Exchange (ETDEWEB)
Arias, Paola; Arza, Ariel; Gamboa, Jorge [Universidad de Santiago de Chile, Departmento de Fisica, Santiago (Chile)
2016-11-15
The effects of an external time-dependent magnetic field in the conversion probability of photon- to axion-like particles are studied. Our findings show that for a certain time regime, the amplitude of the produced axion-like field can be enlarged with respect to the static case, thus enhancing the probability of conversion. (orig.)
Mixing of photons with light pseudoscalars in time-dependent magnetic fields
Arias, Paola; Arza, Ariel; Gamboa, Jorge
2016-11-01
The effects of an external time-dependent magnetic field in the conversion probability of photon- to axion-like particles are studied. Our findings show that for a certain time regime, the amplitude of the produced axion-like field can be enlarged with respect to the static case, thus enhancing the probability of conversion.
Mixing of photons with light pseudoscalars in time-dependent magnetic fields
Arias, Paola; Gamboa, Jorge
2016-01-01
The effects of an external time-dependent magnetic field in the conversion probability of photon-to-axion-like particles are studied. Our findings show that for a certain time regime, the amplitude of the produced axion-like field can be enlarged with respect to the static case, thus, enhancing the probability of conversion.
Time-Dependent Mean-Field Games in the Subquadratic Case
Gomes, Diogo A.
2014-10-14
In this paper we consider time-dependent mean-field games with subquadratic Hamiltonians and power-like local dependence on the measure. We establish existence of classical solutions under a certain set of conditions depending on both the growth of the Hamiltonian and the dimension. This is done by combining regularity estimates for the Hamilton-Jacobi equation based on the Gagliardo-Nirenberg interpolation inequality with polynomial estimates for the Fokker-Planck equation. This technique improves substantially the previous results on the regularity of time-dependent mean-field games.
Plasmon excitations in sodium atomic planes: a time-dependent density functional theory study.
Wang, Bao-Ji; Xu, Yuehua; Ke, San-Huang
2012-08-07
The collective electronic excitation in planar sodium clusters is studied by time-dependent density functional theory calculations. The formation and development of the resonances in photoabsorption spectra are investigated in terms of the shape and size of the two-dimensional (2D) systems. The nature of these resonances is revealed by the frequency-resolved induced charge densities present on a real-space grid. For long double chains, the excitation is similar to that in long single atomic chains, showing longitudinal modes, end and central transverse modes. However, for 2D planes consisting of (n × n) atoms with n being up to 16, new 2D characteristic modes emerge regardless of the symmetries considered. For in-plane excitations, besides the equivalent end mode, mixed modes with contrary polarity occur. The relation between the frequency of the primary modes and the system size is similar to the case of a 2D electron gas but with a correction due to the realistic atomic structure. For excitations perpendicular to the plane there are corner, side center, bulk center, and circuit modes. Our calculation reveals the importance of dimensionality for plasmon excitation and how it evolves from 1D to 2D.
DEFF Research Database (Denmark)
Silva-Junior, Mario R.; Schreiber, Marko; Sauer, Stephan P. A.;
2008-01-01
Time-dependent density functional theory (TD-DFT) and DFT-based multireference configuration interaction (DFT/MRCI) calculations are reported for a recently proposed benchmark set of 28 medium-sized organic molecules. Vertical excitation energies, oscillator strengths, and excited-state dipole...... moments are computed using the same geometries (MP2/6-31G*) and basis set (TZVP) as in our previous ab initio benchmark study on electronically excited states. The results from TD-DFT (with the functionals BP86, B3LYP, and BHLYP) and from DFT/MRCI are compared against the previous high-level ab initio...
Closed-orbit theory for photodetachment in a time-dependent electric field
Yang, B C
2016-01-01
The standard closed-orbit theory is extended for the photodetachment of negative ions in a time-dependent electric field. The time-dependent photodetachment rate is specifically studied in the presence of a single-cycle terahertz pulse, based on exact quantum simulations and semiclassical analysis. We find that the photodetachment rate is unaffected by a weak terahertz field, but oscillates complicatedly when the terahertz pulse gets strong enough. Three types of closed classical orbits are identified for the photoelectron motion in a strong single-cycle terahertz pulse, and their connections with the oscillatory photodetachment rate are established quantitatively by generalizing the standard closed-orbit theory to a time-dependent form. By comparing the negative hydrogen and fluorine ions, both the in-phase and antiphase oscillations can be observed, depending on a simple geometry of the contributed closed classical orbits. On account of its generality, the presented theory provides an intuitive understandin...
Energy Technology Data Exchange (ETDEWEB)
Ibarra-Sierra, V.G.; Sandoval-Santana, J.C. [Departamento de Física, Universidad Autónoma Metropolitana Iztapalapa, Av. San Rafael Atlixco 186, Col. Vicentina, 09340 México D.F. (Mexico); Cardoso, J.L. [Área de Física Teórica y Materia Condensada, Universidad Autónoma Metropolitana Azcapotzalco, Av. San Pablo 180, Col. Reynosa-Tamaulipas, Azcapotzalco, 02200 México D.F. (Mexico); Kunold, A., E-mail: akb@correo.azc.uam.mx [Área de Física Teórica y Materia Condensada, Universidad Autónoma Metropolitana Azcapotzalco, Av. San Pablo 180, Col. Reynosa-Tamaulipas, Azcapotzalco, 02200 México D.F. (Mexico)
2015-11-15
We discuss the one-dimensional, time-dependent general quadratic Hamiltonian and the bi-dimensional charged particle in time-dependent electromagnetic fields through the Lie algebraic approach. Such method consists in finding a set of generators that form a closed Lie algebra in terms of which it is possible to express a quantum Hamiltonian and therefore the evolution operator. The evolution operator is then the starting point to obtain the propagator as well as the explicit form of the Heisenberg picture position and momentum operators. First, the set of generators forming a closed Lie algebra is identified for the general quadratic Hamiltonian. This algebra is later extended to study the Hamiltonian of a charged particle in electromagnetic fields exploiting the similarities between the terms of these two Hamiltonians. These results are applied to the solution of five different examples: the linear potential which is used to introduce the Lie algebraic method, a radio frequency ion trap, a Kanai–Caldirola-like forced harmonic oscillator, a charged particle in a time dependent magnetic field, and a charged particle in constant magnetic field and oscillating electric field. In particular we present exact analytical expressions that are fitting for the study of a rotating quadrupole field ion trap and magneto-transport in two-dimensional semiconductor heterostructures illuminated by microwave radiation. In these examples we show that this powerful method is suitable to treat quadratic Hamiltonians with time dependent coefficients quite efficiently yielding closed analytical expressions for the propagator and the Heisenberg picture position and momentum operators. -- Highlights: •We deal with the general quadratic Hamiltonian and a particle in electromagnetic fields. •The evolution operator is worked out through the Lie algebraic approach. •We also obtain the propagator and Heisenberg picture position and momentum operators. •Analytical expressions for a
Time-dependent density functional methods for Raman spectra in open-shell systems.
Aquino, Fredy W; Schatz, George C
2014-01-16
We present an implementation of a time-dependent density functional theory (TD-DFT) linear response module in NWChem for unrestricted DFT calculations and apply it to the calculation of resonant Raman spectra in open-shell molecular systems using the short-time approximation. The new source code was validated and applied to simulate Raman spectra on several doublet organic radicals (e.g., benzyl, benzosemiquinone, TMPD, trans-stilbene anion and cation, and methyl viologen) and the metal complex copper phthalocyanine. We also introduce a divide-and-conquer approach for the evaluation of polarizabilities in relatively large systems (e.g., copper phthalocyanine). The implemented tool gives comparisons with experiment that are similar to what is commonly found for closed-shell systems, with good agreement for most features except for small frequency shifts, and occasionally large deviations for some modes that depend on the molecular system studied, experimental conditions not being accounted in the modeling such as solvation effects and extra solvent-based peaks, and approximations in the underlying theory. The approximations used in the quantum chemical modeling include (i) choice of exchange-correlation functional and basis set; (ii) harmonic approximation used in the frequency analysis to determine vibrational normal modes; and (iii) short-time approximation (omission of nuclear motion effects) used in calculating resonant Raman spectra.
Wang, H; Kühn, O
2016-01-01
Recent developments in attosecond spectroscopy yield access to the correlated motion of electrons on their intrinsic time scales. Spin-flip dynamics is usually considered in the context of valence electronic states, where spin-orbit coupling is weak and processes related to the electron spin are usually driven by nuclear motion. However, for core-excited states, where the core hole has a nonzero angular momentum, spin-orbit coupling is strong enough to drive spin-flips on a much shorter time scale. Using density matrix based time-dependent restricted active space configuration interaction including spin-orbit coupling, we address an unprecedentedly short spin-crossover for the example of L-edge (2p$\\rightarrow$3d) excited states of a prototypical Fe(II) complex. This process occurs on a time scale, which is faster than that of Auger decay ($\\sim$4\\,fs) treated here explicitly. Modest variations of carrier frequency and pulse duration can lead to substantial changes in the spin-state yield, suggesting its cont...
Hilal, Rifaat
2017-06-19
We aim at providing better insight into the parameters that govern the intramolecular charge transfer (ICT) and photo-injection processes in dyes for dye-sensitised solar cells (DSSC). Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are utilized to study the geometry, electronic structure, electrostatic potential (ESP) and absorption spectrum, for a representative donor-π bridge-acceptor (D–π–A) dye for DSSC. The coplanar geometry of the dye (D1) facilitates strong conjugation and considerable delocalization originating the π CT interaction from donor to acceptor orbitals and the hyper-conjugative interactions involving Rydberg states. A model simulating the adsorption of the dye on the TiO surface is utilized to estimate binding energies. The effect of fluorine substituents in the π-spacer on the quantum efficiency of DSSCs was investigated. Gibb’s free energy values, redox potentials, excited state lifetime, non-linear optical properties (NLO) and driving forces for D1 and its fluorinated derivatives were computed.
Energy Technology Data Exchange (ETDEWEB)
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.
Time-Dependent Density Functional Theory Beyond Kohn-Sham Slater Determinants
Fuks, Johanna I; Ruggenthaler, Michael; Maitra, Neepa T
2016-01-01
When running time-dependent density functional theory (TDDFT) calculations for real-time simulations of non-equilibrium dynamics, the user has a choice of initial Kohn-Sham state, and typically a Slater determinant is used. We explore the impact of this choice on the exchange-correlation potential when the physical system begins in a 50:50 superposition of the ground and first-excited state of the system. We investigate the possibility of judiciously choosing a Kohn-Sham initial state that minimizes errors when adiabatic functionals are used. We find that if the Kohn-Sham state is chosen to have a configuration matching the one that dominates the interacting state, this can be achieved for a finite time duration for some but not all such choices. When the Kohn-Sham system does not begin in a Slater determinant, we further argue that the conventional splitting of the exchange-correlation potential into exchange and correlation parts has limited value, and instead propose a decomposition into a "single-particle...
A time-dependent vector field topology based on streak surfaces.
Uffinger, Markus; Sadlo, Filip; Ertl, Thomas
2013-03-01
It was shown recently how the 2D vector field topology concept, directly applicable to stationary vector fields only, can be generalized to time-dependent vector fields by replacing the role of stream lines by streak lines. The present paper extends this concept to 3D vector fields. In traditional 3D vector field topology separatrices can be obtained by integrating stream lines from 0D seeds corresponding to critical points. We show that in our new concept, in contrast, 1D seeding constructs are required for computing streak-based separatrices. In analogy to the 2D generalization we show that invariant manifolds can be obtained by seeding streak surfaces along distinguished path surfaces emanating from intersection curves between codimension-1 ridges in the forward and reverse finite-time Lyapunov exponent (FTLE) fields. These path surfaces represent a time-dependent generalization of critical points and convey further structure in time-dependent topology of vector fields. Compared to the traditional approach based on FTLE ridges, the resulting streak manifolds ease the analysis of Lagrangian coherent structures (LCS) with respect to visual quality and computational cost, especially when time series of LCS are computed. We exemplify validity and utility of the new approach using both synthetic examples and computational fluid dynamics results.
A relativistic time-dependent density functional study of the excited states of the mercury dimer
Energy Technology Data Exchange (ETDEWEB)
Kullie, Ossama, E-mail: kullie@uni-kassel.de, E-mail: ossama.kullie@unistra.fr [Institute de Chimie de Strasbourg, CNRS et Université de Strasbourg, Laboratoire de Chimie Quantique, 4 rue Blaise Pascal, 67070 Strasbourg, France and Theoretical Physics, Institute for Physics, Department of Mathematics and Natural Science, University of Kassel, D-34127 Kassel (Germany)
2014-01-14
In previous works on Zn{sub 2} and Cd{sub 2} dimers we found that the long-range corrected CAMB3LYP gives better results than other density functional approximations for the excited states, especially in the asymptotic region. In this paper, we use it to present a time-dependent density functional (TDDFT) study for the ground-state as well as the excited states corresponding to the (6s{sup 2} + 6s6p), (6s{sup 2} + 6s7s), and (6s{sup 2} + 6s7p) atomic asymptotes for the mercury dimer Hg{sub 2}. We analyze its spectrum obtained from all-electron calculations performed with the relativistic Dirac-Coulomb and relativistic spinfree Hamiltonian as implemented in DIRAC-PACKAGE. A comparison with the literature is given as far as available. Our result is excellent for the most of the lower excited states and very encouraging for the higher excited states, it shows generally good agreements with experimental results and outperforms other theoretical results. This enables us to give a detailed analysis of the spectrum of the Hg{sub 2} including a comparative analysis with the lighter dimers of the group 12, Cd{sub 2}, and Zn{sub 2}, especially for the relativistic effects, the spin-orbit interaction, and the performance of CAMB3LYP and is enlightened for similar systems. The result shows, as expected, that spinfree Hamiltonian is less efficient than Dirac-Coulomb Hamiltonian for systems containing heavy elements such as Hg{sub 2}.
Atomic and field dynamics in the time-dependent Jaynes-Cummings model with arbitrary detuning
Institute of Scientific and Technical Information of China (English)
无
2000-01-01
We propose a general numerical method for solving the time -dependent Jaynes-Cummings model with arbitrary detuning by integrating relate d groups of coupled equations using Runge-Kutta numerical technique. The atomic and field dynamics such as evolution of atomic population inversion and second -order correlation function of photons are studied in case of different detunin g. The results show that the field tends to exhibit bunching effect due to the I ncreasing of detuning.
Brics, M; Bauer, D
2016-01-01
Recently introduced time-dependent renormalized-natural-orbital theory (TDRNOT) is based on the equations of motion for the so-called natural orbitals, i.e., the eigenfunctions of the one-body reduced density matrix. Exact TDRNOT can be formulated for any time-dependent two-electron system in either spin configuration. In this paper, the method is tested against high-order harmonic generation (HHG) and Fano profiles in absorption spectra with the help of a numerically exactly solvable one-dimensional model He atom, starting from the spin-singlet ground state. Such benchmarks are challenging because Fano profiles originate from transitions involving autoionizing states, and HHG is a strong-field phenomenon well beyond linear response. TDRNOT with just one natural orbital per spin in the helium spin-singlet case is equivalent to time-dependent Hartree-Fock or time-dependent density functional theory (TDDFT) in exact exchange-only approximation. It is not unexpected that TDDFT fails in reproducing Fano profiles ...
A revised electronic Hessian for approximate time-dependent density functional theory.
Ziegler, Tom; Seth, Michael; Krykunov, Mykhaylo; Autschbach, Jochen
2008-11-14
Time-dependent density functional theory (TD-DFT) at the generalized gradient level of approximation (GGA) has shown systematic errors in the calculated excitation energies. This is especially the case for energies representing electron transitions between two separated regions of space or between orbitals of different spatial extents. It will be shown that these limitations can be attributed to the electronic ground state Hessian G(GGA). Specifically, we shall demonstrate that the Hessian G(GGA) can be used to describe changes in energy due to small perturbations of the electron density (Deltarho), but it should not be applied to one-electron excitations involving the density rearrangement (Deltarho) of a full electron charge. This is in contrast to Hartree-Fock theory where G(HF) has a trust region that is accurate for both small perturbations and one-electron excitations. The large trust radius of G(HF) can be traced back to the complete cancellation of Coulomb and exchange terms in Hartree-Fock (HF) theory representing self-interaction (complete self-interaction cancellation, CSIC). On the other hand, it is shown that the small trust radius for G(GGA) can be attributed to the fact that CSIC is assumed for GGA in the derivation of G(GGA) although GGA (and many other approximate DFT schemes) exhibits incomplete self-interaction cancellation (ISIC). It is further shown that one can derive a new matrix G(R-DFT) with the same trust region as G(HF) by taking terms due to ISIC properly into account. Further, with TD-DFT based on G(R-DFT), energies for state-to-state transitions represented by a one-electron excitation (psi(i)-->psi(a)) are approximately calculated as DeltaE(ai). Here DeltaE(ai) is the energy difference between the ground state Kohn-Sham Slater determinant and the energy of a Kohn-Sham Slater determinant where psi(i) has been replaced by psi(a). We make use of the new Hessian in two numerical applications involving charge-transfer excitations. It is
Spin interference in Rashba metal ring in a time-dependent magnetic field
Chen, Ji; Abdul Jalil, Mansoor Bin; Ghee Tan, Seng
2013-05-01
We investigate spin transport in a metal square ring with a strong Rashba spin orbit coupling (RSOC) effect, in the presence of a time-dependent magnetic field. We show that RSOC can be regarded as a spin-dependent gauge field which imparts a spin-dependent geometric phase (Aharonov-Casher phase) to conduction electrons in the ring. Combining the Aharonov-Bohm phase due to the time-dependent magnetic field with the able Aharonov-Casher phase due to RSOC, we are able to construct a spin interference condition, which modulates spin transport in the ring. The spin transport in the system is calculated via the tight-binding non-equilibrium Green's function formalism. Based on our transport calculations, we proposed a potential application of the Rashba square ring system as an alternating spin current generator.
Unitarity Bounds and RG Flows in Time Dependent Quantum Field Theory
Energy Technology Data Exchange (ETDEWEB)
Dong, Xi; Horn, Bart; Silverstein, Eva; Torroba, Gonzalo; /Stanford U., ITP /Stanford U., Phys. Dept. /SLAC
2012-04-05
We generalize unitarity bounds on operator dimensions in conformal field theory to field theories with spacetime dependent couplings. Below the energy scale of spacetime variation of the couplings, their evolution can strongly affect the physics, effectively shifting the infrared operator scaling and unitarity bounds determined from correlation functions in the theory. We analyze this explicitly for large-N double-trace flows, and connect these to UV complete field theories. One motivating class of examples comes from our previous work on FRW holography, where this effect explains the range of flavors allowed in the dual, time dependent, field theory.
Klinkusch, Stefan; Tremblay, Jean Christophe
2016-05-14
In this contribution, we introduce a method for simulating dissipative, ultrafast many-electron dynamics in intense laser fields. The method is based on the norm-conserving stochastic unraveling of the dissipative Liouville-von Neumann equation in its Lindblad form. The N-electron wave functions sampling the density matrix are represented in the basis of singly excited configuration state functions. The interaction with an external laser field is treated variationally and the response of the electronic density is included to all orders in this basis. The coupling to an external environment is included via relaxation operators inducing transition between the configuration state functions. Single electron ionization is represented by irreversible transition operators from the ionizing states to an auxiliary continuum state. The method finds its efficiency in the representation of the operators in the interaction picture, where the resolution-of-identity is used to reduce the size of the Hamiltonian eigenstate basis. The zeroth-order eigenstates can be obtained either at the configuration interaction singles level or from a time-dependent density functional theory reference calculation. The latter offers an alternative to explicitly time-dependent density functional theory which has the advantage of remaining strictly valid for strong field excitations while improving the description of the correlation as compared to configuration interaction singles. The method is tested on a well-characterized toy system, the excitation of the low-lying charge transfer state in LiCN.
Casida, Mark E.; Jamorski, Christine; Casida, Kim C.; Salahub, Dennis R.
1998-03-01
This paper presents an evaluation of the performance of time-dependent density-functional response theory (TD-DFRT) for the calculation of high-lying bound electronic excitation energies of molecules. TD-DFRT excitation energies are reported for a large number of states for each of four molecules: N2, CO, CH2O, and C2H4. In contrast to the good results obtained for low-lying states within the time-dependent local density approximation (TDLDA), there is a marked deterioration of the results for high-lying bound states. This is manifested as a collapse of the states above the TDLDA ionization threshold, which is at -ɛHOMOLDA (the negative of the highest occupied molecular orbital energy in the LDA). The -ɛHOMOLDA is much lower than the true ionization potential because the LDA exchange-correlation potential has the wrong asymptotic behavior. For this reason, the excitation energies were also calculated using the asymptotically correct potential of van Leeuwen and Baerends (LB94) in the self-consistent field step. This was found to correct the collapse of the high-lying states that was observed with the LDA. Nevertheless, further improvement of the functional is desirable. For low-lying states the asymptotic behavior of the exchange-correlation potential is not critical and the LDA potential does remarkably well. We propose criteria delineating for which states the TDLDA can be expected to be used without serious impact from the incorrect asymptotic behavior of the LDA potential.
Breitkreutz, Stephan; Fischer, Andreas; Kaffah, Silmi; Weigl, Stephanie; Eichwald, Irina; Ziemys, Grazvydas; Schmitt-Landsiedel, Doris; Becherer, Markus
2015-05-01
In this paper, the domain wall (DW) nucleation time and the DW nucleation probability of field-coupled magnets with perpendicular magnetic anisotropy are measured by experiment. A well-established Arrhenius model based on thermally activated magnetization reversal is applied to describe the time-dependent DW nucleation probability. Magneto-optical microscopy(MOKE) is used in the experiments to determine the DW nucleation time and the DW nucleation probability in a pNML inverter structure. The DW propagation speed is measured in order to calculate the required DW propagation time for entire magnetization reversal of pNML logic gates. Experimental results are compared to the derived model. Our results show that the interaction in pNML logic gates plays a significant role for the time-dependent DW nucleation probability and therefore for the reliability of field-coupled circuits.
The fields outside a long solenoid with a time-dependent current
McDonald, Kirk T.
1997-12-01
An instructive version of this well-known problem is the case of a current that is zero to t0. A generally excellent discussion of this case by Abbott and Griffiths features, however, a singularity in the fields at any point at the moment they first become nonzero. This singularity can be avoided by careful approximation, derived here using expressions for time-dependent fields rather than potentials. The result is that while the fields assume a quasistatic character for long times after the current has started to flow, they include a small amount of radiation at short times. Such an effect was observed in a simple experiment involving a kitchen appliance.
Omiste, Juan J
2016-01-01
We present a theoretical study of the mixed-field-orientation of asymmetric top molecules in tilted static electric field and non-resonant linearly polarized laser pulse by solving the time-dependent Schr\\"odinger equation. Within this framework, we compute the mixed-field orientation of a state selected molecular beam of benzonitrile (C$_7$H$_5$N) and compare with the experimental observations [J. L. Hansen et al., Phys. Rev. A 83, 023406 (2011)], and with our previous time-independent descriptions [J. J. Omiste et al., Phys. Chem. Chem. Phys. 13, 18815 (2011)]. For an excited rotational state, we investigate the field-dressed dynamics for several field configurations as those used in the mixed-field experiments. The non-adiabatic phenomena and their consequences on the rotational dynamics are analyzed in detail.
Energy Technology Data Exchange (ETDEWEB)
Nascimento, Daniel R.; DePrince, A. Eugene, E-mail: deprince@chem.fsu.edu [Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390 (United States)
2015-12-07
We present a combined cavity quantum electrodynamics/ab initio electronic structure approach for simulating plasmon-molecule interactions in the time domain. The simple Jaynes-Cummings-type model Hamiltonian typically utilized in such simulations is replaced with one in which the molecular component of the coupled system is treated in a fully ab initio way, resulting in a computationally efficient description of general plasmon-molecule interactions. Mutual polarization effects are easily incorporated within a standard ground-state Hartree-Fock computation, and time-dependent simulations carry the same formal computational scaling as real-time time-dependent Hartree-Fock theory. As a proof of principle, we apply this generalized method to the emergence of a Fano-like resonance in coupled molecule-plasmon systems; this feature is quite sensitive to the nanoparticle-molecule separation and the orientation of the molecule relative to the polarization of the external electric field.
Time dependent solitons of noncommutative Chern-Simons theory coupled to scalar fields
Hadasz, L; Rocek, M; Von Unge, R; Hadasz, Leszek; Lindstrom, Ulf; Rocek, Martin; Unge, Rikard von
2003-01-01
We study one- and two-soliton solutions of noncommutative Chern-Simons theory coupled to a nonrelativistic or a relativistic scalar field. In the nonrelativistic case it is not possible to find the dynamics of the solitons using traditional moduli space techniques. To do better we have found exact time dependent one soliton solutions to the full equations of motion. They represent solitons moving in straight lines with constant velocity. Surprisingly we find that the set of allowed velocities is quantized! The allowed velocities are proportional to the square root of an integer. In the relativistic case we find the metric on the two soliton moduli space and using techinques developed in the nonrelativistic case we also find exact time dependent one-soliton solutions. Again the allowed velocities are quantized, though in a slightly more complicated fashion.
Energy Technology Data Exchange (ETDEWEB)
Tretiak, Sergei [Los Alamos National Laboratory
2008-01-01
Four different numerical algorithms suitable for a linear scaling implementation of time-dependent Hartree-Fock and Kohn-Sham self-consistent field theories are examined. We compare the performance of modified Lanczos, Arooldi, Davidson, and Rayleigh quotient iterative procedures to solve the random-phase approximation (RPA) (non-Hermitian) and Tamm-Dancoff approximation (TDA) (Hermitian) eigenvalue equations in the molecular orbital-free framework. Semiempirical Hamiltonian models are used to numerically benchmark algorithms for the computation of excited states of realistic molecular systems (conjugated polymers and carbon nanotubes). Convergence behavior and stability are tested with respect to a numerical noise imposed to simulate linear scaling conditions. The results single out the most suitable procedures for linear scaling large-scale time-dependent perturbation theory calculations of electronic excitations.
Nabert, Christian; Othmer, Carsten; Glassmeier, Karl-Heinz
2017-05-01
The interaction of the solar wind with a planetary magnetic field causes electrical currents that modify the magnetic field distribution around the planet. We present an approach to estimating the planetary magnetic field from in situ spacecraft data using a magnetohydrodynamic (MHD) simulation approach. The method is developed with respect to the upcoming BepiColombo mission to planet Mercury aimed at determining the planet's magnetic field and its interior electrical conductivity distribution. In contrast to the widely used empirical models, global MHD simulations allow the calculation of the strongly time-dependent interaction process of the solar wind with the planet. As a first approach, we use a simple MHD simulation code that includes time-dependent solar wind and magnetic field parameters. The planetary parameters are estimated by minimizing the misfit of spacecraft data and simulation results with a gradient-based optimization. As the calculation of gradients with respect to many parameters is usually very time-consuming, we investigate the application of an adjoint MHD model. This adjoint MHD model is generated by an automatic differentiation tool to compute the gradients efficiently. The computational cost for determining the gradient with an adjoint approach is nearly independent of the number of parameters. Our method is validated by application to THEMIS (Time History of Events and Macroscale Interactions during Substorms) magnetosheath data to estimate Earth's dipole moment.
Tapavicza, Enrico; Tavernelli, Ivano; Rothlisberger, Ursula; Filippi, Claudia; Casida, Mark E.
2008-01-01
We present a mixed time-dependent density-functional theory (TDDFT)/classical trajectory surface hopping (SH) study of the photochemical ring opening in oxirane. Previous preparatory work limited to the symmetric CC ring-opening pathways of oxirane concluded that the Tamm-Dancoff approximation (TDA)
Grozema, FC; Telesca, R; Snijders, JG; Siebbeles, LDA
2003-01-01
This paper discusses a time-dependent density functional theory study of the effect of molecular structure on the excited state polarizability of conjugated molecules. A short phenylenevinylene oligomer containing three phenyl rings (PV2, distyryl benzene) is taken as a model system. Introduction of
Linear Scaling Solution of the Time-Dependent Self-Consistent-Field Equations
Directory of Open Access Journals (Sweden)
Matt Challacombe
2014-03-01
Full Text Available A new approach to solving the Time-Dependent Self-Consistent-Field equations is developed based on the double quotient formulation of Tsiper 2001 (J. Phys. B. Dual channel, quasi-independent non-linear optimization of these quotients is found to yield convergence rates approaching those of the best case (single channel Tamm-Dancoff approximation. This formulation is variational with respect to matrix truncation, admitting linear scaling solution of the matrix-eigenvalue problem, which is demonstrated for bulk excitons in the polyphenylene vinylene oligomer and the (4,3 carbon nanotube segment.
Li, Yonghui; Ullrich, Carsten
2013-03-01
The time-dependent transition density matrix (TDM) is a useful tool to visualize and interpret the induced charges and electron-hole coherences of excitonic processes in large molecules. Combined with time-dependent density functional theory on a real-space grid (as implemented in the octopus code), the TDM is a computationally viable visualization tool for optical excitation processes in molecules. It provides real-time maps of particles and holes which gives information on excitations, in particular those that have charge-transfer character, that cannot be obtained from the density alone. Some illustration of the TDM and comparison with standard density difference plots will be shown for photoexcited organic donor-acceptor molecules. This work is supported by NSF Grant DMR-1005651
Modeling multiband emissions from two young SNRs with a time-dependent magnetic field
Institute of Scientific and Technical Information of China (English)
Yun-Yong Tang; Zu-Cheng Dai; Li Zhang
2013-01-01
The nonthermal components in hard X-rays have been detected in two young supernova remnants (SNRs):SN 1006 and Kepler's SNR.Various theoretical models showed that the amplification of the magnetic field was crucial to explain their multiband emission properties.We investigate the evolution of the magnetic field and model the multiband emissions from these two young SNRs with a time-dependent injection model.The results indicate that (1) the radio and X-ray emissions are reproduced by synchrotron radiation of the injected electrons,while the γ-rays can be explained as inverse Compton scattering of the relativistic electrons and proton-proton interaction of the high-energy protons; and (2) the amplification of the magnetic field spontaneously happens with reasonable parameters.
Lopata, Kenneth; Govind, Niranjan
2011-05-10
The response of matter to external fields forms the basis for a vast wealth of fundamental physical processes ranging from light harvesting to nanoscale electron transport. Accurately modeling ultrafast electron dynamics in excited systems thus offers unparalleled insight but requires an inherently nonlinear time-resolved approach. To this end, an efficient and massively parallel real-time real-space time-dependent density functional theory (RT-TDDFT) implementation in NWChem is presented. The implementation is first validated against linear-response TDDFT and experimental results for a series of molecules subjected to small electric field perturbations. Second, nonlinear excitation of green fluorescent protein is studied, which shows a blue-shift in the spectrum with increasing perturbation, as well as a saturation in absorption. Next, the charge dynamics of optically excited zinc porphyrin is presented in real time and real space, with relevance to charge injection in photovoltaic devices. Finally, intermolecular excitation in an adenine-thymine base pair is studied using the BNL range separated functional [ Baer , R. ; Neuhauser , D. Phys. Rev. Lett. 2005 , 94 , 043002 ], demonstrating the utility of a real-time approach in capturing charge transfer processes.
Energy Technology Data Exchange (ETDEWEB)
Kullie, Ossama [CNRS et Universite de Strasbourg, Institut de Chimie, Laboratoire de Chimie Quantique, 1 Rue Blaise Pascal, F- 67008 Strasbourg cedex (France)
2012-07-01
In this poster I present a (time-dependent) density functional study of the 20 low-lying excited states as well the ground states of the zinc dimer Zn{sub 2}. I analyze the spectrum of the dimer obtained form all electrons calculations which are performed using time-depended density functional with a relativistic 4-components-, and spin-free-Hamiltonian. I show results for different well-known density functional approximations, in comparing with literature and experimental values, the results are very encouraging, especially for the lowest excited states of these dimers. However, the results show that only the long-range corrected functionals such CAMB3LYP gives the correct asymptotic behavior for the higher states, for which the best result is obtained, and a comparable result is obtained from PBE0 functional.
Partovi-Azar, Pouya; Kaghazchi, Payam
2017-04-15
We report on real-time time-dependent density functional theory calculations on direction-dependent electron and hole transfer processes in molecular systems. As a model system, we focus on α-sulfur. It is shown that time scale of the electron transfer process from a negatively charged S8 molecule to a neighboring neutral monomer is comparable to that of a strong infrared-active molecular vibrations of the dimer with one negatively charged monomer. This results in a strong coupling between the electrons and the nuclei motion which eventually leads to S8 ring opening before the electron transfer process is completed. The open-ring structure is found to be stable. The similar infrared-active peak in the case of hole transfer, however, is shown to be very weak and hence no significant scattering by the nuclei is possible. The presented approach to study the charge transfer processes in sulfur has direct applications in the increasingly growing research field of charge transport in molecular systems. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.
Electrical analysis of wideband and distributed windows using time-dependent field codes
Shang, C. C.; Caplan, M.; Nickel, H. U.; Thumm, M.
1993-09-01
Windows, which provide the barrier to maintain the vacuum envelope in a microwave tube, are critical components in high-average-power microwave sources, especially at millimeter wavelengths. As RF power levels approach the 100's of kWs to 1 MW range (CW), the window assembly experiences severe thermal and mechanical stresses. Depending on the source, the bandwidth of the window may be less than 1 GHz for gyrotron oscillators or up to approximately 20 GHz for the FOM Institute's fast-tunable, free-electron-maser. The bandwidth requirements give rise to a number of window configurations where the common goal is locally distributed heat dissipation. In order to better understand the transmission and RF properties of these microwave structures, the authors use detailed time-dependent field solvers.
Time-dependent Relativistic Mean-field Theory and Random Phase Approximation
Institute of Scientific and Technical Information of China (English)
P.Ring; D.Vretenar; A.Wandelt; NguyenVanGiai; MAZhong-yu; CAOLi-gang
2001-01-01
The relativistic random phase approximation (RRPA) is derived from the time-dependent relativistic mean field (TD RMF) theory in the limit of small amplitude oscillations. In the no-sea approximation of the RMF theory, the RRPA configuration space includes not only the usual particle-hole ph-states, but also ah configurations, i.e. pairs formed from occupied states in the Fermi sea and empty negative-energy states in the Dirac sea. The contribution of the negative energy states to the RRPA matrices is examined in a schematic model, and the large effect of Dirac sea states on isoscalar strength distributions is illustrated for the giant monopole resonance in 116Sn. It is shown that
Time-dependent mean-field games in the superquadratic case
Gomes, Diogo A.
2016-04-06
We investigate time-dependent mean-field games with superquadratic Hamiltonians and a power dependence on the measure. Such problems pose substantial mathematical challenges as key techniques used in the subquadratic case, which was studied in a previous publication of the authors, do not extend to the superquadratic setting. The main objective of the present paper is to address these difficulties. Because of the superquadratic structure of the Hamiltonian, Lipschitz estimates for the solutions of the Hamilton−Jacobi equation are obtained here through a novel set of techniques. These explore the parabolic nature of the problem through the nonlinear adjoint method. Well-posedness is proven by combining Lipschitz regularity for the Hamilton−Jacobi equation with polynomial estimates for solutions of the Fokker−Planck equation. Existence of classical solutions is then established under conditions depending only on the growth of the Hamiltonian and the dimension. Our results also add to current understanding of superquadratic Hamilton−Jacobi equations.
Energy Technology Data Exchange (ETDEWEB)
Morzan, Uriel N.; Ramírez, Francisco F.; Scherlis, Damián A., E-mail: damian@qi.fcen.uba.ar, E-mail: mcgl@qb.ffyb.uba.ar [Departamento de Química Inorgánica, Analítica y Química Física/INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab. II, Buenos Aires (C1428EHA) (Argentina); Oviedo, M. Belén; Sánchez, Cristián G. [Departamento de Matemática y Física, Facultad de Ciencias Químicas, INFIQC, Universidad Nacional de Córdoba, Ciudad Universitaria, X5000HUA Córdoba (Argentina); Lebrero, Mariano C. González, E-mail: damian@qi.fcen.uba.ar, E-mail: mcgl@qb.ffyb.uba.ar [Instituto de Química y Fisicoquímica Biológicas, IQUIFIB, CONICET (Argentina)
2014-04-28
This article presents a time dependent density functional theory (TDDFT) implementation to propagate the Kohn-Sham equations in real time, including the effects of a molecular environment through a Quantum-Mechanics Molecular-Mechanics (QM-MM) hamiltonian. The code delivers an all-electron description employing Gaussian basis functions, and incorporates the Amber force-field in the QM-MM treatment. The most expensive parts of the computation, comprising the commutators between the hamiltonian and the density matrix—required to propagate the electron dynamics—, and the evaluation of the exchange-correlation energy, were migrated to the CUDA platform to run on graphics processing units, which remarkably accelerates the performance of the code. The method was validated by reproducing linear-response TDDFT results for the absorption spectra of several molecular species. Two different schemes were tested to propagate the quantum dynamics: (i) a leap-frog Verlet algorithm, and (ii) the Magnus expansion to first-order. These two approaches were confronted, to find that the Magnus scheme is more efficient by a factor of six in small molecules. Interestingly, the presence of iron was found to seriously limitate the length of the integration time step, due to the high frequencies associated with the core-electrons. This highlights the importance of pseudopotentials to alleviate the cost of the propagation of the inner states when heavy nuclei are present. Finally, the methodology was applied to investigate the shifts induced by the chemical environment on the most intense UV absorption bands of two model systems of general relevance: the formamide molecule in water solution, and the carboxy-heme group in Flavohemoglobin. In both cases, shifts of several nanometers are observed, consistently with the available experimental data.
Morzan, Uriel N; Ramírez, Francisco F; Oviedo, M Belén; Sánchez, Cristián G; Scherlis, Damián A; Lebrero, Mariano C González
2014-04-28
This article presents a time dependent density functional theory (TDDFT) implementation to propagate the Kohn-Sham equations in real time, including the effects of a molecular environment through a Quantum-Mechanics Molecular-Mechanics (QM-MM) hamiltonian. The code delivers an all-electron description employing Gaussian basis functions, and incorporates the Amber force-field in the QM-MM treatment. The most expensive parts of the computation, comprising the commutators between the hamiltonian and the density matrix-required to propagate the electron dynamics-, and the evaluation of the exchange-correlation energy, were migrated to the CUDA platform to run on graphics processing units, which remarkably accelerates the performance of the code. The method was validated by reproducing linear-response TDDFT results for the absorption spectra of several molecular species. Two different schemes were tested to propagate the quantum dynamics: (i) a leap-frog Verlet algorithm, and (ii) the Magnus expansion to first-order. These two approaches were confronted, to find that the Magnus scheme is more efficient by a factor of six in small molecules. Interestingly, the presence of iron was found to seriously limitate the length of the integration time step, due to the high frequencies associated with the core-electrons. This highlights the importance of pseudopotentials to alleviate the cost of the propagation of the inner states when heavy nuclei are present. Finally, the methodology was applied to investigate the shifts induced by the chemical environment on the most intense UV absorption bands of two model systems of general relevance: the formamide molecule in water solution, and the carboxy-heme group in Flavohemoglobin. In both cases, shifts of several nanometers are observed, consistently with the available experimental data.
Time-dependent density functional theory for nonlinear properties of open-shell systems.
Rinkevicius, Zilvinas; Jha, Prakash Chandra; Oprea, Corneliu I; Vahtras, Olav; Agren, Hans
2007-09-21
This paper presents response theory based on a spin-restricted Kohn-Sham formalism for computation of time-dependent and time-independent nonlinear properties of molecules with a high spin ground state. The developed approach is capable to handle arbitrary perturbations and constitutes an efficient procedure for evaluation of electric, magnetic, and mixed properties. Apart from presenting the derivation of the proposed approach, we show results from illustrating calculations of static and dynamic hyperpolarizabilities of small Si(3n+1)H(6n+3) (n=0,1,2) clusters which mimic Si(111) surfaces with dangling bond defects. The results indicate that the first hyperpolarizability tensor components of Si(3n+1)H(6n+3) have an ordering compatible with the measurements of second harmonic generation in SiO2/Si(111) interfaces and, therefore, support the hypothesis that silicon surface defects with dangling bonds are responsible for this phenomenon. The results exhibit a strong dependence on the quality of basis set and exchange-correlation functional, showing that an appropriate set of diffuse functions is required for reliable predictions of the first hyperpolarizability of open-shell compounds.
Energy Technology Data Exchange (ETDEWEB)
Di Tullo, Pamela, E-mail: pamela.ditullo@univ-pau.fr [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement (LCABIE), Université de Pau et des Pays de l' Adour/CNRS, UMR 5254, IPREM, Hélioparc, 2 Avenue du Président Angot, 64053 Pau Cedex 9 (France); Andra, Research and Development Division, Parc de la Croix Blanche, 1-7 rue Jean Monnet, 92298 Châtenay-Malabry Cedex (France); Pannier, Florence, E-mail: florence.pannier@univ-pau.fr [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement (LCABIE), Université de Pau et des Pays de l' Adour/CNRS, UMR 5254, IPREM, Hélioparc, 2 Avenue du Président Angot, 64053 Pau Cedex 9 (France); Thiry, Yves, E-mail: yves.thiry@andra.fr [Andra, Research and Development Division, Parc de la Croix Blanche, 1-7 rue Jean Monnet, 92298 Châtenay-Malabry Cedex (France); Le Hécho, Isabelle, E-mail: isabelle.lehecho@univ-pau.fr [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement (LCABIE), Université de Pau et des Pays de l' Adour/CNRS, UMR 5254, IPREM, Hélioparc, 2 Avenue du Président Angot, 64053 Pau Cedex 9 (France); Bueno, Maïté, E-mail: maite.bueno@univ-pau.fr [Laboratoire de Chimie Analytique Bio-Inorganique et Environnement (LCABIE), Université de Pau et des Pays de l' Adour/CNRS, UMR 5254, IPREM, Hélioparc, 2 Avenue du Président Angot, 64053 Pau Cedex 9 (France)
2016-08-15
A better understanding of selenium fate in soils at both short and long time scales is mandatory to consolidate risk assessment models relevant for managing both contamination and soil fertilization issues. The purpose of this study was thus to investigate Se retention processes and their kinetics by monitoring time-dependent distribution/speciation changes of both ambient and freshly added Se, in the form of stable enriched selenite-77, over a 2-years field experiment. This study clearly illustrates the complex reactivity of selenium in soil considering three methodologically defined fractions (i.e. soluble, exchangeable, organic). Time-dependent redistribution of Se-77 within solid-phases having different reactivity could be described as a combination of chemical and diffusion controlled processes leading to its stronger retention. Experimental data and their kinetic modeling evidenced that transfer towards less labile bearing phases are controlled by slow processes limiting the overall sorption of Se in soils. These results were used to estimate time needed for {sup 77}Se to reach the distribution of naturally present selenium which may extend up to several decades. Ambient Se speciation accounted for 60% to 100% of unidentified species as function of soil type whereas {sup 77}Se(IV) remained the more abundant species after 2-years field experiment. Modeling Se in the long-term without taking account these slow sorption kinetics would thus result in underestimation of Se retention. When using models based on K{sub d} distribution coefficient, they should be at least reliant on ambient Se which is supposed to be at equilibrium.
Weisman, Jennifer L.; Lee, Timothy J.; Salama, Farid; Gordon-Head, Martin; Kwak, Dochan (Technical Monitor)
2002-01-01
We investigate the electronic absorption spectra of several maximally pericondensed polycyclic aromatic hydrocarbon radical cations with time dependent density functional theory calculations. We find interesting trends in the vertical excitation energies and oscillator strengths for this series containing pyrene through circumcoronene, the largest species containing more than 50 carbon atoms. We discuss the implications of these new results for the size and structure distribution of the diffuse interstellar band carriers.
Mazur, Grzegorz; Włodarczyk, Radosław
2009-04-15
Dressed Time-Dependent Density Functional Theory (Maitra et al., J Chem Phys 2004, 120, 5932) is applied to selected linear polyenes. Limits of validity of the approximation are briefly discussed. The implementation strategy is described. Results for the 2(1)B(u) and 2(1)A(g) states of selected linear polyenes are presented and compared with accessible experimental and theoretical results.
Wierzcholski, Krzysztof
2014-01-01
The present paper is concerned with the calculation of the human hip joint parameters for periodic, stochastic unsteady, motion with asymmetric probability density function for gap height. The asymmetric density function indicates that the stochastic probabilities of gap height decreasing are different in comparison with the probabilities of the gap height increasing. The models of asymmetric density functions are considered on the grounds of experimental observations. Some methods are proposed for calculation of pressure distributions and load carrying capacities for unsteady stochastic conditions in a super thin layer of biological synovial fluid inside the slide biobearing gap limited by a spherical bone acetabulum. Numerical calculations are performed in Mathcad 12 Professional Program, by using the method of finite differences. This method assures stability of numerical solutions of partial differential equations and gives proper values of pressure and load carrying capacity forces occurring in human hip joints.
The importance of three dimensional dune morphology on the time dependent flow field
Hardy, Richard; Parsons, Dan; Reesink, Arnold; Best, Jim
2017-04-01
The flow field over dunes has been extensively studied and there is general understanding of the nature of the flow over dunes formed over two dimensional dunes under equilibrium flow conditions. This model is typically used to explain flow fields over all dunes fields. However, fluvial systems typically experience unsteady flow and therefore the sediment-water interface is constantly reorganizing to form complex three-dimensional morphologies (ripples, dunes and bar forms). Here we investigate how flow over natural three dimensional dunes differs from the accepted model of flow of two dimensional dunes. A series of experiments were undertaken in a flume where fine sand was water worked under a range of unsteady hydraulic conditions to generate quasi-equilibrium three dimensional bed forms. On four occasions, the flume was drained and the bed topography measured with terrestrial LiDAR to create digital elevation models (DEM). Here to demonstrate the approach we choose the DEM with the greatest topographic variation and apply a new Large Eddy Simulation model with an wall-adapting local eddy-viscosity (WALE) turbulence model and a non-linear higher-order numerical differencing scheme. This provided a three dimensional time dependent prediction of the flow field over the static three-dimensional dune morphology at millimeter and hertz scale resolution. The numerically predicted flows were analyzed by standard Reynolds decomposition approaches and Eulerian and Lagrangian coherent flow structure identification methods. The results show that the superimposed bed forms can cause changes in the nature of the classical separated flow regions, in particularly the number of locations where vortices are shed and the points of flow reattachment. Coalescence of vortices generated downstream and can be seen to move to the free surface and form kolk signatures. These structures also correlate in space and time showing a clear flow morphology feedback. The modified flow field
Spin Switch and Qubit Register from a Spin Particle Controlled by a Time-Dependent Magnetic Field
Institute of Scientific and Technical Information of China (English)
WANG Shun-Jin; JIA Cheng-Long; AN Jun-Hong; LUO Hong- Gang
2004-01-01
@@ A spin particle subjected to any time-dependent magnetic field is investigated in detail at different magnetic field configurations. Spin flip probability, spin alignment, cyclic and noncyclic nonadiabatic geometric phases are calculated exactly and their analytical expressions are presented. Our theoretical study shows that a spin particle controlled by a resonant time-dependent magnetic field can be used as efficient controllable devices of spin switch or qubit register.
Mewes, Stefanie A; Plasser, Felix; Dreuw, Andreas
2015-11-01
Excited-state descriptors based on the one-particle transition density matrix referring to the exciton picture have been implemented for time-dependent density functional theory. State characters such as local, extended ππ(∗), Rydberg, or charge transfer can be intuitively classified by simple comparison of these descriptors. Strong effects of the choice of the exchange-correlation kernel on the physical nature of excited states can be found and decomposed in detail leading to a new perspective on functional performance and the design of new functionals.
Tempel, David G; Aspuru-Guzik, Alán
2012-01-01
We prove that the theorems of TDDFT can be extended to a class of qubit Hamiltonians that are universal for quantum computation. The theorems of TDDFT applied to universal Hamiltonians imply that single-qubit expectation values can be used as the basic variables in quantum computation and information theory, rather than wavefunctions. From a practical standpoint this opens the possibility of approximating observables of interest in quantum computations directly in terms of single-qubit quantities (i.e. as density functionals). Additionally, we also demonstrate that TDDFT provides an exact prescription for simulating universal Hamiltonians with other universal Hamiltonians that have different, and possibly easier-to-realize two-qubit interactions. This establishes the foundations of TDDFT for quantum computation and opens the possibility of developing density functionals for use in quantum algorithms.
Energy Technology Data Exchange (ETDEWEB)
Baczewski, Andrew David; Shulenburger, Luke; Desjarlais, Michael Paul; Magyar, Rudolph J.
2014-02-01
In recent years, DFT-MD has been shown to be a useful computational tool for exploring the properties of WDM. These calculations achieve excellent agreement with shock compression experiments, which probe the thermodynamic parameters of the Hugoniot state. New X-ray Thomson Scattering diagnostics promise to deliver independent measurements of electronic density and temperature, as well as structural information in shocked systems. However, they require the development of new levels of theory for computing the associated observables within a DFT framework. The experimentally observable x-ray scattering cross section is related to the electronic density-density response function, which is obtainable using TDDFT - a formally exact extension of conventional DFT that describes electron dynamics and excited states. In order to develop a capability for modeling XRTS data and, more generally, to establish a predictive capability for rst principles simulations of matter in extreme conditions, real-time TDDFT with Ehrenfest dynamics has been implemented in an existing PAW code for DFT-MD calculations. The purpose of this report is to record implementation details and benchmarks as the project advances from software development to delivering novel scienti c results. Results range from tests that establish the accuracy, e ciency, and scalability of our implementation, to calculations that are veri ed against accepted results in the literature. Aside from the primary XRTS goal, we identify other more general areas where this new capability will be useful, including stopping power calculations and electron-ion equilibration.
Evolution of localized states in Lieb lattices under time-dependent magnetic fields
Gouveia, J. D.; Maceira, I. A.; Dias, R. G.
2016-11-01
We study the slow time evolution of localized states of the open-boundary Lieb lattice when a magnetic flux is applied perpendicularly to the lattice and increased linearly in time. In this system, Dirac cones periodically disappear, reappear, and touch the flat band as the flux increases. We show that the slow time evolution of a localized state in this system is analogous to that of a zero-energy state in a three-level system whose energy levels intersect periodically and that this evolution can be mapped into a classical precession motion with a precession axis that rotates as times evolves. Beginning with a localized state of the Lieb lattice, as the magnetic flux is increased linearly and slowly, the evolving state precesses around a state with a small itinerant component and the amplitude of its localized component oscillates around a constant value (below but close to 1), except at multiples of the flux quantum where it may vary sharply. This behavior reflects the existence of an electric field (generated by the time-dependent magnetic field) which breaks the C4 symmetry of the constant flux Hamiltonian.
Time-dependent flow fields around the spherical colonial alga Volvox carteri
Brumley, Douglas; Polin, Marco; Morez, Constant; Goldstein, Raymond; Pedley, Timothy
2011-11-01
Volvox carteri is a spherical colonial alga, consisting of thousands of biflagellate cells. The somatic cells embedded on the surface of the colony beat their flagella approximately towards the south pole, producing a net fluid motion. Using high-speed imaging and particle image velocimetry (PIV) we have been able to accurately analyse the time-dependent flow fields around such colonies. The somatic cells on the colony surface may beat their flagella in a perfectly synchronised fashion, or may exhibit behaviour in which the coordination wanders periodically between forward and backward propagating metachronal waves. We analyse the dependence of this synchronisation on fundamental parameters in the system such as colony radius, characterise the speed and wavelength of metachronal waves propagating on the surface, and investigate the extent to which hydrodynamic interactions are responsible for the exhibited behaviour. The time-averaged flow fields agree with previous experiments involving freely swimming colonies (Phys. Rev. Lett. 105:168101, 2010) and Blake's squirmer model (J. Fluid Mech. 46, 199-208, 1971b).
Thorvaldsen, Andreas J.; Ruud, Kenneth; Kristensen, Kasper; Jørgensen, Poul; Coriani, Sonia
2008-12-01
A general method is presented for the calculation of molecular properties to arbitrary order at the Kohn-Sham density functional level of theory. The quasienergy and Lagrangian formalisms are combined to derive response functions and their residues by straightforward differentiation of the quasienergy derivative Lagrangian using the elements of the density matrix in the atomic orbital representation as variational parameters. Response functions and response equations are expressed in the atomic orbital basis, allowing recent advances in the field of linear-scaling methodology to be used. Time-dependent and static perturbations are treated on an equal footing, and atomic basis sets that depend on the applied frequency-dependent perturbations may be used, e.g., frequency-dependent London atomic orbitals. The 2n+1 rule may be applied if computationally favorable, but alternative formulations using higher-order perturbed density matrices are also derived. These may be advantageous in order to minimize the number of response equations that needs to be solved, for instance, when one of the perturbations has many components, as is the case for the first-order geometrical derivative of the hyperpolarizability.
Thorvaldsen, Andreas J; Ruud, Kenneth; Kristensen, Kasper; Jørgensen, Poul; Coriani, Sonia
2008-12-07
A general method is presented for the calculation of molecular properties to arbitrary order at the Kohn-Sham density functional level of theory. The quasienergy and Lagrangian formalisms are combined to derive response functions and their residues by straightforward differentiation of the quasienergy derivative Lagrangian using the elements of the density matrix in the atomic orbital representation as variational parameters. Response functions and response equations are expressed in the atomic orbital basis, allowing recent advances in the field of linear-scaling methodology to be used. Time-dependent and static perturbations are treated on an equal footing, and atomic basis sets that depend on the applied frequency-dependent perturbations may be used, e.g., frequency-dependent London atomic orbitals. The 2n+1 rule may be applied if computationally favorable, but alternative formulations using higher-order perturbed density matrices are also derived. These may be advantageous in order to minimize the number of response equations that needs to be solved, for instance, when one of the perturbations has many components, as is the case for the first-order geometrical derivative of the hyperpolarizability.
Mapping axonal density and average diameter using non-monotonic time-dependent gradient-echo MRI
Nunes, Daniel; Cruz, Tomás L.; Jespersen, Sune N.; Shemesh, Noam
2017-04-01
White Matter (WM) microstructures, such as axonal density and average diameter, are crucial to the normal function of the Central Nervous System (CNS) as they are closely related with axonal conduction velocities. Conversely, disruptions of these microstructural features may result in severe neurological deficits, suggesting that their noninvasive mapping could be an important step towards diagnosing and following pathophysiology. Whereas diffusion based MRI methods have been proposed to map these features, they typically entail the application of powerful gradients, which are rarely available in the clinic, or extremely long acquisition schemes to extract information from parameter-intensive models. In this study, we suggest that simple and time-efficient multi-gradient-echo (MGE) MRI can be used to extract the axon density from susceptibility-driven non-monotonic decay in the time-dependent signal. We show, both theoretically and with simulations, that a non-monotonic signal decay will occur for multi-compartmental microstructures - such as axons and extra-axonal spaces, which were here used as a simple model for the microstructure - and that, for axons parallel to the main magnetic field, the axonal density can be extracted. We then experimentally demonstrate in ex-vivo rat spinal cords that its different tracts - characterized by different microstructures - can be clearly contrasted using the MGE-derived maps. When the quantitative results are compared against ground-truth histology, they reflect the axonal fraction (though with a bias, as evident from Bland-Altman analysis). As well, the extra-axonal fraction can be estimated. The results suggest that our model is oversimplified, yet at the same time evidencing a potential and usefulness of the approach to map underlying microstructures using a simple and time-efficient MRI sequence. We further show that a simple general-linear-model can predict the average axonal diameters from the four model parameters, and
Institute of Scientific and Technical Information of China (English)
Liu Dan-Dan; Zhang Hong
2011-01-01
We report theoretical studies on the plasmon resonances in linear Au atomic chains by using ab initio timedependent density functional theory. The dipole responses are investigated each as a function of chain length. They converge into a single resonance in the longitudinal mode but split into two transverse modes. As the chain length increases,the longitudinal plasmon mode is redshifted in energy while the transverse modes shift in the opposite direction (blueshifts). In addition,the energy gap between the two transverse modes reduces with chain length increasing. We find that there are unique characteristics,different from those of other metallic chains. These characteristics are crucial to atomic-scale engineering of single-molecule sensing,optical spectroscopy,and so on.
Electron-pair densities with time-dependent quantum Monte-Carlo
Christov, Ivan P
2013-01-01
In this paper we use sets of de Broglie-Bohm trajectories to describe the quantum correlation effects which take place between the electrons in helium atom due to exchange and Coulomb interactions. A short-range screening of the Coulomb potential is used to modify the repulsion between the same spin electrons in physical space in order to comply with the Pauli's exclusion principle. By calculating the electron-pair density for ortho-helium we found that the shape of the exchange hole can be controlled uniquely by a simple screening parameter. For para-helium the inter-electronic distance, and hence the Coulomb hole, results from the combined action of the Coulomb repulsion and the non-local quantum correlations. In this way a robust and self-interaction-free approach is present to find both the ground state and the time evolution of non-relativistic quantum systems.
Romaniello, P; de Boeij, P L
2005-04-22
We included relativistic effects in the formulation of the time-dependent current-density-functional theory for the calculation of linear response properties of metals [P. Romaniello and P. L. de Boeij, Phys. Rev. B (to be published)]. We treat the dominant scalar-relativistic effects using the zeroth-order regular approximation in the ground-state density-functional theory calculations, as well as in the time-dependent response calculations. The results for the dielectric function of gold calculated in the spectral range of 0-10 eV are compared with experimental data reported in literature and recent ellipsometric measurements. As well known, relativistic effects strongly influence the color of gold. We find that the onset of interband transitions is shifted from around 3.5 eV, obtained in a nonrelativistic calculation, to around 1.9 eV when relativity is included. With the inclusion of the scalar-relativistic effects there is an overall improvement of both real and imaginary parts of the dielectric function over the nonrelativistic ones. Nevertheless some important features in the absorption spectrum are not well reproduced, but can be explained in terms of spin-orbit coupling effects. The remaining deviations are attributed to the underestimation of the interband gap (5d-6sp band gap) in the local-density approximation and to the use of the adiabatic local-density approximation in the response calculation.
Chaplin, Vernon H.; Bellan, Paul M.
2015-12-01
A time-dependent two-fluid model has been developed to understand axial variations in the plasma parameters in a very high density (peak ne≳ 5 ×1019 m-3 ) argon inductively coupled discharge in a long 1.1 cm radius tube. The model equations are written in 1D with radial losses to the tube walls accounted for by the inclusion of effective particle and energy sink terms. The ambipolar diffusion equation and electron energy equation are solved to find the electron density ne(z ,t ) and temperature Te(z ,t ) , and the populations of the neutral argon 4s metastable, 4s resonant, and 4p excited state manifolds are calculated to determine the stepwise ionization rate and calculate radiative energy losses. The model has been validated through comparisons with Langmuir probe ion saturation current measurements; close agreement between the simulated and measured axial plasma density profiles and the initial density rise rate at each location was obtained at pA r=30 -60 mTorr . We present detailed results from calculations at 60 mTorr, including the time-dependent electron temperature, excited state populations, and energy budget within and downstream of the radiofrequency antenna.
Excitation dynamics in a lattice Bose gas within the time-dependent Gutzwiller mean-field approach
Energy Technology Data Exchange (ETDEWEB)
Krutitsky, Konstantin V. [Fakultaet fuer Physik der Universitaet Duisburg-Essen, Campus Duisburg, Lotharstrasse 1, D-47048 Duisburg (Germany); Navez, Patrick [Fakultaet fuer Physik der Universitaet Duisburg-Essen, Campus Duisburg, Lotharstrasse 1, D-47048 Duisburg (Germany); Institut fuer Theoretische Physik, TU Dresden, D-01062 Dresden (Germany)
2011-09-15
The dynamics of the collective excitations of a lattice Bose gas at zero temperature is systematically investigated using the time-dependent Gutzwiller mean-field approach. The excitation modes are determined within the framework of the linear-response theory as solutions of the generalized Bogoliubov-de Gennes equations valid in the superfluid and Mott-insulator phases at arbitrary values of parameters. The expression for the sound velocity derived in this approach coincides with the hydrodynamic relation. We calculate the transition amplitudes for the excitations in the Bragg scattering process and show that the higher excitation modes make significant contributions. We simulate the dynamics of the density perturbations and show that their propagation velocity in the limit of week perturbation is satisfactorily described by the predictions of the linear-response analysis.
Modeling Spin Fluctuations and Magnetic Excitations from Time-Dependent Density Functional Theory
Gorni, Tommaso; Timrov, Iurii; Dal Corso, Andrea; Baroni, Stefano
Harnessing spin fluctuations and magnetic excitations in materials is key in many fields of technology, spanning from memory devices to information transfer and processing, to name but a few. A proper understanding of the interplay between collective and single-particle spin excitations is still lacking, and it is expected that first-principle simulations based on TDDFT may shed light on this interplay, as well as on the role of important effects such as relativistic ones and related magnetic anisotropies. All the numerical approaches proposed so far to tackle this problem are based on the computationally demanding solution of the Sternheimer equations for the response orbitals or the even more demanding solution of coupled Dyson equations for the spin and charge susceptibilities. The Liouville-Lanczos approach to TDDFT has already proven to be a valuable alternative, the most striking of its features being the avoidance of sums over unoccupied single-particle states and the frequency-independence of the main numerical bottleneck. In this work we present an extension of this methodology to magnetic systems and its implementation in the Quantum ESPRESSO distribution, together with a few preliminary results on the magnon dispersions in bulk Fe.
Indian Academy of Sciences (India)
Surajit Ghosh; K V S Girish; Subhadip Ghosh
2013-07-01
Intramolecular charge transfer of 4-,-dimethylamino cinnamaldehyde (DMACA) in vacuum and in five different aprotic solvents has been studied by using time-dependent density functional theory (TDDFT). Polarizable continuum model (PCM) was employed to consider solvent-solute interactions. The potential energy curves were constructed at different torsional angle of ,-dimethylamino moiety with respect to the adjacent phenyl ring. A large bathochromic shift in our calculated emission and absorption energies for polar solvents is a clear reminiscent of charge transfer nature of the excited state. Finally, the reported results are in agreement with experimental findings.
Curchod, Basile F E; Penfold, Thomas J; Rothlisberger, Ursula; Tavernelli, Ivano
2013-01-01
The implementation of local control theory using nonadiabatic molecular dynamics within the framework of linear-response time-dependent density functional theory is discussed. The method is applied to study the photoexcitation of lithium fluoride, for which we demonstrate that this approach can efficiently generate a pulse, on-the-fly, able to control the population transfer between two selected electronic states. Analysis of the computed control pulse yields insights into the photophysics of the process identifying the relevant frequencies associated to the curvature of the initial and final state potential energy curves and their energy differences. The limitations inherent to the use of the trajectory surface hopping approach are also discussed.
Ge, Xiaochuan; Rocca, Dario; Gebauer, Ralph; Baroni, Stefano
2014-01-01
We present a new release of the turboTDDFT code featuring an implementation of hybrid functionals, a recently introduced pseudo-Hermitian variant of the Liouville-Lanczos approach to time-dependent density-functional perturbation theory, and a newly developed Davidson-like algorithm to compute selected interior eigenvalues/vectors of the Liouvillian super-operator. Our implementation is thoroughly validated against benchmark calculations performed on the cyanin (C$_{21}$O$_{11}$H$_{21}$) molecule using the Gaussian09 and turboTDDFT 1.0 codes.
Energy Technology Data Exchange (ETDEWEB)
Maitra, Neepa [Hunter College City University of New York, New York, NY (United States)
2016-07-14
This project investigates the accuracy of currently-used functionals in time-dependent density functional theory, which is today routinely used to predict and design materials and computationally model processes in solar energy conversion. The rigorously-based electron-ion dynamics method developed here sheds light on traditional methods and overcomes challenges those methods have. The fundamental research undertaken here is important for building reliable and practical methods for materials discovery. The ultimate goal is to use these tools for the computational design of new materials for solar cell devices of high efficiency.
He, Shenglai; Russakoff, Arthur; Li, Yonghui; Varga, Kálmán
2016-07-01
The spatial current distribution in H-terminated zigzag graphene nanoribbons (ZGNRs) under electrical bias is investigated using time-dependent density-functional theory solved on a real-space grid. A projected complex absorbing potential is used to minimize the effect of reflection at simulation cell boundary. The calculations show that the current flows mainly along the edge atoms in the hydrogen terminated pristine ZGNRs. When a vacancy is introduced to the ZGNRs, loop currents emerge at the ribbon edge due to electrons hopping between carbon atoms of the same sublattice. The loop currents hinder the flow of the edge current, explaining the poor electric conductance observed in recent experiments.
DEFF Research Database (Denmark)
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...
Ronca, Enrico; Angeli, Celestino; Belpassi, Leonardo; De Angelis, Filippo; Tarantelli, Francesco; Pastore, Mariachiara
2014-09-09
Making use of the recently developed excited state charge displacement analysis [E. Ronca et al., J. Chem. Phys. 140, 054110 (2014)], suited to quantitatively characterize the charge fluxes coming along an electronic excitation, we investigate the role of the density relaxation effects in the overall description of electronically excited states of different nature, namely, valence, ionic, and charge transfer (CT), considering a large set of prototypical small and medium-sized molecular systems. By comparing the response densities provided by time-dependent density functional theory (TDDFT) and the corresponding relaxed densities obtained by applying the Z-vector postlinear-response approach [N. C. Handy and H. F. Schaefer, J. Chem. Phys. 81, 5031 (1984)] with those obtained by highly correlated state-of-the-art wave function calculations, we show that the inclusion of the relaxation effects is imperative to get an accurate description of the considered excited states. We also examine what happens at the quality of the response function when an increasing amount of Hartree-Fock (HF) exchange is included in the functional, showing that the usually improved excitation energies in the case of CT states are not always the consequence of an improved description of their overall properties. Remarkably, we find that the relaxation of the response densities is always able to reproduce, independently of the extent of HF exchange in the functional, the benchmark wave function densities. Finally, we propose a novel and computationally convenient strategy, based on the use of the natural orbitals derived from the relaxed TDDFT density to build zero-order wave function for multireference perturbation theory calculations. For a significant set of different excited states, the proposed approach provided accurate excitation energies, comparable to those obtained by computationally demanding ab initio calculations.
Spin-adapted open-shell time-dependent density functional theory. II. Theory and pilot application.
Li, Zhendong; Liu, Wenjian; Zhang, Yong; Suo, Bingbing
2011-04-07
The excited states of open-shell systems calculated by unrestricted Kohn-Sham-based time-dependent density functional theory (U-TD-DFT) are often heavily spin-contaminated and hence meaningless. This is solved ultimately by the recently proposed spin-adapted time-dependent density functional theory (TD-DFT) (S-TD-DFT) [J. Chem. Phys. 133, 064106 (2010)]. Unlike the standard restricted open-shell Kohn-Sham-based TD-DFT (R-TD-DFT) which can only access the singlet-coupled single excitations, the S-TD-DFT can capture both the singlet- and triplet-coupled single excitations with the same computational effort as the U-TD-DFT. The performances of the three approaches (U-TD-DFT, R-TD-DFT, and S-TD-DFT) are compared for both the spin-conserving and spin-flip excitations of prototypical open-shell systems, the nitrogen (N(2)(+)) and naphthalene (C(10)H(8)(+)) cations. The results show that the S-TD-DFT gives rise to balanced descriptions of excited states of open-shell systems.
Energy Technology Data Exchange (ETDEWEB)
Lopata, Kenneth A.; Govind, Niranjan
2013-11-12
We present a real-time time-dependent density functional theory (RT-TDDFT) prescription for capturing near and post-ionization excitations based on non-Hermitian von Neumann density matrix propagation with atom-centered basis sets, tuned range-separated DFT, and a phenomenological imaginary molecular orbital-based absorbing potential to mimic coupling to the continuum. The computed extreme ultraviolet absorption spectra for acetylene (C2H2), water (H2O), and Freon 12 (CF2Cl2) agree well with electron energy loss spectroscopy (EELS) data over the range 0 to 50 eV. The absorbing potential removes spurious high energy finite basis artifacts, yielding correct bound to bound transitions, metastable (autoionizing) resonance states, and consistent overall absorption shapes.
Lopata, Kenneth; Govind, Niranjan
2013-11-12
We present a real-time time-dependent density functional theory (RT-TDDFT) prescription for capturing near and post-ionization excitations based on non-Hermitian von Neumann density matrix propagation with atom-centered basis sets, tuned range-separated DFT, and a phenomenological imaginary molecular orbital-based absorbing potential to mimic coupling to the continuum. The computed extreme ultraviolet absorption spectra for acetylene (C2H2), water (H2O), and Freon 12 (CF2Cl2) agree well with electron energy loss spectroscopy (EELS) data over the range of 0-50 eV. The absorbing potential removes spurious high-energy finite basis artifacts, yielding correct bound-to-bound transitions, metastable (autoionizing) resonance states, and consistent overall absorption shapes.
Chai, Shuo; Yu, Jie; Han, Yong-Chang; Cong, Shu-Lin
2013-11-01
Aminopyrazine (AP) and AP-methanol complexes have been theoretically studied by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The excited-state hydrogen bonds are discussed in detail. In the ground state the intermolecular multiple hydrogen bonds can be formed between AP molecule and protic solvents. The AP monomer and hydrogen-bonded complex of AP with one methanol are photoexcited initially to the S2 state, and then transferred to the S1 state via internal conversion. However the complex of AP with two methanol molecules is directly excited to the S1 state. From the calculated electronic excited energies and simulated absorption spectra, we find that the intermolecular hydrogen bonds are strengthened in the electronic excited states. The strengthening is confirmed by the optimized excited-state geometries. The photochemical processes in the electronic excited states are significantly influenced by the excited-state hydrogen bond strengthening.
Kiyokawa, Shuji
2007-04-01
We give the derivation of the Fano profile (the resonance energy position, the resonance width Γ , and q value) from the time-dependent nonrelativistic density-functional theory (DFT) and propose a scheme for calculating the photoabsorption cross section of hot dense plasmas. As a consequence of this derivation, we show the line profile is obtained as a superposition of Fano and Lorentz profiles when the competition of two optically allowed bound-bound and bound-free transitions occurs. We also show the results of the photoabsorption cross section by applying our scheme to an Fe plasma (density is 7.85g/cm3 , temperature is 100eV ), where the calculation is carried out without numerical divergence for any photon energy. The calculated results are in good agreement with those of Grimaldi.
Pastore, Mariachiara; Assfeld, Xavier; Mosconi, Edoardo; Monari, Antonio; Etienne, Thibaud
2017-07-01
We report a theoretical study on the analysis of the relaxed one-particle difference density matrix characterizing the passage from the ground to the excited state of a molecular system, as obtained from time-dependent density functional theory. In particular, this work aims at using the physics contained in the so-called Z-vector, which differentiates between unrelaxed and relaxed difference density matrices to analyze excited states' nature. For this purpose, we introduce novel quantum-mechanical quantities, based on the detachment/attachment methodology, for analysing the Z-vector transformation for different molecules and density functional theory functionals. A derivation pathway of these novel descriptors is reported, involving a numerical integration to be performed in the Euclidean space on the density functions. This topological analysis is then applied to two sets of chromophores, and the correlation between the level of theory and the behavior of our descriptors is properly rationalized. In particular, the effect of range-separation on the relaxation amplitude is discussed. The relaxation term is finally shown to be system-specific (for a given level of theory) and independent of the number of electrons (i.e., the relaxation amplitude is not simply the result of a collective phenomenon).
Fonseca, I. C.; Bakke, K.
2017-01-01
The quantum description of an atom with a magnetic quadrupole moment in the presence of a time-dependent magnetic field is analysed. It is shown that the time-dependent magnetic field induces an electric field that interacts with the magnetic quadrupole moment of the atom and gives rise to a Landau-type quantization. It is also shown that a time-independent Schrödinger equation can be obtained, i.e., without existing the interaction between the magnetic quadrupole moment of the atom and the time-dependent magnetic field, therefore, the Schrödinger equation can be solved exactly. It is also analysed this system subject to scalar potentials.
Vacuum pair production of charged scalar bosons in time-dependent electric fields
Li, Zi-Liang; Xie, Bai-Song
2013-01-01
Based on the quantum mechanical scattering model, the dynamical assist effect and the multiple-slit interference effect in electron-positron pair production from vacuum are generalized to vacuum pair production of charged scalar bosons. For the former effect some combinations of a strong but slowly varying electric field and a weak but rapidly varying one with different time delay are studied. Results indicate that the oscillation intensity of momentum spectrum and the number density of created bosons reduce with increasing of the time delay. Obviously, they achieve the maximum if the time delay equals zero. For the latter effect, it is shown that this effect does not exist for equal-sign $N$-pulse electric field in contrast to its existence for alternating-sign $N$-pulse. An approximate solution of boson momentum spectrum is got and it is agreeable well with the exact numerical one in alternating-sign $N$-pulse electric field, especially for $2$-pulse field and for small longitudinal momentum. The difference...
Hu, W H; Song, Z
2012-01-01
The exact propagators of two one-dimensional systems with time-dependent external fields are presented by following the path-integral method. It is shown that the Bloch acceleration theorem can be generalized to the impulse-momentum theorem in quantum version. We demonstrate that an evolved Gaussian wave packet always keeps its shape in an arbitrary time-dependent homogeneous driven field. Moreover, that stopping and accelerating of a wave packet can be achieved by the pulsed field in a diabatic way.
Nakai, Hiromi; Yoshikawa, Takeshi
2017-03-01
In this study, we developed an excited-state calculation method for large systems using dynamical polarizabilities at the time-dependent density functional theory level. Three equivalent theories, namely, coupled-perturbed self-consistent field (CPSCF), random phase approximation (RPA), and Green function (GF), were extended to linear-scaling methods using the divide-and-conquer (DC) technique. The implementations of the standard and DC-based CPSCF, RPA, and GF methods are described. Numerical applications of these methods to polyene chains, single-wall carbon nanotubes, and water clusters confirmed the accuracy and efficiency of the DC-based methods, especially DC-GF.
Directory of Open Access Journals (Sweden)
Muhammad Mus-’ab Anas
2015-01-01
Full Text Available This paper presents a systematic study of the absorption spectrum of various sizes of small hydrogenated silicon quantum dots of quasi-spherical symmetry using the time-dependent density functional theory (TDDFT. In this study, real-time and real-space implementation of TDDFT involving full propagation of the time-dependent Kohn-Sham equations were used. The experimental results for SiH4 and Si5H12 showed good agreement with other earlier calculations and experimental data. Then these calculations were extended to study larger hydrogenated silicon quantum dots with diameter up to 1.6 nm. It was found that, for small quantum dots, the absorption spectrum is atomic-like while, for relatively larger (1.6 nm structure, it shows bulk-like behavior with continuous plateau with noticeable peak. This paper also studied the absorption coefficient of silicon quantum dots as a function of their size. Precisely, the dependence of dot size on the absorption threshold is elucidated. It was found that the silicon quantum dots exhibit direct transition of electron from HOMO to LUMO states; hence this theoretical contribution can be very valuable in discerning the microscopic processes for the future realization of optoelectronic devices.
Anomalous transport in fluid field with random waiting time depending on the preceding jump length
Zhang, Hong; Li, Guo-Hua
2016-11-01
Anomalous (or non-Fickian) transport behaviors of particles have been widely observed in complex porous media. To capture the energy-dependent characteristics of non-Fickian transport of a particle in flow fields, in the present paper a generalized continuous time random walk model whose waiting time probability distribution depends on the preceding jump length is introduced, and the corresponding master equation in Fourier-Laplace space for the distribution of particles is derived. As examples, two generalized advection-dispersion equations for Gaussian distribution and lévy flight with the probability density function of waiting time being quadratic dependent on the preceding jump length are obtained by applying the derived master equation. Project supported by the Foundation for Young Key Teachers of Chengdu University of Technology, China (Grant No. KYGG201414) and the Opening Foundation of Geomathematics Key Laboratory of Sichuan Province, China (Grant No. scsxdz2013009).
Energy Technology Data Exchange (ETDEWEB)
Hirata, So; Head-Gordon, Martin P; Szczepanski, Jan; Vala, Martin
2003-06-19
A uniform, comprehensive theoretical interpretation of spectroscopic data is presented for 53 radical ion species of polycyclic aromatic hydrocarbons (PAHs) with the aid of (Tamm–Dancoff) time-dependent density functional theory (TDDFT). TDDFT is capable of predicting the transition energies to the low-lying excited states of PAH ions with quantitative accuracy (the standard deviation from experimental results being less than 0.3 eV) and their intensity patterns qualitatively correctly. The accuracy is hardly affected by the sizes of PAH ions (azulene through dinaphthocoronene), the types of transitions (Koopmans or satellite transitions), the types of orbi-tals involved (π* ← π, π* ← σ, or σ* ← π transitions), the types of ions (cations or anions), or other geometrical or electronic perturbations (non-planarity, sp^{3} carbons, or heterocyclic or non-benzenoid rings).
Energy Technology Data Exchange (ETDEWEB)
Wang, RuLin [Beijing Computational Science Research Center, No. 3 He-Qing Road, Beijing 100084 (China); Zheng, Xiao, E-mail: xz58@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Kwok, YanHo; Xie, Hang; Chen, GuanHua [Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong (China); Yam, ChiYung, E-mail: yamcy@csrc.ac.cn [Beijing Computational Science Research Center, No. 3 He-Qing Road, Beijing 100084 (China); Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong (China)
2015-04-14
Understanding electronic dynamics on material surfaces is fundamentally important for applications including nanoelectronics, inhomogeneous catalysis, and photovoltaics. Practical approaches based on time-dependent density functional theory for open systems have been developed to characterize the dissipative dynamics of electrons in bulk materials. The accuracy and reliability of such approaches depend critically on how the electronic structure and memory effects of surrounding material environment are accounted for. In this work, we develop a novel squared-Lorentzian decomposition scheme, which preserves the positive semi-definiteness of the environment spectral matrix. The resulting electronic dynamics is guaranteed to be both accurate and convergent even in the long-time limit. The long-time stability of electronic dynamics simulation is thus greatly improved within the current decomposition scheme. The validity and usefulness of our new approach are exemplified via two prototypical model systems: quasi-one-dimensional atomic chains and two-dimensional bilayer graphene.
Wang, RuLin; Zheng, Xiao; Kwok, YanHo; Xie, Hang; Chen, GuanHua; Yam, ChiYung
2015-04-01
Understanding electronic dynamics on material surfaces is fundamentally important for applications including nanoelectronics, inhomogeneous catalysis, and photovoltaics. Practical approaches based on time-dependent density functional theory for open systems have been developed to characterize the dissipative dynamics of electrons in bulk materials. The accuracy and reliability of such approaches depend critically on how the electronic structure and memory effects of surrounding material environment are accounted for. In this work, we develop a novel squared-Lorentzian decomposition scheme, which preserves the positive semi-definiteness of the environment spectral matrix. The resulting electronic dynamics is guaranteed to be both accurate and convergent even in the long-time limit. The long-time stability of electronic dynamics simulation is thus greatly improved within the current decomposition scheme. The validity and usefulness of our new approach are exemplified via two prototypical model systems: quasi-one-dimensional atomic chains and two-dimensional bilayer graphene.
Energy Technology Data Exchange (ETDEWEB)
Hayashi, Masahiko, E-mail: m-hayashi@ed.akita-u.ac.jp [Faculty of Education and Human Studies, Akita University, Akita 010-8502 (Japan); Takane, Yositake [Department of Quantum Matter, Graduate School of Advanced Sciences of Matter, Hiroshima University, Higashi-Hiroshima 739-8530 (Japan); Ebisawa, Hiromichi [Institute of Liberal Arts and Sciences, Tohoku University, Sendai 980-8576 (Japan)
2015-03-01
Time-dependent Ginzburg–Landau equation (TDGL) for charge-density-wave (CDW) conductors is discussed. At first, we study a purely one-dimensional case, where the current electrodes are attached from the sides. One of the characteristics of our TDGL is that the non-equilibrium chemical potential for right-moving and left-moving electrons are taken into account as dynamical variables. Then the dynamical interaction between the condensate and the quasiparticles is demonstrated in an apparent form. We present some results of the numerical simulation of the sliding of CDW based on our TDGL. Possible extension to quasi-one dimensional (three-dimensional) systems is also discussed.
Wong, Bryan M; 10.1021/ct100529s
2010-01-01
The optoelectronic and excitonic properties in a series of linear acenes (naphthalene up to heptacene) are investigated using range-separated methods within time-dependent density functional theory (TDDFT). In these rather simple systems, it is well-known that TDDFT methods using conventional hybrid functionals surprisingly fail in describing the low-lying La and Lb valence states, resulting in large, growing errors for the La state and an incorrect energetic ordering as a function of molecular size. In this work, we demonstrate that the range-separated formalism largely eliminates both of these errors and also provides a consistent description of excitonic properties in these systems. We further demonstrate that re-optimizing the percentage of Hartree-Fock exchange in conventional hybrids to match wavefunction-based benchmark calculations still yields serious errors, and a full 100% Hartree-Fock range separation is essential for simultaneously describing both of the La and Lb transitions. Based on an analysi...
Wang, RuLin; Zheng, Xiao; Kwok, YanHo; Xie, Hang; Chen, GuanHua; Yam, ChiYung
2015-04-14
Understanding electronic dynamics on material surfaces is fundamentally important for applications including nanoelectronics, inhomogeneous catalysis, and photovoltaics. Practical approaches based on time-dependent density functional theory for open systems have been developed to characterize the dissipative dynamics of electrons in bulk materials. The accuracy and reliability of such approaches depend critically on how the electronic structure and memory effects of surrounding material environment are accounted for. In this work, we develop a novel squared-Lorentzian decomposition scheme, which preserves the positive semi-definiteness of the environment spectral matrix. The resulting electronic dynamics is guaranteed to be both accurate and convergent even in the long-time limit. The long-time stability of electronic dynamics simulation is thus greatly improved within the current decomposition scheme. The validity and usefulness of our new approach are exemplified via two prototypical model systems: quasi-one-dimensional atomic chains and two-dimensional bilayer graphene.
Liaw, Chih-Chuang; Chang, Jia-Lin; Chen, Shou-Fong; Huang, Jhih-Hong; Sie, Jyun-Fu; Cheng, Yung-Yi
2011-11-01
We present the first theoretical study on a pair of diterpene enantiomers of formula C 21H 34O 5, which were newly isolated from plants and identified as 3β,5β-dihydroxy-16 α/ β-methoxyhalima-13(14)-en-15,16-olide. The equilibrium geometries and harmonic vibrational frequencies of their low-lying conformers were obtained by using the AM1 and B3LYP/6-31+G(d) methods. At the optimized geometries, rotatory strengths of six excited states of each conformer were computed by the time-dependent density functional theory. The electronic circular dichroism spectra were simulated by taking Boltzmann averaging and considering the solvent effect, from which the absolute configurations of the enantiomers were determined. Their vibrational circular dichroism spectra were also predicted.
Zhang, Ruili; He, Yang; Xiao, Jianyuan; Liu, Jian; Qin, Hong; Tang, Yifa
2016-01-01
Relativistic dynamics of a charged particle in time-dependent electromagnetic fields has theoretical significance and a wide range of applications. It is often multi-scale and requires accurate long-term numerical simulations using symplectic integrators. For modern large-scale particle simulations in complex, time-dependent electromagnetic field, explicit symplectic algorithms are much more preferable. In this paper, we treat the relativistic dynamics of a particle as a Hamiltonian system on the cotangent space of the space-time, and construct for the first time explicit symplectic algorithms for relativistic charged particles of order 2 and 3 using the sum-split technique and generating functions.
Energy Technology Data Exchange (ETDEWEB)
Abdel-Khalek, S., E-mail: sayedquantum@yahoo.co.uk [Mathematics Department, Faculty of Science, Sohag University, 82524 Sohag (Egypt); The Abdus Salam International Centre for Theoretical Physics, Strada Costiera 11, Miramare-Trieste (Italy); Berrada, K. [The Abdus Salam International Centre for Theoretical Physics, Strada Costiera 11, Miramare-Trieste (Italy); Al Imam Mohammad Ibn Saud Islamic University (IMSIU), College of Science, Department of Physics, Riyadh (Saudi Arabia); Eleuch, H. [Department of Physics, McGill University, 3600 rue University, Montreal, QC, H3A 2T8 (Canada); Department of Physics, Université de Montréal, 2900 boul. douard-Montpetit, Montreal, QC, H3T 1J4 (Canada)
2015-10-15
The dynamics of a superconducting (SC) qubit interacting with a field under decoherence with and without time-dependent coupling effect is analyzed. Quantum features like the collapse–revivals for the dynamics of population inversion, sudden birth and sudden death of entanglement, and statistical properties are investigated under the phase damping effect. Analytic results for certain parametric conditions are obtained. We analyze the influence of decoherence on the negativity and Wehrl entropy for different values of the physical parameters. We also explore an interesting relation between the SC-field entanglement and Wehrl entropy behavior during the time evolution. We show that the amount of SC-field entanglement can be enhanced as the field tends to be more classical. The studied model of SC-field system with the time-dependent coupling has high practical importance due to their experimental accessibility which may open new perspectives in different tasks of quantum formation processing.
Nakatsukasa, Takashi
2012-01-01
We present the basic concepts and our recent developments in the density functional approaches with the Skyrme functionals for describing nuclear dynamics at low energy. The time-dependent density-functional theory (TDDFT) is utilized for the exact linear response with an external perturbation. For description of collective dynamics beyond the perturbative regime, we present a theory of a decoupled collective submanifold to describe for a slow motion based on the TDDFT. Selected applications are shown to demonstrate the quality of their performance and feasibility. Advantages and disadvantages in the numerical aspects are also discussed.
Quantum work statistics of charged Dirac particles in time-dependent fields.
Deffner, Sebastian; Saxena, Avadh
2015-09-01
The quantum Jarzynski equality is an important theorem of modern quantum thermodynamics. We show that the Jarzynski equality readily generalizes to relativistic quantum mechanics described by the Dirac equation. After establishing the conceptual framework we solve a pedagogical, yet experimentally relevant, system analytically. As a main result we obtain the exact quantum work distributions for charged particles traveling through a time-dependent vector potential evolving under Schrödinger as well as under Dirac dynamics, and for which the Jarzynski equality is verified. Special emphasis is put on the conceptual and technical subtleties arising from relativistic quantum mechanics.
Time-dependent restricted-active-space self-consistent-field theory for bosonic many-body systems
Lévêque, Camille; Bojer Madsen, Lars
2017-04-01
We develop an ab initio time-dependent wavefunction based theory for the description of a many-body system of cold interacting bosons. Like the multi-configurational time-dependent Hartree method for bosons (MCTDHB), the theory is based on a configurational interaction Ansatz for the many-body wavefunction with time-dependent self-consistent-field orbitals. The theory generalizes the MCTDHB method by incorporating restrictions on the active space of the orbital excitations. The restrictions are specified based on the physical situation at hand. The equations of motion of this time-dependent restricted-active-space self-consistent-field (TD-RASSCF) theory are derived. The similarity between the formal development of the theory for bosons and fermions is discussed. The restrictions on the active space allow the theory to be evaluated under conditions where other wavefunction based methods due to exponential scaling in the numerical effort cannot, and to clearly identify the excitations that are important for an accurate description, significantly beyond the mean-field approach. For ground state calculations we find it to be important to allow a few particles to have the freedom to move in many orbitals, an insight facilitated by the flexibility of the restricted-active-space Ansatz. Moreover, we find that a high accuracy can be obtained by including only even excitations in the many-body self-consistent-field wavefunction. Time-dependent simulations of harmonically trapped bosons subject to a quenching of their noncontact interaction, show failure of the mean-field Gross-Pitaevskii approach within a fraction of a harmonic oscillation period. The TD-RASSCF theory remains accurate at much reduced computational cost compared to the MCTDHB method. Exploring the effect of changes of the restricted-active-space allows us to identify that even self-consistent-field excitations are mainly responsible for the accuracy of the method.
Institute of Scientific and Technical Information of China (English)
Li Hua-Mei
2005-01-01
By using the mapping method and an appropriate transformation, we find new exact solutions of nonlinear Gross-Pitaevskii equation with weak bias magnetic and time-dependent laser fields. The solutions obtained in this paper include Jacobian elliptic function solutions, combined Jacobian elliptic function solutions , triangular function solutions, bright and dark solitons, and soliton-like solutions.
Hu, Chunping; Sugino, Osamu; Tateyama, Yoshitaka
2009-02-11
Time-dependent density functional theory (TDDFT) has become a standard tool for investigation of electronic excited states. However, for certain types of electronic excitations, TDDFT is known to give systematically inaccurate results, which has been attributed to the insufficiency of conventional exchange-correlation functionals, such as the local density approximation (LDA). To improve TDDFT performance within LDA, a modified linear response (MLR) scheme was recently proposed, in which the responses from not only the ground state, but also the intermediate excited states are taken into account. This scheme was shown to greatly improve TDDFT performance on the prediction of Rydberg and charge-transfer excitation energies of molecules. Yet, for a validation of this TDDFT-MLR scheme for excitation energies, there remain issues to be resolved regarding Rydberg transitions of single atoms before going to larger systems. In the present work, we show an adapted algorithm to construct the intermediate excited states for rare-gas atoms. With the technique, Rydberg transition energies can be well decoded from LDA, as will also be shown in the application of the TDDFT-MLR scheme to other types of atoms.
Goings, Joshua J; Li, Xiaosong
2016-06-21
One of the challenges of interpreting electronic circular dichroism (ECD) band spectra is that different states may have different rotatory strength signs, determined by their absolute configuration. If the states are closely spaced and opposite in sign, observed transitions may be washed out by nearby states, unlike absorption spectra where transitions are always positive additive. To accurately compute ECD bands, it is necessary to compute a large number of excited states, which may be prohibitively costly if one uses the linear-response time-dependent density functional theory (TDDFT) framework. Here we implement a real-time, atomic-orbital based TDDFT method for computing the entire ECD spectrum simultaneously. The method is advantageous for large systems with a high density of states. In contrast to previous implementations based on real-space grids, the method is variational, independent of nuclear orientation, and does not rely on pseudopotential approximations, making it suitable for computation of chiroptical properties well into the X-ray regime.
Wong, Bryan M; Piacenza, Manuel; Della Sala, Fabio
2009-06-14
The absorption and fluorescence properties in a class of oligothiophene push-pull biomarkers are investigated with a long-range-corrected (LC) density functional method. Using linear-response time-dependent density functional theory (TDDFT), we calculate excitation energies, fluorescence energies, oscillator strengths, and excited-state dipole moments. To benchmark and assess the quality of the LC-TDDFT formalism, an extensive comparison is made between LC-BLYP excitation energies and approximate coupled cluster singles and doubles (CC2) calculations. When using a properly-optimized value of the range parameter, mu, we find that the LC technique provides an accurate description of charge-transfer excitations as a function of biomarker size and chemical functionalization. In contrast, we find that re-optimizing the fraction of Hartree Fock exchange in conventional hybrid functionals still yields an inconsistent description of excitation energies and oscillator strengths for the two lowest excited states in our series of biomarkers. The results of the present study emphasize the importance of a distance-dependent contribution of exchange in TDDFT for investigating excited-state properties.
Energy Technology Data Exchange (ETDEWEB)
Kühn, Michael [Institut für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstraße 12, 76131 Karlsruhe (Germany); Weigend, Florian, E-mail: florian.weigend@kit.edu [Institut für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstraße 12, 76131 Karlsruhe (Germany); Institut für Nanotechnologie, Karlsruher Institut für Technologie, Postfach 3640, 76021 Karlsruhe (Germany)
2014-12-14
“Spin-forbidden” transitions are calculated for an eight-membered set of iridium-containing candidate molecules for organic light-emitting diodes (OLEDs) using two-component time-dependent density functional theory. Phosphorescence lifetimes (obtained from averaging over relevant excitations) are compared to experimental data. Assessment of parameters like non-distorted and distorted geometric structures, density functionals, relativistic Hamiltonians, and basis sets was done by a thorough study for Ir(ppy){sub 3} focussing not only on averaged phosphorescence lifetimes, but also on the agreement of the triplet substate structure with experimental data. The most favorable methods were applied to an eight-membered test set of OLED candidate molecules; Boltzmann-averaged phosphorescence lifetimes were investigated concerning the convergence with the number of excited states and the changes when including solvent effects. Finally, a simple model for sorting out molecules with long averaged phosphorescence lifetimes is developed by visual inspection of computationally easily achievable one-component frontier orbitals.
DEFF Research Database (Denmark)
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......-order harmonic generation spectra of a one-dimensional model of atomic beryllium interacting with a strong laser pulse, the TD-RASSCF method is reasonably accurate while largely reducing the computational complexity. The TD-RASSCF method has the potential to treat large atoms and molecules beyond the capability...
Information entropy of a time-dependent three-level trapped ion interacting with a laser field
Abdel-Aty, Mahmoud
2005-10-01
Trapped and laser-cooled ions are increasingly used for a variety of modern high-precision experiments, frequency standard applications and quantum information processing. Therefore, in this communication we present a comprehensive analysis of the pattern of information entropy arising in the time evolution of an ion interacting with a laser field. A general analytic approach is proposed for a three-level trapped-ion system in the presence of the time-dependent couplings. By working out an exact analytic solution, we conclusively analyse the general properties of the von Neumann entropy and quantum information entropy. It is shown that the information entropy is affected strongly by the time-dependent coupling and exhibits long time periodic oscillations. This feature attributed to the fact that in the time-dependent region Rabi oscillation is time dependent. Using parameters corresponding to a specific three-level ionic system, a single beryllium ion in a RF-(Paul) trap, we obtain illustrative examples of some novel aspects of this system in the dynamical evolution. Our results establish an explicit relation between the exact information entropy and the entanglement between the multi-level ion and the laser field. We show that different nonclassical effects arise in the dynamics of the ionic population inversion, depending on the initial states of the vibrational motion/field and on the values of Lamb-Dicke parameter η.
Performance Analysis of High-Order Numerical Methods for Time-Dependent Acoustic Field Modeling
Moy, Pedro Henrique Rocha
2012-07-01
The discretization of time-dependent wave propagation is plagued with dispersion in which the wavefield is perceived to travel with an erroneous velocity. To remediate the problem, simulations are run on dense and computationally expensive grids yielding plausible approximate solutions. This work introduces an error analysis tool which can be used to obtain optimal simulation parameters that account for mesh size, orders of spatial and temporal discretizations, angles of propagation, temporal stability conditions (usually referred to as CFL conditions), and time of propagation. The classical criteria of 10-15 nodes per wavelength for second-order finite differences, and 4-5 nodes per wavelength for fourth-order spectral elements are shown to be unrealistic and overly-optimistic simulation parameters for different propagation times. This work analyzes finite differences, spectral elements, optimally-blended spectral elements, and isogeometric analysis.
Energy Technology Data Exchange (ETDEWEB)
Malloci, G., E-mail: giuliano.malloci@dsf.unica.it [Istituto Officina dei Materiali (CNR-IOM), Unità di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Italy); Cappellini, G. [Istituto Officina dei Materiali (CNR-IOM), Unità di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Italy); Dipartimento di Fisica, Università degli Studi di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Italy); Mulas, G. [INAF-Osservatorio Astronomico di Cagliari, Strada 54, Località Poggio dei Pini, I-09012 Capoterra (Italy); Mattoni, A. [Istituto Officina dei Materiali (CNR-IOM), Unità di Cagliari, Cittadella Universitaria, I-09042 Monserrato (Italy)
2013-09-30
We report a comparative study of the optoelectronic properties of small acenes (benzene, anthracene, and pentacene) and their bis-triisopropylsilylethynyl (TIPS) functionalized counterparts. We computed the fundamental gap using density functional theory (DFT) in the framework of the ΔSCF scheme, and the optical absorption spectra by means of time-dependent DFT. Upon TIPS functionalization we observed a lowering of the ionization energy and a rise of the electron affinity; we consequently predict a systematic reduction of the fundamental electronic gap which decreases from ∼ 40% for benzene to ∼ 16% for pentacene. This trend is reflected in the computed optical absorption spectra: for all TIPS-molecules the onset of absorption is red-shifted as compared to their plain precursors. In the case of TIPS-pentacene, in particular, the computed spectrum agrees with the available experimental data. - Highlights: • We evaluate the effect of triisopropylsilylethynyl (TIPS)-substitution on acenes. • We compared the fundamental gap and the optical absorption as a function of size. • We found a general gap reduction following TIPS functionalization. • The gap reduction decreases at increasing size, from 40% for n = 1 to 16% for n = 5. • The onset of absorption is red-shifted as compared to TIPS precursors.
Zhang, Xing; Herbert, John M.
2015-02-01
We revisit the formalism for analytic derivative couplings between excited states in time-dependent density functional theory (TDDFT). We derive and implement these couplings using quadratic response theory, then numerically compare this response-theory formulation to couplings implemented previously based on a pseudo-wavefunction formalism and direct differentiation of the Kohn-Sham determinant. Numerical results, including comparison to full configuration interaction calculations, suggest that the two approaches perform equally well for many molecular systems, provided that the underlying DFT method affords accurate potential energy surfaces. The response contributions are found to be important for certain systems with high symmetry, but can be calculated with only a moderate increase in computational cost beyond what is required for the pseudo-wavefunction approach. In the case of spin-flip TDDFT, we provide a formal proof that the derivative couplings obtained using response theory are identical to those obtained from the pseudo-wavefunction formulation, which validates our previous implementation based on the latter formalism.
Ji, Min; Lan, Xin; Han, Zhenping; Hao, Ce; Qiu, Jieshan
2012-11-19
The electronically excited state and luminescence property of metal-organic framework MOF-5 were investigated using relativistic density functional theory (DFT) and time-dependent DFT (TDDFT). The geometry, IR spectra, and UV-vis spectra of MOF-5 in the ground state were calculated using relativistic DFT, leading to good agreement between the experimental and theoretical results. The frontier molecular orbitals and electronic configuration indicated that the luminescence mechanism in MOF-5 follows ligand-to-ligand charge transfer (LLCT), namely, π* → π, rather than emission with the ZnO quantum dot (QD) proposed by Bordiga et al. The geometry and IR spectra of MOF-5 in the electronically excited state have been calculated using the relativistic TDDFT and compared with those for the ground state. The comparison reveals that the Zn4O13 QD is rigid, whereas the ligands BDC(2-) are nonrigid. In addition, the calculated emission band of MOF-5 is in good agreement with the experimental result and is similar to that of the ligand H2BDC. The combined results confirmed that the luminescence mechanism for MOF-5 should be LLCT with little mixing of the ligand-to-metal charge transfer. The reason for the MOF-5 luminescence is explained by the excellent coplanarity between the six-membered ring consisting of zinc, oxygen, carbon, and the benzene ring.
Oliveira, Micael J T; Sousa, José R F; Nogueira, Fernando; Gueorguiev, Gueorgui K
2013-01-01
Systematic study of the optical and magnetic excitations of twelve MSi$_{12}$ and four MSi$_{10}$ transition metal encapsulating Si cages has been carried out by employing real time time-dependent density functional theory. Criteria for the choice of transition metals (M) are clusters' stability, synthesizability, and diversity. It was found that both the optical absorption and the spin-susceptibility spectra are mainly determined by, in decreasing order of importance: 1) the cage shape, 2) the group in the Periodic Table M belongs to, and 3) the period of M in the Periodic Table. Cages with similar structures and metal species that are close to each other in the Periodic Table possess spectra sharing many similarities, e. g., the optical absorption spectra of the MSi$_{12}$ (M = V, Nb, Ta, Cr, Mo, and W), which are highly symmetric and belong to groups 4 and 5 of the Periodic Table, all share a very distinctive peak at around 4 eV. In all cases, although some of the observed transitions are located at the Si...
Lima, Frederico A; Bjornsson, Ragnar; Weyhermüller, Thomas; Chandrasekaran, Perumalreddy; Glatzel, Pieter; Neese, Frank; DeBeer, Serena
2013-12-28
X-ray absorption spectroscopy (XAS) is a widely used experimental technique capable of selectively probing the local structure around an absorbing atomic species in molecules and materials. When applied to heavy elements, however, the quantitative interpretation can be challenging due to the intrinsic spectral broadening arising from the decrease in the core-hole lifetime. In this work we have used high-energy resolution fluorescence detected XAS (HERFD-XAS) to investigate a series of molybdenum complexes. The sharper spectral features obtained by HERFD-XAS measurements enable a clear assignment of the features present in the pre-edge region. Time-dependent density functional theory (TDDFT) has been previously shown to predict K-pre-edge XAS spectra of first row transition metal compounds with a reasonable degree of accuracy. Here we extend this approach to molybdenum K-edge HERFD-XAS and present the necessary calibration. Modern pure and hybrid functionals are utilized and relativistic effects are accounted for using either the Zeroth Order Regular Approximation (ZORA) or the second order Douglas-Kroll-Hess (DKH2) scalar relativistic approximations. We have found that both the predicted energies and intensities are in excellent agreement with experiment, independent of the functional used. The model chosen to account for relativistic effects also has little impact on the calculated spectra. This study provides an important calibration set for future applications of molybdenum HERFD-XAS to complex catalytic systems.
Malloci, G.; Cappellini, G.; Mulas, G.; Mattoni, A.
2011-06-01
Homologous classes of polycyclic aromatic hydrocarbons (PAHs) in their crystalline state are among the most promising materials for organic opto-electronics. Following previous works on oligoacenes we present a systematic comparative study of the electronic, optical, and transport properties of oligoacenes, phenacenes, circumacenes, and oligorylenes. Using density functional theory (DFT) and time-dependent DFT we computed: (i) electron affinities and first ionization energies; (ii) quasiparticle correction to the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap; (iii) molecular reorganization energies and (iv) electronic absorption spectra of neutral and ±1 charged systems. The excitonic effects are estimated by comparing the optical gap and the quasiparticle corrected HOMO-LUMO energy gap. For each molecular property computed, general trends as a function of molecular size and charge state are discussed. Overall, we find that circumacenes have the best transport properties, displaying a steeper decrease of the molecular reorganization energy at increasing sizes, while oligorylenes are much more efficient in absorbing low-energy photons in comparison to the other classes.
König, Carolin; Schlüter, Nicolas; Neugebauer, Johannes
2013-01-01
In subsystem time-dependent density functional theory (TDDFT) [J. Neugebauer, J. Chem. Phys. 126, 134116 (2007), 10.1063/1.2713754] localized excitations are used to calculate delocalized excitations in large chromophore aggregates. We have extended this formalism to allow for the Tamm-Dancoff approximation (TDA). The resulting response equations have a form similar to a perturbative configuration interaction singles (CIS) approach. Thus, the inter-subsystem matrix elements in subsystem TDA can, in contrast to the full subsystem-TDDFT case, directly be interpreted as exciton coupling matrix elements. Here, we present the underlying theory of subsystem TDDFT within the TDA as well as first applications. Since for some classes of pigments, such as linear polyenes and carotenoids, TDA has been reported to perform better than full TDDFT, we also report applications of this formalism to exciton couplings in dimers of such pigments and in mixed bacteriochlorophyll-carotenoid systems. The improved description of the exciton couplings can be traced back to a more balanced description of the involved local excitations.
Zhang, Xing; Herbert, John M
2015-02-14
We revisit the formalism for analytic derivative couplings between excited states in time-dependent density functional theory (TDDFT). We derive and implement these couplings using quadratic response theory, then numerically compare this response-theory formulation to couplings implemented previously based on a pseudo-wavefunction formalism and direct differentiation of the Kohn-Sham determinant. Numerical results, including comparison to full configuration interaction calculations, suggest that the two approaches perform equally well for many molecular systems, provided that the underlying DFT method affords accurate potential energy surfaces. The response contributions are found to be important for certain systems with high symmetry, but can be calculated with only a moderate increase in computational cost beyond what is required for the pseudo-wavefunction approach. In the case of spin-flip TDDFT, we provide a formal proof that the derivative couplings obtained using response theory are identical to those obtained from the pseudo-wavefunction formulation, which validates our previous implementation based on the latter formalism.
Zhang, Xing; Herbert, John M
2014-08-14
We revisit the calculation of analytic derivative couplings for configuration interaction singles (CIS), and derive and implement these couplings for its spin-flip variant for the first time. Our algorithm is closely related to the CIS analytic energy gradient algorithm and should be straightforward to implement in any quantum chemistry code that has CIS analytic energy gradients. The additional cost of evaluating the derivative couplings is small in comparison to the cost of evaluating the gradients for the two electronic states in question. Incorporation of an exchange-correlation term provides an ad hoc extension of this formalism to time-dependent density functional theory within the Tamm-Dancoff approximation, without the need to invoke quadratic response theory or evaluate third derivatives of the exchange-correlation functional. Application to several different conical intersections in ethylene demonstrates that minimum-energy crossing points along conical seams can be located at substantially reduced cost when analytic derivative couplings are employed, as compared to use of a branching-plane updating algorithm that does not require these couplings. Application to H3 near its D(3h) geometry demonstrates that correct topology is obtained in the vicinity of a conical intersection involving a degenerate ground state.
Yost, Dillon C.; Yao, Yi; Kanai, Yosuke
2017-09-01
In ion irradiation processes, electronic stopping power describes the energy transfer rate from the irradiating ion to the target material's electrons. Due to the scarcity and significant uncertainties in experimental electronic stopping power data for materials beyond simple solids, there has been growing interest in the use of first-principles theory for calculating electronic stopping power. In recent years, advances in high-performance computing have opened the door to fully first-principles nonequilibrium simulations based on real-time time-dependent density functional theory (RT-TDDFT). While it has been demonstrated that the RT-TDDFT approach is capable of predicting electronic stopping power for a wide range of condensed matter systems, there has yet to be an exhaustive examination of the physical and numerical approximations involved and their effects on the calculated stopping power. We discuss the results of such a study for crystalline silicon with protons as irradiating ions. We examine the influences of key approximations in RT-TDDFT nonequilibrium simulations on the calculated electronic stopping power, including approximations related to basis sets, finite size effects, exchange-correlation approximation, pseudopotentials, and more. Finally, we propose a simple and efficient correction scheme to account for the contribution from core-electron excitations to the stopping power, as it was found to be significant for large proton velocities.
Liu, Jie; Herbert, John M.
2015-07-01
A novel formulation of time-dependent density functional theory (TDDFT) is derived, based on non-orthogonal, absolutely-localized molecular orbitals (ALMOs). We call this approach TDDFT(MI), in reference to ALMO-based methods for describing molecular interactions (MI) that have been developed for ground-state applications. TDDFT(MI) is intended for efficient excited-state calculations in systems composed of multiple, weakly interacting chromophores. The efficiency is based upon (1) a local excitation approximation; (2) monomer-based, singly-excited basis states; (3) an efficient localization procedure; and (4) a one-step Davidson method to solve the TDDFT(MI) working equation. We apply this methodology to study molecular dimers, water clusters, solvated chromophores, and aggregates of naphthalene diimide that form the building blocks of self-assembling organic nanotubes. Absolute errors of 0.1-0.3 eV with respect to supersystem methods are achievable for these systems, especially for cases involving an excited chromophore that is weakly coupled to several explicit solvent molecules. Excited-state calculations in an aggregate of nine naphthalene diimide monomers are ˜40 times faster than traditional TDDFT calculations.
Electron-Positron Pair Production in Space- or Time-Dependent Electric Fields
Kleinert, Hagen; Xue, She-Sheng
2008-01-01
Treating the production of electron and positron pairs by a strong electric field from the vacuum as a quantum tunneling process we derive, in semiclassical approximation, a general expression for the pair production rate in a $z$-dependent electric field $E(z)$ pointing in the $z$-direction. We also allow for a smoothly varying magnetic field parallel to $E(z)$. The result is applied to a confined field $E(z)\
Energy Technology Data Exchange (ETDEWEB)
Tussupbayev, Samat; Govind, Niranjan; Lopata, Kenneth A.; Cramer, Christopher J.
2015-03-10
We assess the performance of real-time time-dependent density functional theory (RT-TDDFT) for the calculation of absorption spectra of 12 organic dye molecules relevant to photovoltaics and dye sensitized solar cells with 8 exchange-correlation functionals (3 traditional, 3 global hybrids, and 2 range-separated hybrids). We compare the calculations with traditional linear-response (LR) TDDFT. In addition, we demonstrate the efficacy of the RT-TDDFT approach to calculate wide absorption spectra of two large chromophores relevant to photovoltaics and molecular switches.
Coomar, Arunima; Arntsen, Christopher; Lopata, Kenneth A; Pistinner, Shlomi; Neuhauser, Daniel
2011-08-28
We develop near-field (NF), a very efficient finite-difference time-dependent (FDTD) approach for simulating electromagnetic systems in the near-field regime. NF is essentially a time-dependent version of the quasistatic frequency-dependent Poisson algorithm. We assume that the electric field is longitudinal, and hence propagates only a set of time-dependent polarizations and currents. For near-field scales, the time step (dt) is much larger than in the usual Maxwell FDTD approach, as it is not related to the velocity of light; rather, it is determined by the rate of damping and plasma oscillations in the material, so dt = 2.5 a.u. was well converged in our simulations. The propagation in time is done via a leapfrog algorithm much like Yee's method, and only a single spatial convolution is needed per time step. In conjunction, we also develop a new and very accurate 8 and 9 Drude-oscillators fit to the permittivity of gold and silver, desired here because we use a large time step. We show that NF agrees with Mie-theory in the limit of small spheres and that it also accurately describes the evolution of the spectral shape as a function of the separation between two gold or silver spheres. The NF algorithm is especially efficient for systems with small scale dynamics and makes it very simple to introduce additional effects such as embedding.
Directory of Open Access Journals (Sweden)
K. Ide
2002-01-01
Full Text Available In this paper we develop analytical and numerical methods for finding special hyperbolic trajectories that govern geometry of Lagrangian structures in time-dependent vector fields. The vector fields (or velocity fields may have arbitrary time dependence and be realized only as data sets over finite time intervals, where space and time are discretized. While the notion of a hyperbolic trajectory is central to dynamical systems theory, much of the theoretical developments for Lagrangian transport proceed under the assumption that such a special hyperbolic trajectory exists. This brings in new mathematical issues that must be addressed in order for Lagrangian transport theory to be applicable in practice, i.e. how to determine whether or not such a trajectory exists and, if it does exist, how to identify it in a sequence of instantaneous velocity fields. We address these issues by developing the notion of a distinguished hyperbolic trajectory (DHT. We develop an existence criteria for certain classes of DHTs in general time-dependent velocity fields, based on the time evolution of Eulerian structures that are observed in individual instantaneous fields over the entire time interval of the data set. We demonstrate the concept of DHTs in inhomogeneous (or "forced" time-dependent linear systems and develop a theory and analytical formula for computing DHTs. Throughout this work the notion of linearization is very important. This is not surprising since hyperbolicity is a "linearized" notion. To extend the analytical formula to more general nonlinear time-dependent velocity fields, we develop a series of coordinate transforms including a type of linearization that is not typically used in dynamical systems theory. We refer to it as Eulerian linearization, which is related to the frame independence of DHTs, as opposed to the Lagrangian linearization, which is typical in dynamical systems theory, which is used in the computation of Lyapunov exponents. We
On the integration of fields and quanta in time dependent backgrounds
Castillo, Esteban; Palma, Gonzalo
2013-01-01
Field theories with global continuous symmetries may admit configurations in which time translation invariance is broken by the movement of homogeneous background fields evolving along the flat directions implied by the symmetries. In this context, the field fluctuations along the broken symmetry are well parametrized by a Goldstone boson field that may non-trivially interact with other fields present in the theory. These interactions violate Lorentz invariance as a result of the broken time translation invariance of the background, producing a mixing between the field content and the particle spectrum of the theory. In this article we study the effects of such interactions on the low energy dynamics of the Goldstone boson quanta, paying special attention to the role of the particle spectrum of the theory. By studying the particular case of a canonical two-field model with a mexican-hat potential, we analyze the derivation of the low energy effective field theory for the Goldstone boson, and discuss in detail...
Gavrilov, S P; 10.1140/epjc/s10052-009-1135-7
2009-01-01
Recently the paper "Schwinger Mechanism for Gluon Pair Production in the Presence of Arbitrary Time Dependent Chromo-Electric Field" by G. C. Nayak was published [Eur. Phys. J. C 59, 715 (2009); arXiv:0708.2430]. Its aim is to obtain an exact expression for the probability of non-perturbative gluon pair production per unit time per unit volume and per unit transverse momentum in an arbitrary time-dependent chromo-electric background field. We believe that the obtained expression is open to question. We demonstrate its inconsistency on some well-known examples. We think that this is a consequence of using the so-called "shift theorem" [arXiv:hep-th/0609192] in deriving the expression for the probability. We make some critical comments on the theorem and its applicability to the problem in question.
Modified light cone condition via vacuum polarization in a time dependent field
Hu, Huayu
2014-01-01
The appearance of unconventional vacuum properties in intense fields has long been an active field of research. In this paper the vacuum polarization effect is investigated via a pump probe scheme of a probe light propagating in the vacuum excited by two counter-propagating laser beams. The modified light cone condition of the probe light is derived analytically for the situation that it passes through the electric/magnetic antinode plane of the pump field. The derivation does not follow the commonly adopted assumption of treating the pump field as a constant field. Differences from the conventional light cone conditions are identified. The implications of the result are discussed with a consideration of the vacuum birefringence measurement.
Peng, Degao; van Aggelen, Helen; Steinmann, Stephan; Yang, Yang; Yang, Weitao; Duke University Team
2014-03-01
The particle-particle random-phase approximation (pp-RPA) recently attracts extensive interests in quantum chemistry recently. Pp-RPA is a versatile model to calculate ground-state correlation energies, and double ionization potential/double electron affinity. We inspect particle-particle random-phase approximation in different perspectives to further understand its theoretical fundamentals. Viewed as summation of all ladder diagrams, the pp-RPA correlation energy is proved to be analytically equivalent to the ladder coupled-cluster doubles (ladder-CCD) theory. With this equivalence, we can make use of various well-established coupled-cluster techniques to study pp-RPA. Furthermore, we establish linear-response time-dependent density-functional theory with pairing fields (TDDFT-PF), where pp-RPA can be interpreted as the mean-field approximation to a general theory. TDDFT-PF is closely related to the density-functional theory of superconductors, but is applied to normal systems to capture exact N plus/minus 2 excitations. In the linear-response regime, both the adiabatic and non-adiabatic TDDFT-PF equations are established. This sets the fundamentals for further density-functional developments aiming for pp-RPA. These theoretical perspectives will be very helpful for future study.
Kamal, C; Ghanty, T K; Banerjee, Arup; Chakrabarti, Aparna
2009-10-28
We employ all-electron ab initio time-dependent density functional theory based method to calculate the long-range dipole-dipole dispersion coefficient, namely, the van der Waals (vdW) coefficient (C(6)) between fullerenes and finite-length carbon nanotubes as well as between these structures and different small molecules. Our aim is to accurately estimate the strength of the long-range vdW interaction in terms of the C(6) coefficients between these systems and also compare these values as a function of shape and size. The dispersion coefficients are obtained via Casimir-Polder relation. The calculations are carried out with the asymptotically correct exchange-correlation potential-the statistical average of orbital potential. It is observed from our calculations that the C(6) coefficients of the carbon nanotubes increase nonlinearly with length, which implies a much stronger vdW interaction between the longer carbon nanostructures compared with the shorter ones. Additionally, it is found that the values of C(6) and polarizability are about 40%-50% lower for the carbon cages when compared with the results corresponding to the quasi-one-dimensional nanotubes with equivalent number of atoms. From our calculations of the vdW coefficients between the small molecules and the carbon nanostructures, it is observed that for H(2), the C(6) value is much larger compared with that of He. It is found that the rare gas atoms have very low values of vdW coefficient with the carbon nanostructures. In contrast, it is found that other gas molecules, including the ones that are environmentally important, possess much higher C(6) values. Carbon tetrachloride as well as chlorine molecule show very high C(6) values with themselves as well as with the carbon nanostructures. This is due to the presence of the weakly bound seven electrons in the valence state for the halogen atoms, which makes these compounds much more polarizable compared with the others.
Wu, Fangqin; Liu, Wenjian; Zhang, Yong; Li, Zhendong
2011-11-08
To circumvent the cubic scaling and convergence difficulties encountered in the standard top-down localization of the global canonical molecular orbitals (CMOs), a bottom-up localization scheme is proposed based on the idea of "from fragments to molecule". That is, the global localized MOs (LMOs), both occupied and unoccupied, are to be synthesized from the primitive fragment LMOs (pFLMOs) obtained from subsystem calculations. They are orthonormal but are still well localized on the parent fragments of the pFLMOs and can hence be termed as "fragment LMOs" (FLMOs). This has been achieved by making use of two important factors. Physically, it is the transferability of the locality of the fragments that serves as the basis. Mathematically, it is the special block-diagonalization of the Kohn-Sham matrix that allows retention of the locality: The occupied-occupied and virtual-virtual diagonal blocks are only minimally modified when the occupied-virtual off-diagonal blocks are annihilated. Such a bottom-up localization scheme is applicable to systems composed of all kinds of chemical bonds. It is then shown that, by a simple prescreening of the particle-hole pairs, the FLMO-based time-dependent density functional theory (TDDFT) can achieve linear scaling with respect to the system size, with a very small prefactor. As a proof of principle, representative model systems are taken as examples to demonstrate the accuracy and efficiency of the algorithms. As both the orbital picture and integral number of electrons are retained, the FLMO-TDDFT offers a clear characterization of the nature of the excited states in line with chemical/physical intuition.
Holland, Jason P; Green, Jennifer C
2010-04-15
The electronic absorption spectra of a range of copper and zinc complexes have been simulated by using time-dependent density functional theory (TD-DFT) calculations implemented in Gaussian03. In total, 41 exchange-correlation (XC) functionals including first-, second-, and third-generation (meta-generalized gradient approximation) DFT methods were compared in their ability to predict the experimental electronic absorption spectra. Both pure and hybrid DFT methods were tested and differences between restricted and unrestricted calculations were also investigated by comparison of analogous neutral zinc(II) and copper(II) complexes. TD-DFT calculated spectra were optimized with respect to the experimental electronic absorption spectra by use of a Matlab script. Direct comparison of the performance of each XC functional was achieved both qualitatively and quantitatively by comparison of optimized half-band widths, root-mean-squared errors (RMSE), energy scaling factors (epsilon(SF)), and overall quality-of-fit (Q(F)) parameters. Hybrid DFT methods were found to outperform all pure DFT functionals with B1LYP, B97-2, B97-1, X3LYP, and B98 functionals providing the highest quantitative and qualitative accuracy in both restricted and unrestricted systems. Of the functionals tested, B1LYP gave the most accurate results with both average RMSE and overall Q(F) unity (>0.990) for the copper complexes. The XC functional performance in spin-restricted TD-DFT calculations on the zinc complexes was found to be slightly worse. PBE1PBE, mPW1PW91 and B1LYP gave the most accurate results with typical RMSE and Q(F) values between 5.3 and 7.3%, and epsilon(SF) around 0.930. These studies illustrate the power of modern TD-DFT calculations for exploring excited state transitions of metal complexes.
Energy Technology Data Exchange (ETDEWEB)
Malloci, G., E-mail: giuliano.malloci@dsf.unica.it [CNR-IOM and Dipartimento di Fisica, Universita degli Studi di Cagliari, Cittadella Universitaria, Strada Prov. le Monserrato-Sestu Km 0.700, I-09042 Monserrato (Italy); Cappellini, G. [CNR-IOM and Dipartimento di Fisica, Universita degli Studi di Cagliari, Cittadella Universitaria, Strada Prov. le Monserrato-Sestu Km 0.700, I-09042 Monserrato (Italy); INAF-Osservatorio Astronomico di Cagliari-Astrochemistry Group, Strada 54, Localita Poggio dei Pini, I-09012 Capoterra (Italy); Mulas, G. [INAF-Osservatorio Astronomico di Cagliari-Astrochemistry Group, Strada 54, Localita Poggio dei Pini, I-09012 Capoterra (Italy); Mattoni, A. [CNR-IOM and Dipartimento di Fisica, Universita degli Studi di Cagliari, Cittadella Universitaria, Strada Prov. le Monserrato-Sestu Km 0.700, I-09042 Monserrato (Italy)
2011-06-16
Graphical abstract: Electronic absorption spectra of the neutral molecules of the four PAH classes considered, as computed using the real-time real-space TD-DFT. Highlights: {yields}We present a systematic comparative study of families of PAHs. {yields} We computed electronic, optical, and transport properties as a function of size. {yields} We considered oligoacenes, phenacenes, circumacenes, and oligorylenes. {yields} Circumacenes have the best transport properties compared to the other classes. {yields} Oligorylenes are much more efficient in absorbing low-energy photons. - Abstract: Homologous classes of polycyclic aromatic hydrocarbons (PAHs) in their crystalline state are among the most promising materials for organic opto-electronics. Following previous works on oligoacenes we present a systematic comparative study of the electronic, optical, and transport properties of oligoacenes, phenacenes, circumacenes, and oligorylenes. Using density functional theory (DFT) and time-dependent DFT we computed: (i) electron affinities and first ionization energies; (ii) quasiparticle correction to the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap; (iii) molecular reorganization energies and (iv) electronic absorption spectra of neutral and {+-}1 charged systems. The excitonic effects are estimated by comparing the optical gap and the quasiparticle corrected HOMO-LUMO energy gap. For each molecular property computed, general trends as a function of molecular size and charge state are discussed. Overall, we find that circumacenes have the best transport properties, displaying a steeper decrease of the molecular reorganization energy at increasing sizes, while oligorylenes are much more efficient in absorbing low-energy photons in comparison to the other classes.
Li, Zhendong; Liu, Wenjian
2011-11-21
The recently proposed spin-adapted time-dependent density functional theory (S-TD-DFT) [Z. Li and W. Liu, J. Chem. Phys. 133, 064106 (2010)] resolves the spin-contamination problem in describing singly excited states of high spin open-shell systems. It is an extension of the standard restricted open-shell Kohn-Sham-based TD-DFT which can only access those excited states due to singlet-coupled single excitations. It is also far superior over the unrestricted Kohn-Sham-based TD-DFT (U-TD-DFT) which suffers from severe spin contamination for those excited states due to triplet-coupled single excitations. Nonetheless, the accuracy of S-TD-DFT for high spin open-shell systems is still inferior to TD-DFT for well-behaved closed-shell systems. The reason can be traced back to the violation of the spin degeneracy conditions (SDC) by approximate exchange-correlation (XC) functionals. Noticing that spin-adapted random phase approximation (S-RPA) can indeed maintain the SDC by virtue of the Wigner-Eckart theorem, a hybrid ansatz combining the good of S-TD-DFT and S-RPA can immediately be envisaged. The resulting formalism, dubbed as X-TD-DFT, is free of spin contamination and can also be viewed as a S-RPA correction to the XC kernel of U-TD-DFT. Compared with S-TD-DFT, X-TD-DFT leads to much improved results for the low-lying excited states of, e.g., N(2)(+), yet with much reduced computational cost. Therefore, X-TD-DFT can be recommended for routine calculations of excited states of high spin open-shell systems.
Accurate Ground-State Energies of Solids and Molecules from Time-Dependent Density-Functional Theory
DEFF Research Database (Denmark)
Olsen, Thomas; Thygesen, Kristian Sommer
2014-01-01
We demonstrate that ground-state energies approaching chemical accuracy can be obtained by combining the adiabatic-connection fluctuation-dissipation theorem with time-dependent densityfunctional theory. The key ingredient is a renormalization scheme, which eliminates the divergence...
Time-dependent Suppression of Oscillatory Power in Evolving Solar Magnetic Fields
Krishna Prasad, S.; Jess, D. B.; Jain, R.; Keys, P. H.
2016-05-01
Oscillation amplitudes are generally smaller within magnetically active regions like sunspots and plage when compared to their surroundings. Such magnetic features, when viewed in spatially resolved power maps, appear as regions of suppressed power due to reductions in the oscillation amplitudes. Employing high spatial- and temporal-resolution observations from the Dunn Solar Telescope (DST) in New Mexico, we study the power suppression in a region of evolving magnetic fields adjacent to a pore. By utilizing wavelet analysis, we study for the first time how the oscillatory properties in this region change as the magnetic field evolves with time. Image sequences taken in the blue continuum, G-band, Ca ii K, and Hα filters were used in this study. It is observed that the suppression found in the chromosphere occupies a relatively larger area, confirming previous findings. Also, the suppression is extended to structures directly connected to the magnetic region, and is found to get enhanced as the magnetic field strength increased with time. The dependence of the suppression on the magnetic field strength is greater at longer periods and higher formation heights. Furthermore, the dominant periodicity in the chromosphere was found to be anti-correlated with increases in the magnetic field strength.
Fuks, Johanna I
2014-01-01
We explore an asymmetric two-fermion Hubbard dimer to test the accuracy of the adiabatic approximation of time-dependent density functional theory in modelling time-resolved charge transfer. We show that the model shares essential features of a ground state long-range molecule in real-space, and by applying a resonant field we show that the model also reproduces essential traits of the CT dynamics. The simplicity of the model allows us to propagate with an "adiabatically-exact" approximation, i.e. one that uses the exact ground-state exchange-correlation functional, and compare with the exact propagation. This allows us to study the impact of the time-dependent charge-transfer step feature in the exact correlation potential of real molecules on the resulting dynamics. Tuning the parameters of the dimer allows a study both of charge-transfer between open-shell fragments and between closed-shell fragments. We find that the adiabatically-exact functional is unable to properly transfer charge, even in situations ...
Omiste, Juan J.; González-Férez, Rosario
2016-12-01
We present a theoretical study of the mixed-field-orientation of asymmetric-top molecules in tilted static electric field and nonresonant linearly polarized laser pulse by solving the time-dependent Schrödinger equation. Within this framework, we compute the mixed-field orientation of a state-selected molecular beam of benzonitrile (C7H5N ) and compare with the experimental observations [J. L. Hansen et al., Phys. Rev. A 83, 023406 (2011), 10.1103/PhysRevA.83.023406] and with our previous time-independent descriptions [J. J. Omiste et al., Phys. Chem. Chem. Phys. 13, 18815 (2011), 10.1039/c1cp21195a]. For an excited rotational state, we investigate the field-dressed dynamics for several field configurations as those used in the mixed-field experiments. The nonadiabatic phenomena and their consequences on the rotational dynamics are analyzed in detail.
Guan, Jingang; Wang, Fan; Ziegler, Tom; Cox, Hazel
2006-07-28
Orbital energies, ionization potentials, molecular constants, potential energy curves, and the excitation spectrum of O(2) are calculated using time-dependent density functional theory (TDDFT) with Tamm-Dancoff approximation (TDA). The calculated negative highest occupied molecular orbital energy (-epsilon(HOMO)) is compared with the energy difference ionization potential for five exchange correlation functionals consisting of the local density approximation (LDAxc), gradient corrected Becke exchange plus Perdew correlation (B(88X)+P(86C)), gradient regulated asymptotic correction (GRAC), statistical average of orbital potentials (SAOP), and van Leeuwen and Baerends asymptotically correct potential (LB94). The potential energy curves calculated using TDDFT with the TDA at internuclear distances from 1.0 to 1.8 A are divided into three groups according to the electron configurations. The 1pi(u) (4)1pi(g) (2) electron configuration gives rise to the X (3)Sigma(g) (-), a (1)Delta(g), and b (1)Sigma(g) (+) states; the 1pi(u) (3)1pi(g) (3) electron configuration gives rise to the c (1)Sigma(u) (-), C (3)Delta(u), and A (3)Sigma(u) (+) states; and the B (3)Sigma(u) (-), A (1)Delta(u), and f (1)Sigma(u) (+) states are determined by the mixing of two or more electron configurations. The excitation spectrum of the oxygen molecule, calculated with the aforementioned exchange correlation functionals, shows that the results are quite sensitive to the choice of functional. The LDAxc and the B(88X)+P(86C) functionals produce similar spectroscopic patterns with a single strongly absorbing band positioned at 19.82 and 19.72 eV, respectively, while the asymptotically corrected exchange correlation functionals of the SAOP and the LB94 varieties yield similar excitation spectra where the computed strongly absorbing band is located at 16.09 and 16.42 eV, respectively. However, all of the exchange correlation functionals yield only one strongly absorbing band (oscillator strength
Geometric Phase of the Gyromotion for Charged Particles in a Time-dependent Magnetic Field
Energy Technology Data Exchange (ETDEWEB)
Jian Liu and Hong Qin
2011-07-18
We study the dynamics of the gyrophase of a charged particle in a magnetic field which is uniform in space but changes slowly with time. As the magnetic field evolves slowly with time, the changing of the gyrophase is composed of two parts. The rst part is the dynamical phase, which is the time integral of the instantaneous gyrofrequency. The second part, called geometric gyrophase, is more interesting, and it is an example of the geometric phase which has found many important applications in different branches of physics. If the magnetic field returns to the initial value after a loop in the parameter space, then the geometric gyrophase equals the solid angle spanned by the loop in the parameter space. This classical geometric gyrophase is compared with the geometric phase (the Berry phase) of the spin wave function of an electron placed in the same adiabatically changing magnetic field. Even though gyromotion is not the classical counterpart of the quantum spin, the similarities between the geometric phases of the two cases nevertheless reveal the similar geometric nature of the different physics laws governing these two physics phenomena.
Geometric Phase of the Gyromotion for Charged Particles in a Time-dependent Magnetic Field
Energy Technology Data Exchange (ETDEWEB)
Jian Liu and Hong Qin
2011-07-18
We study the dynamics of the gyrophase of a charged particle in a magnetic field which is uniform in space but changes slowly with time. As the magnetic field evolves slowly with time, the changing of the gyrophase is composed of two parts. The rst part is the dynamical phase, which is the time integral of the instantaneous gyrofrequency. The second part, called geometric gyrophase, is more interesting, and it is an example of the geometric phase which has found many important applications in different branches of physics. If the magnetic field returns to the initial value after a loop in the parameter space, then the geometric gyrophase equals the solid angle spanned by the loop in the parameter space. This classical geometric gyrophase is compared with the geometric phase (the Berry phase) of the spin wave function of an electron placed in the same adiabatically changing magnetic field. Even though gyromotion is not the classical counterpart of the quantum spin, the similarities between the geometric phases of the two cases nevertheless reveal the similar geometric nature of the different physics laws governing these two physics phenomena.
Fu, Chuan-Ji; Zhu, Qin-Sheng; Wu, Shao-Yi
2010-06-01
Based on algebraic dynamics and the concept of the concurrence of the entanglement, we investigate the evolutive properties of the two-qubit entanglement that formed by Heisenberg XXX models under a time-depending external held. For this system, the property of the concurrence that is only dependent on the coupling constant J and total values of the external field is proved. Furthermore, we found that the thermal concurrence of the system under a static random external field is a function of the coupling constant J, temperature T, and the magnitude of external held.
Sato, Takeshi; Brezinova, Iva; Lackner, Fabian; Nagele, Stefan; Burgdorfer, Joachim
2016-01-01
We present the numerical implementation of the time-dependent complete-active-space self-consistent-field (TD-CASSCF) method [Phys. Rev. A, 88, 023402 (2013)] for atoms driven by a strong linearly polarized laser pulse. The present implementation treats the problem in its full dimensionality and introduces a gauge-invariant frozen-core approximation, an efficient evaluation of the Coulomb mean field scaling linearly with the number of basis functions, and a split-operator method specifically designed for stable propagation of stiff spatial derivative operators. We apply this method to high-harmonic generation in helium, beryllium, and neon and explore the role of electron correlations.
Craven, Galen T; Hernandez, Rigoberto
2015-01-01
When a chemical reaction is driven by an external field, the transition state that the system must pass through as it changes from reactant to product -for example, an energy barrier- becomes time-dependent. We show that for periodic forcing the rate of barrier crossing can be determined through stability analysis of the non-autonomous transition state. Specifically, strong agreement is observed between the difference in the Floquet exponents describing stability of the transition state trajectory, which defines a recrossing-free dividing surface [G. T. Craven, T. Bartsch, and R. Hernandez, Phys. Rev. E 89, 040801(R) (2014)], and the rates calculated by simulation of ensembles of trajectories. This result opens the possibility to extract rates directly from the intrinsic stability of the transition state, even when it is time-dependent, without requiring a numerically-expensive simulation of the long-time dynamics of a large ensemble of trajectories.
Time-dependent suppression of oscillatory power in evolving solar magnetic fields
Prasad, S Krishna; Jain, R; Keys, P H
2016-01-01
Oscillation amplitudes are generally smaller within magnetically active regions like sunspots and plage, when compared to their surroundings. Such magnetic features, when viewed in spatially-resolved powermaps, appear as regions of suppressed power due to reductions in the oscillation amplitudes. Employing high spatial- and temporal-resolution observations from the Dunn Solar Telescope (DST) in New Mexico, we study the power suppression in a region of evolving magnetic fields adjacent to a pore. By utilising wavelet analysis, we study for the first time, how the oscillatory properties in this region change as the magnetic field evolves with time. Image sequences taken in the blue continuum, G-band, Ca~\\textsc{ii}~K and H$\\alpha$ filters were used in this study. It is observed that the suppression found in the chromosphere occupies a relatively larger area confirming previous findings. Also, the suppression is extended to structures directly connected to the magnetic region and is found to get enhanced as the ...
On the dynamics of excited atoms in time dependent electromagnetic fields
Energy Technology Data Exchange (ETDEWEB)
Foerre, Morten
2004-06-01
This thesis is composed of seven scientific publications written in the period 2001-2004. The focus has been set on Rydberg atoms of hydrogen and lithium in relatively weak electromagnetic fields. Such atoms have been studied extensively during many years, both experimentally and theoretically, They are relatively easy to handle in the laboratory. Their willingness to react to conventional field sources and their long lifetimes, are two reasons for this. Much new insight into fundamental quantum mechanics has been extracted from such studies. By exciting a non-hydrogenic ground state atom or molecule into a highly excited state, many properties of atomic hydrogen are adopted. In many cases the dynamics of such systems can be accurately described by the hydrogenic theory, or alternatively by some slightly modified version like quantum defect theory. In such theories the Rydberg electron(s) of the non-hydrogenic Rydberg system is treated like it is confined in a modified Coulomb potential, which arises from the non-hydrogenic core. defined by the non-excited electrons and the nucleus. The more heavily bound core electrons are less influenced from external perturbations than the excited electrons, giving rise to the so-called frozen-core approximation. where the total effect of the core electrons is put into a modified Coulomb potential. A major part of this thesis has been allocated to the study of core effects in highly excited states of lithium. In collaboration with time experimental group of Erik Horsdal-Pedersen at Aarhus University, we have considered several hydrogenic and non-hydrogenic aspects of such states, when exposed to weak slowly varying electromagnetic fields. The dynamics was restricted to one principal shell (intrashell). Two general features were observed, either the hydrogenic theory applied or alternatively, in case of massive deviation, the dynamics was accurately described by quantum defect theory, clearly demonstrating the usefulness of such
Quantum logic gates from time-dependent global magnetic field in a system with constant exchange
Energy Technology Data Exchange (ETDEWEB)
Nenashev, A. V., E-mail: nenashev@isp.nsc.ru; Dvurechenskii, A. V. [Rzhanov Institute of Semiconductor Physics SB RAS, 630090 Novosibirsk (Russian Federation); Novosibirsk State University, 630090 Novosibirsk (Russian Federation); Zinovieva, A. F. [Rzhanov Institute of Semiconductor Physics SB RAS, 630090 Novosibirsk (Russian Federation); Gornov, A. Yu.; Zarodnyuk, T. S. [Institute for System Dynamics and Control Theory SB RAS, 664033 Irkutsk (Russian Federation)
2015-03-21
We propose a method that implements a universal set of one- and two-quantum-bit gates for quantum computation in a system of coupled electron pairs with constant non-diagonal exchange interaction. In our proposal, suppression of the exchange interaction is performed by the continual repetition of single-spin rotations. A small g-factor difference between the electrons allows for addressing qubits and avoiding strong magnetic field pulses. Numerical experiments were performed to show that, to implement the one- and two-qubit operations, it is sufficient to change the strength of the magnetic field by a few Gauss. This introduces one and then the other electron in a resonance. To determine the evolution of the two-qubit system, we use the algorithms of optimal control theory.
Time dependence of 50 Hz magnetic fields in apartment buildings with indoor transformer stations.
Yitzhak, Nir-Mordechay; Hareuveny, Ronen; Kandel, Shaiela; Ruppin, Raphael
2012-04-01
Twenty-four hour measurements of 50 Hz magnetic fields (MFs) in apartment buildings containing transformer stations have been performed. The apartments were classified into four types, according to their location relative to the transformer room. Temporal correlation coefficients between the MF in various apartments, as well as between MF and transformer load curves, were calculated. It was found that, in addition to their high average MF, the apartments located right above the transformer room also exhibit unique temporal correlation properties.
A time-dependent Ginzburg-Landau phase field formalism for shock-induced phase transitions
Haxhimali, Tomorr; Belof, Jonathan L.; Benedict, Lorin X.
2017-01-01
Phase-field models have become popular in the last two decades to describe a host of free-boundary problems. The strength of the method relies on implicitly describing the dynamics of surfaces and interfaces by a continuous scalar field that enters the global grand free energy functional of the system. Here we explore the potential utility of this method in order to describe shock-induced phase transitions. To this end we make use of the Multiphase Field Theory (MFT) to account for the existence of multiple phases during the transition, and we couple MFT to a hydrodynamic model in the context of a new LLNL code for phase transitions, SAMSA. As a demonstration of this approach, we apply our code to the α - ɛ-Fe phase transition under shock wave loading conditions and compare our results with experiments of Jensen et. al. [J. Appl. Phys., 105:103502 (2009)] and Barker and Hollenbach [J. Appl. Phys., 45:4872 (1974)].
Flick, Johannes; Ruggenthaler, Michael; Appel, Heiko; Rubio, Angel
2015-12-15
The density-functional approach to quantum electrodynamics extends traditional density-functional theory and opens the possibility to describe electron-photon interactions in terms of effective Kohn-Sham potentials. In this work, we numerically construct the exact electron-photon Kohn-Sham potentials for a prototype system that consists of a trapped electron coupled to a quantized electromagnetic mode in an optical high-Q cavity. Although the effective current that acts on the photons is known explicitly, the exact effective potential that describes the forces exerted by the photons on the electrons is obtained from a fixed-point inversion scheme. This procedure allows us to uncover important beyond-mean-field features of the effective potential that mark the breakdown of classical light-matter interactions. We observe peak and step structures in the effective potentials, which can be attributed solely to the quantum nature of light; i.e., they are real-space signatures of the photons. Our findings show how the ubiquitous dipole interaction with a classical electromagnetic field has to be modified in real space to take the quantum nature of the electromagnetic field fully into account.
Wang, Feng; Yao, Yugui; Calvayrac, Florent; Zhang, Fengshou
2016-09-01
The determination of the state-resolved physical information within the framework of time-dependent density functional theory has remained a widely open question. We demonstrated the ability to extract the state-resolved probability from the knowledge of only the time-dependent density, which has been used as the basic variable within the time-dependent density functional theory, with the help of state-resolved single-electron capture experiments for collisions of protons on helium in the energy range of 2-100 keV/amu. The present theoretical results for capture into states of H(1s), H(2s), and H(2p) are in good agreement with the most sophisticated experimental results of H+ + He(1s2) system, validating our approach and numerical implementation.
New Time Dependent Sensitivity Corrections and Updated Flat Fields for the ACS/SBC
Avila, Roberto J.; Kossakowski, Diana
2017-06-01
The sensitivity of the Solar Blind Channel on the Advanced Camera for Surveys changes with time. Until now there was no correction available for this effect. Here we present the new corrections, derived for all the imaging filters using observations that date back to installation, more than 15 years worth of data. The sensitivity can now be continuously monitored and the correction updated as necessary. Additionaly, we present a new set of flat fields for all imaging filters. These are necessary because of the previous discovery of a change in the high frequency pattern in the flats currently in use. The new flats were derived using an improved algorithm than what was used for the previous versions, employing MCMC fitting techniques.
Kishi, Ryohei; Nakano, Masayoshi
2011-04-21
A novel method for the calculation of the dynamic polarizability (α) of open-shell molecular systems is developed based on the quantum master equation combined with the broken-symmetry (BS) time-dependent density functional theory within the Tamm-Dancoff approximation, referred to as the BS-DFTQME method. We investigate the dynamic α density distribution obtained from BS-DFTQME calculations in order to analyze the spatial contributions of electrons to the field-induced polarization and clarify the contributions of the frontier orbital pair to α and its density. To demonstrate the performance of this method, we examine the real part of dynamic α of singlet 1,3-dipole systems having a variety of diradical characters (y). The frequency dispersion of α, in particular in the resonant region, is shown to strongly depend on the exchange-correlation functional as well as on the diradical character. Under sufficiently off-resonant condition, the dynamic α is found to decrease with increasing y and/or the fraction of Hartree-Fock exchange in the exchange-correlation functional, which enhances the spin polarization, due to the decrease in the delocalization effects of π-diradical electrons in the frontier orbital pair. The BS-DFTQME method with the BHandHLYP exchange-correlation functional also turns out to semiquantitatively reproduce the α spectra calculated by a strongly correlated ab initio molecular orbital method, i.e., the spin-unrestricted coupled-cluster singles and doubles.
Dermez, Rasim
2016-10-01
It is solved a time-dependent Hamiltonian using a unitary transformation method which Λ(t) type is used to engineer a cascade Ξ scheme interaction between the vibrational phonons and trapped three-level ion. Quantum entanglement is characterized by comparing concurrence and negativity of the time-dependent ionic-phononic system. In this quantum system, we obtain that the amount of concurrence can be tuned between 0 and 0.99 while the amount of negativity changes between 0 and 0.49.
Energy Technology Data Exchange (ETDEWEB)
Aakeson, P.
1996-10-01
Gadodiamide injection was comparable to Gd-DTPA with regard to both safety and diagnostic efficiency in the central nervous system. The contrast effect of Gd contrast agents is higher at 1.5 T than at 0.3 T both in phantoms and patients with a maximum ratio (signal lesion/signal grey matter) more than 50% higher at 1.5 T. To achieve high contrast effect, heavily T1-weighted images are important. Prolonging the TR from 400 ms to 600 ms reduced the ratio by 15-45% depending on concentration. The effective time window for imaging of BBB (Blood-Brain Barrier) damage is between 2-5 and 25-30 minutes after injection and several scans can be performed without loss of enhancement. To provide maximum detectability of BBB damage in patients, higher doses of Gd contrast media should be useful, especially at low field strengths, as the doses used clinically today do not utilize the maximum contrast effect. High-dose (0.3 mmol/kg b.w.) contrast enhanced MRI (0.3 T) with Gadodiamide injection allowed detection of significantly more and smaller metastases (i.e. BBB damage) than standard dose (0.1 mmol/kg b.w.) High dose contrast-enhanced MRI (0.3 T) did not increase the diagnostic information for the evaluation of patients with failed back surgery syndrome compared to standard dose MRI. 55 refs, 9 figs, 10 tabs.
Directory of Open Access Journals (Sweden)
Jeong Ryeol eChoi
2014-08-01
Full Text Available Quantum characteristics of a charged particle traveling under the influence of an external time-dependent magnetic field in ionized plasma are investigated using the invariant operator method. The Hamiltonian that gives the radial part of the classical equation of motion for the charged particle is dependent on time. The corresponding invariant operator that satisfies Liouville-von Neumann equation is constructed using fundamental relations. The exact radial wave functions are derived by taking advantage of the eigenstates of the invariant operator. Quantum properties of the system is studied using these wave functions. Especially, the time behavior of the radial component of the quantized energy is addressed in detail.
Energy Technology Data Exchange (ETDEWEB)
Hong Qin and Ronald C. Davidson
2011-07-19
In a linear trap confining a one-component nonneutral plasma, the external focusing force is a linear function of the configuration coordinates and/or the velocity coordinates. Linear traps include the classical Paul trap and the Penning trap, as well as the newly proposed rotating-radio- frequency traps and the Mobius accelerator. This paper describes a class of self-similar nonlinear solutions of nonneutral plasma in general time-dependent linear focusing devices, with self-consistent electrostatic field. This class of nonlinear solutions includes many known solutions as special cases.
Institute of Scientific and Technical Information of China (English)
BIAN Xue-Bin; LIU Hong-Ping; SHI Ting-Yun
2008-01-01
A robust time-dependent approach to the high-resolution photoabsorption spectrum of Rydberg atoms in magnetic fields is presented. Traditionally we have to numerically diagonalize a huge matrix to solve the eigen-problem and then to obtain the spectral information. This matrix operation requires high-speed computers with large memories. Alternatively we present a unitary but very easily parallelized time-evolution method in an inexpensive way, which is very accurate and stable even in long-time scale evolution. With this method, we perform the spectral calculation of hydrogen atom in magnetic field, which agrees well with the experimental observation. It can be extended to study the dynamics of Rydberg atoms in more complicated cases such as in combined electric and magnetic fields.
Woodward, Jonathan R; Foster, Timothy J; Salaoru, Adrian T; Vink, Claire B
2008-07-21
A rapidly switched (magnetic field was employed to directly observe magnetic fields from f-pair reactions of radical pairs in homogeneous solution. Geminate radical pairs from the photoabstraction reaction of benzophenone from cyclohexanol were observed directly using a pump-probe pulsed magnetic field method to determine their existence time. No magnetic field effects from geminate pairs were observed at times greater than 100 ns after initial photoexcitation. By measuring magnetic field effects for fields applied continuously only after this initial geminate period, f-pair effects could be directly observed. Measurement of the time-dependence of the field effect for the photolysis of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone in cyclohexanol using time-resolved infrared spectroscopy revealed not only the presence of f-pair magnetic field effects but also the ability of the time dependence of the MARY spectra to observe the changing composition of the randomly encountering pairs throughout the second order reaction period.
Sato, Takeshi
2014-01-01
The time-dependent multiconfiguration self-consistent-field method based on the occupation-restricted multiple active space model is proposed (TD-ORMAS) for multielectron dynamics in intense laser fields. Extending the previously proposed time-dependent complete-active-space self-consistent-field method [TD-CASSCF; Phys. Rev. A, {\\bf 88}, 023402 (2013)], which divides the occupied orbitals into core and active orbitals, the TD-ORMAS method {\\it further} subdivides the active orbitals into an arbitrary number of subgroups, and poses the {\\it occupation restriction} by giving the minimum and maximum number of electrons distributed in each subgroup. This enables highly flexible construction of the configuration interaction (CI) space, allowing a large-active-space simulation of dynamics, e.g., the core excitation or ionization. The equations of motion both for CI coefficients and spatial orbitals are derived based on the time-dependent variational principle, and an efficient algorithm is proposed to solve for th...
Craven, Galen T; Bartsch, Thomas; Hernandez, Rigoberto
2014-07-28
When a chemical reaction is driven by an external field, the transition state that the system must pass through as it changes from reactant to product--for example, an energy barrier--becomes time-dependent. We show that for periodic forcing the rate of barrier crossing can be determined through stability analysis of the non-autonomous transition state. Specifically, strong agreement is observed between the difference in the Floquet exponents describing stability of the transition state trajectory, which defines a recrossing-free dividing surface [G. T. Craven, T. Bartsch, and R. Hernandez, "Persistence of transition state structure in chemical reactions driven by fields oscillating in time," Phys. Rev. E 89, 040801(R) (2014)], and the rates calculated by simulation of ensembles of trajectories. This result opens the possibility to extract rates directly from the intrinsic stability of the transition state, even when it is time-dependent, without requiring a numerically expensive simulation of the long-time dynamics of a large ensemble of trajectories.
Valsson, O.; Filippi, C.; Casida, M.E.
2015-01-01
The excited-state relaxation of retinal protonated Schiff bases (PSBs) is an important test case for biological applications of time-dependent (TD) density-functional theory (DFT). While well-known shortcomings of approximate TD-DFT might seem discouraging for application to PSB relaxation, progress
Dodonov, V V
2016-01-01
An exact infinite set of coupled ordinary differential equations, describing the evolution of the modes of the classical electromagnetic field inside an ideal cavity, containing a thin slab with the time-dependent conductivity $\\sigma(t)$ and dielectric permittivity $\\varepsilon(t)$, is derived for the dispersion-less media. This problem is analyzed in connection with the attempts to simulate the so called Dynamical Casimir Effect in three-dimensional electromagnetic cavities, containing a thin semiconductor slab, periodically illuminated by strong laser pulses. Therefore it is assumed that functions $\\sigma(t)$ and $\\delta\\varepsilon(t)=\\varepsilon(t)-\\varepsilon(0)$ are different from zero during short time intervals (pulses) only. The main goal is to find the conditions, under which the initial nonzero classical field could be amplified after a single pulse (or a series of pulses). Approximate solutions to the dynamical equations are obtained in the cases of "small" and "big" maximal values of the function...
Energy Technology Data Exchange (ETDEWEB)
Wopperer, P. [CNRS, LPT (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Université de Toulouse, UPS, Laboratoire de Physique Théorique (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Dinh, P.M., E-mail: dinh@irsamc.ups-tlse.fr [CNRS, LPT (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Université de Toulouse, UPS, Laboratoire de Physique Théorique (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Reinhard, P.-G. [Institut für Theoretische Physik, Universität Erlangen, Staudtstrasse 7, D-91058 Erlangen (Germany); Suraud, E. [CNRS, LPT (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Université de Toulouse, UPS, Laboratoire de Physique Théorique (IRSAMC), 118 route de Narbonne, F-31062 Toulouse Cédex (France); Physics Department, University at Buffalo, The State University New York, Buffalo, NY 14260 (United States)
2015-02-28
There are various ways to analyze the dynamical response of clusters and molecules to electromagnetic perturbations. Particularly rich information can be obtained from measuring the properties of electrons emitted in the course of the excitation dynamics. Such an analysis of electron signals covers observables such as total ionization, Photo-Electron Spectra (PES), Photoelectron Angular Distributions (PAD), and ideally combined PES/PAD. It has a long history in molecular physics and was increasingly used in cluster physics as well. Recent progress in the design of new light sources (high intensity, high frequency, ultra short pulses) opens new possibilities for measurements and thus has renewed the interest on these observables, especially for the analysis of various dynamical scenarios, well beyond a simple access to electronic density of states. This, in turn, has motivated many theoretical investigations of the dynamics of electronic emission for molecules and clusters up to such a complex and interesting system as C{sub 60}. A theoretical tool of choice is here Time-Dependent Density Functional Theory (TDDFT) propagated in real time and on a spatial grid, and augmented by a Self-Interaction Correction (SIC). This provides a pertinent, robust, and efficient description of electronic emission including the detailed pattern of PES and PAD. A direct comparison between experiments and well founded elaborate microscopic theories is thus readily possible, at variance with more demanding observables such as for example fragmentation or dissociation cross sections. The purpose of this paper is to describe the theoretical tools developed on the basis of real-time and real-space TDDFT and to address in a realistic manner the analysis of electronic emission following irradiation of clusters and molecules by various laser pulses. After a general introduction, we shall present in a second part the available experimental results motivating such studies, starting from the
Wopperer, P.; Dinh, P. M.; Reinhard, P.-G.; Suraud, E.
2015-02-01
There are various ways to analyze the dynamical response of clusters and molecules to electromagnetic perturbations. Particularly rich information can be obtained from measuring the properties of electrons emitted in the course of the excitation dynamics. Such an analysis of electron signals covers observables such as total ionization, Photo-Electron Spectra (PES), Photoelectron Angular Distributions (PAD), and ideally combined PES/PAD. It has a long history in molecular physics and was increasingly used in cluster physics as well. Recent progress in the design of new light sources (high intensity, high frequency, ultra short pulses) opens new possibilities for measurements and thus has renewed the interest on these observables, especially for the analysis of various dynamical scenarios, well beyond a simple access to electronic density of states. This, in turn, has motivated many theoretical investigations of the dynamics of electronic emission for molecules and clusters up to such a complex and interesting system as C60. A theoretical tool of choice is here Time-Dependent Density Functional Theory (TDDFT) propagated in real time and on a spatial grid, and augmented by a Self-Interaction Correction (SIC). This provides a pertinent, robust, and efficient description of electronic emission including the detailed pattern of PES and PAD. A direct comparison between experiments and well founded elaborate microscopic theories is thus readily possible, at variance with more demanding observables such as for example fragmentation or dissociation cross sections. The purpose of this paper is to describe the theoretical tools developed on the basis of real-time and real-space TDDFT and to address in a realistic manner the analysis of electronic emission following irradiation of clusters and molecules by various laser pulses. After a general introduction, we shall present in a second part the available experimental results motivating such studies, starting from the simplest
Vignale, Giovanni
2011-01-01
In a paper recently published in Phys. Rev. A [arXiv:1010.4223], Schirmer has criticized an earlier work of mine [arXiv:0803.2727], as well as the foundations of time-dependent density functional theory. In Ref.[2], I showed that the so-called "causality paradox" - i.e., the failure of the exchange-correlation potential derived from the Runge-Gross time-dependent variational principle to satisfy causality requirements - can be solved by a careful reformulation of that variational principle. F...
Rüger, Robert; Heine, Thomas; Visscher, Lucas
2016-01-01
We propose a new method of calculating electronically excited states that combines a density functional theory (DFT) based ground state calculation with a linear response treatment that employs approximations used in the time-dependent density functional based tight binding (TD-DFTB) approach. The new method termed TD-DFT+TB does not rely on the DFTB parametrization and is therefore applicable to systems involving all combinations of elements. We show that the new method yields UV/Vis absorption spectra that are in excellent agreement with computationally much more expensive time-dependent density functional theory (TD-DFT) calculations. Errors in vertical excitation energies are reduced by a factor of two compared to TD-DFTB.
Pétri, J
2014-01-01
Pulsars are believed to loose their rotational kinetic energy primarily by a large amplitude low frequency electromagnetic wave which is eventually converted into particle creation, acceleration and followed by a broad band radiation spectrum. To date, there exist no detailed calculation of the exact spin-down luminosity with respect to the neutron star magnetic moment and spin frequency, including general-relativistic effects. Estimates are usually given according to the flat spacetime magnetodipole formula. The present paper pursue our effort to look for accurate solutions of the general-relativistic electromagnetic field around a slowly rotating magnetized neutron star. In a previous work, we already found approximate stationary solutions to this problem. Here we address again this problem but using a more general approach. We indeed solve the full set of time-dependent Maxwell equations in a curved vacuum space-time following the 3+1 formalism. The numerical code is based on our pseudo-spectral method exp...
Krause, Pascal; Schlegel, H. Bernhard
2014-11-01
The strong field ionization rates for ethylene, trans 1,3-butadiene, and trans,trans 1,3,5-hexatriene have been calculated using time-dependent configuration interaction with single excitations and a complex absorbing potential (TDCIS-CAP). The calculations used the aug-cc-pVTZ basis set with a large set of diffuse functions (3 s, 2 p, 3 d, and 1 f) on each atom. The absorbing boundary was placed 3.5 times the van der Waals radius from each atom. The simulations employed a seven-cycle cosine squared pulse with a wavelength of 800 nm. Ionization rates were calculated for intensities ranging from 0.3 × 1014 W/cm2 to 3.5 × 1014 W/cm2. Ionization rates along the molecular axis increased markedly with increasing conjugation length. By contrast, ionization rates perpendicular to the molecular axis were almost independent of the conjugation length.
Response of a quantum system to a time-dependent external field and dynamical symmetry of the system
Wang, S J; Weiguny, A; Wiese, H
1998-01-01
The response of a quantum system to a time-dependent periodic external field is investigated in connection with the dynamical symmetry breaking and level dynamics of the adiabatic states of the system. The main results are as follows. (A) When the periodic external field preserves the dynamical symmetry of the system, its response is like that of elastic matter. (B) When the periodic external field breaks the dynamical symmetry, several cases may occur: (a) in the adiabatic limit, the system still responds elastically; (b) if the initial state is an eigenstate of the evolution operator U(T) for one period T of the external field, the system evolves in time cyclically and responds quasi-elastically; (c) if the initial state is not an eigenstate of the evolution operator U(T), the system evolves in time non-cyclically and responds non-elastically. The detailed non-elastic behaviour depends on the statistical nature of the adiabatic eigenstates of the system. If the adiabatic spectrum is chaotic, the non-elastic...
Chen, Wenjun; Ma, Hong; Yu, De; Zhang, Hua
2016-03-04
A nuclear magnetic resonance (NMR) experiment for measurement of time-dependent magnetic fields was introduced. To improve the signal-to-interference-plus-noise ratio (SINR) of NMR data, a new method for interference cancellation and noise reduction (ICNR) based on singular value decomposition (SVD) was proposed. The singular values corresponding to the radio frequency interference (RFI) signal were identified in terms of the correlation between the FID data and the reference data, and then the RFI and noise were suppressed by setting the corresponding singular values to zero. The validity of the algorithm was verified by processing the measured NMR data. The results indicated that, this method has a significantly suppression of RFI and random noise, and can well preserve the FID signal. At present, the major limitation of the proposed SVD-based ICNR technique is that the threshold value for interference cancellation needs to be manually selected. Finally, the inversion waveform of the applied alternating magnetic field was given by fitting the processed experimental data.
DEFF Research Database (Denmark)
Norman, Patrick; Bishop, David M.; Jensen, Hans Jørgen Aa;
2001-01-01
Computationally tractable expressions for the evaluation of the linear response function in the multiconfigurational self-consistent field approximation were derived and implemented. The finite lifetime of the electronically excited states was considered and the linear response function was shown...
DEFF Research Database (Denmark)
Yan, Jun; Jacobsen, Karsten W.; Thygesen, Kristian S.
2012-01-01
First-principles calculations of the conventional and acoustic surface plasmons (CSPs and ASPs) on the (111) surfaces of Cu, Ag, and Au are presented. The effect of s-d interband transitions on both types of plasmons is investigated by comparing results from the local density approximation...
Structures of the mycotoxin zearalenone and its analogs were investigated using density functional theory methods to gain insight into the ground state and excited state properties related to detection. Zearalenone is an estrogenic mycotoxin that can occur in agricultural commodities, and ultraviole...
Johnson, C. W.; Totten, E. J.; Burgmann, R.
2015-12-01
To improve understanding of the link between injection/production activity and seismicity, we apply an Epidemic Type Aftershock Sequence (ETAS) model to an earthquake catalog from The Geysers geothermal field (GGF) between 2005-2015 using >140,000 events and Mc 0.8 . We partition the catalog along a northeast-southwest trending divide, which corresponds to regions of high and low levels of enhanced geothermal stimulation (EGS) across the field. The ETAS model is fit to the seismicity data using a 6-month sliding window with a 1-month time step to determine the background seismicity rate. We generate monthly time series of the time-dependent background seismicity rate in 1-km depth intervals from 0-5km. The average wellhead depth is 2-3 km and the background seismicity rates above this depth do not correlate well with field-wide injected masses over the time period of interest. The auto correlation results show a 12-month period for monthly time series proximal to the average wellhead depths (2-3km and 3-4km) for northwest GGF strongly correlates with field-wide fluid injection masses, with a four-month phase shift between the two depth intervals as fluid migrates deeper. This periodicity is not observed for the deeper depth interval of 4-5 km, where monthly background seismicity rates reduce to near zero. Cross-correlation analysis using the monthly time series for background seismicity rate and the field-wide injection, production and net injection (injection minus production) suggest that injection most directly modulates seismicity. Periodicity in the background seismicity is not observed as strongly in the time series for the southeast field. We suggest that the variation in background seismicity rate is a proxy for pore-pressure diffusion of injected fluids at depth. We deduce that the contrast between the background seismicity rates in the northwest and southeast GGF is a result of reduced EGS activity in the southeast region.
Mapping axonal density and average diameter using non-monotonic time-dependent gradient-echo MRI
DEFF Research Database (Denmark)
Nunes, Daniel; Cruz, Tomás L; Jespersen, Sune N
2017-01-01
Abstract White Matter (WM) microstructures, such as axonal density and average diameter, are crucial to the normal function of the Central Nervous System (CNS) as they are closely related with axonal conduction velocities. Conversely, disruptions of these microstructural features may result....... While clearly further modelling and theoretical developments are necessary, we conclude that salient WM microstructural features can be extracted from these simple, SNR-efficient multi-gradient echo MRI, and that this paves the way towards easier estimation of WM microstructure in vivo....
Energy Technology Data Exchange (ETDEWEB)
Krause, Pascal; Schlegel, H. Bernhard [Department of Chemistry, Wayne State University, Detroit, Michigan 48202-3489 (United States)
2014-11-07
The strong field ionization rates for ethylene, trans 1,3-butadiene, and trans,trans 1,3,5-hexatriene have been calculated using time-dependent configuration interaction with single excitations and a complex absorbing potential (TDCIS-CAP). The calculations used the aug-cc-pVTZ basis set with a large set of diffuse functions (3 s, 2 p, 3 d, and 1 f) on each atom. The absorbing boundary was placed 3.5 times the van der Waals radius from each atom. The simulations employed a seven-cycle cosine squared pulse with a wavelength of 800 nm. Ionization rates were calculated for intensities ranging from 0.3 × 10{sup 14} W/cm{sup 2} to 3.5 × 10{sup 14} W/cm{sup 2}. Ionization rates along the molecular axis increased markedly with increasing conjugation length. By contrast, ionization rates perpendicular to the molecular axis were almost independent of the conjugation length.
Jensen, Lasse; Govind, Niranjan
2009-09-10
In this work, we present a study of the excitation energies of adenine, cytosine, guanine, thymine, and the adenine-thymine (AT) and guanine-cytosine (GC) base pairs using long-range corrected (LC) density functional theory. We compare three recent LC functionals, BNL, CAM-B3LYP, and LC-PBE0, with B3LYP and coupled cluster results from the literature. We find that the best overall performance is for the BNL functional based on LDA. However, in order to achieve this good agreement, a smaller attenuation parameter is needed, which leads to nonoptimum performance for ground-state properties. B3LYP, on the other hand, severely underestimates the charge-transfer (CT) transitions in the base pairs. Surprisingly, we also find that the CAM-B3LYP functional also underestimates the CT excitation energy for the GC base pair but correctly describes the AT base pair. This illustrates the importance of retaining the full long-range exact exchange even at distances as short as that of the DNA base pairs. The worst overall performance is obtained with the LC-PBE0 functional, which overestimates the excitations for the individual bases as well as the base pairs. It is therefore crucial to strike a good balance between the amount of local and long-range exact exchange. Thus, this work highlights the difficulties in obtained LC functionals, which provides a good description of both ground- and excited-state properties.
Nazarov, Vladimir U
2017-06-09
We find an exact analytical solution to the exchange-only time-dependent density-functional theory (TDDFT) problem for a significant class of quasi-low-dimensional (QLD) materials: QLD electron gas with only one band filled in the direction perpendicular to the layer or wire. The theory yields the TD exchange potential as an explicit nonlocal operator of the TD spin density. The dressed interband (image states) excitation spectra of quasi-two-dimensional electron gas are obtained, while the comparison with the Kohn-Sham transitions provides insights into the qualitative and quantitative role of the many-body interactions. Important cancellations between the Hartree f_{H} and the exchange f_{x} kernels of TDDFT are found in the low-density regime, elucidating the interrelations between the Kohn-Sham and the many-body dynamics in mesoscopic systems.
Nazarov, Vladimir U.
2017-06-01
We find an exact analytical solution to the exchange-only time-dependent density-functional theory (TDDFT) problem for a significant class of quasi-low-dimensional (QLD) materials: QLD electron gas with only one band filled in the direction perpendicular to the layer or wire. The theory yields the TD exchange potential as an explicit nonlocal operator of the TD spin density. The dressed interband (image states) excitation spectra of quasi-two-dimensional electron gas are obtained, while the comparison with the Kohn-Sham transitions provides insights into the qualitative and quantitative role of the many-body interactions. Important cancellations between the Hartree fH and the exchange fx kernels of TDDFT are found in the low-density regime, elucidating the interrelations between the Kohn-Sham and the many-body dynamics in mesoscopic systems.
Eguchi, Akihiro; Neymotin, Samuel A; Stringer, Simon M
2014-01-01
Although many computational models have been proposed to explain orientation maps in primary visual cortex (V1), it is not yet known how similar clusters of color-selective neurons in macaque V1/V2 are connected and develop. In this work, we address the problem of understanding the cortical processing of color information with a possible mechanism of the development of the patchy distribution of color selectivity via computational modeling. Each color input is decomposed into a red, green, and blue representation and transmitted to the visual cortex via a simulated optic nerve in a luminance channel and red-green and blue-yellow opponent color channels. Our model of the early visual system consists of multiple topographically-arranged layers of excitatory and inhibitory neurons, with sparse intra-layer connectivity and feed-forward connectivity between layers. Layers are arranged based on anatomy of early visual pathways, and include a retina, lateral geniculate nucleus, and layered neocortex. Each neuron in the V1 output layer makes synaptic connections to neighboring neurons and receives the three types of signals in the different channels from the corresponding photoreceptor position. Synaptic weights are randomized and learned using spike-timing-dependent plasticity (STDP). After training with natural images, the neurons display heightened sensitivity to specific colors. Information-theoretic analysis reveals mutual information between particular stimuli and responses, and that the information reaches a maximum with fewer neurons in the higher layers, indicating that estimations of the input colors can be done using the output of fewer cells in the later stages of cortical processing. In addition, cells with similar color receptive fields form clusters. Analysis of spiking activity reveals increased firing synchrony between neurons when particular color inputs are presented or removed (ON-cell/OFF-cell).
Muñoz Burgos, J. M.; Barbui, T.; Schmitz, O.; Stutman, D.; Tritz, K.
2016-11-01
Helium line-ratios for electron temperature (Te) and density (ne) plasma diagnostic in the Scrape-Off-Layer (SOL) and edge regions of tokamaks are widely used. Due to their intensities and proximity of wavelengths, the singlet, 667.8 and 728.1 nm, and triplet, 706.5 nm, visible lines have been typically preferred. Time-dependency of the triplet line (706.5 nm) has been previously analyzed in detail by including transient effects on line-ratios during gas-puff diagnostic applications. In this work, several line-ratio combinations within each of the two spin systems are analyzed with the purpose of eliminating transient effects to extend the application of this powerful diagnostic to high temporal resolution characterization of plasmas. The analysis is done using synthetic emission modeling and diagnostic for low electron density NSTX SOL plasma conditions by several visible lines. Quasi-static equilibrium and time-dependent models are employed to evaluate transient effects of the atomic population levels that may affect the derived electron temperatures and densities as the helium gas-puff penetrates the plasma. The analysis of a wider range of spectral lines will help to extend this powerful diagnostic to experiments where the wavelength range of the measured spectra may be constrained either by limitations of the spectrometer or by other conflicting lines from different ions.
Kuter, David; Venter, Gerhard A; Naidoo, Kevin J; Egan, Timothy J
2012-10-01
Speciation of ferriprotoporphyrin IX, Fe(III)PPIX, in aqueous solution is complex. Despite the use of its characteristic spectroscopic features for identification, the theoretical basis of the unique UV-visible absorbance spectrum of μ-[Fe(III)PPIX](2)O has not been explored. To investigate this and to establish a structural and spectroscopic model for Fe(III)PPIX species, density functional theory (DFT) calculations were undertaken for H(2)O-Fe(III)PPIX and μ-[Fe(III)PPIX](2)O. The models agreed with related Fe(III)porphyrin crystal structures and reproduced vibrational spectra well. The UV-visible absorbance spectra of H(2)O-Fe(III)PPIX and μ-[Fe(III)PPIX](2)O were calculated using time-dependent DFT and reproduced major features of the experimental spectra of both. Transitions contributing to calculated excitations have been identified. The features of the electronic spectrum calculated for μ-[Fe(III)PPIX](2)O were attributed to delocalization of electron density between the two porphyrin rings of the dimer, the weaker ligand field of the axial ligand, and antiferromagnetic coupling of the Fe(III) centers. Room temperature magnetic circular dichroism (MCD) spectra have been recorded and are shown to be useful in distinguishing between these two Fe(III)PPIX species. Bands underlying major spectroscopic features were identified through simultaneous deconvolution of UV-visible and MCD spectra. Computed UV-visible spectra were compared to deconvoluted spectra. Interpretation of the prominent bands of H(2)O-Fe(III)PPIX largely conforms to previous literature. Owing to the weak paramagnetism of μ-[Fe(III)PPIX](2)O at room temperature and the larger number of underlying excitations, interpretation of its experimental UV-visible spectrum was necessarily tentative. Nonetheless, comparison with the calculated spectra of antiferromagnetically coupled and paramagnetic forms of the μ-oxo dimer of Fe(III)porphine suggested that the composition of the Soret band involves
DEFF Research Database (Denmark)
Martinez, Jose Ignacio; García Lastra, Juan Maria; Lopez, M. J.
2010-01-01
The optical spectra of sandwich clusters formed by transition metal atoms (titanium, vanadium, and chromium) intercalated between parallel benzene molecules have been studied by time-dependent density functional theory (TDDFT) and many-body perturbation theory. Sandwiches with different number...... the optical properties according to specific functionality targets. The differences in the spectra could be used to identify relative abundances of isomers with different spins in experimental studies. As a salient feature, this theoretical spectroscopic analysis predicts the metallization of the infinite (Ti...
Imamura, Yutaka; Kamiya, Muneaki; Nakajima, Takahito
2016-03-01
We study spin-forbidden transitions of Os polypyridyl sensitizers by two-component relativistic time-dependent density functional theory with the spin-orbit interaction based on Tamm-Dancoff approximation. The absorption spectra, including spin-forbidden-transition peaks, for the Os complexes are reasonably reproduced in comparison with the experimental ones. The extension of the conjugated lengths in the Os complexes is investigated and found to be effective to enhance photo absorption for spin-allowed transitions as well as spin-forbidden ones. This study provides fruitful information for a design of new dyes in terms of conjugation lengths.
Jun, Ye
2015-12-24
Low-lying band shapes of absorption and fluorescence spectra for a member of a newly synthesized family of phenylene-containing oligoacenes (POA 6) reported in J. Am. Chem. Soc. 2012 , 134 , 15351 are studied theoretically with two different approaches with TIPS-anthracene as a comparison. Underlying photophysics and exciton-phonon interactions in both molecules are investigated in details with the aid of the time-dependent density functional theory and multimode Brownian oscillator model. The first two low-lying excited-states of POA 6 were found to exhibit excitation characteristics spanning entire conjugated backbone despite the presence of antiaromatic phenylene section. Absorption and fluorescence spectra calculated from both time-dependent density functional theory and multimode Brownian oscillator model are shown to reach good agreement with experimental ones. The coupling between phonon modes and optical transitions is generally weak as suggested by the multimode Brownian oscillator model. Broader peaks of POA 6 spectra are found to relate to stronger coupling between low frequency phonon modes such as backbone twisting (with frequency <300 cm(-1)) and optical transitions. Furthermore, POA 6 exhibits weaker exciton-phonon coupling for the phonon modes above 1000 cm(-1) compared to TIPS-anthracene owing to extended conjugated backbone. A significant coupling between an in-plane breathing mode localized around the antiaromatic phenylene segment with frequency at 1687 cm(-1) and optical transitions for the first two excited-states of POA 6 is also observed.
Schuck, Peter; Tohyama, Mitsuru
2016-04-01
The Bogoliubov-Born-Green-Kirkwood-Yvon or time-dependent density matrix (TDDM) hierarchy of equations for higher density matrices is truncated at the three-body level in approximating the three-body correlation function by a quadratic form of two-body ones, closing the equations in this way. The procedure is discussed in detail and it is shown in nontrivial model cases that the approximate inclusion of three-body correlation functions is very important to obtain precise results. A small amplitude approximation of this time-dependent nonlinear equation for the two-body correlation function is performed (STDDM*-b) and it is shown that the one-body sector of this generalized nonlinear second random phase approximation (RPA) equation is equivalent to the self-consistent RPA (SCRPA) approach which had been derived previously by different techniques. It is discussed in which way SCRPA also contains the three-body correlations. TDDM and SCRPA are tested versus exactly solvable model cases.
Rebolini, Elisa
2015-01-01
We present a range-separated linear-response time-dependent density-functional theory (TDDFT) which combines a density-functional approximation for the short-range response kernel and a frequency-dependent second-order Bethe-Salpeter approximation for the long-range response kernel. This approach goes beyond the adiabatic approximation usually used in linear-response TDDFT and aims at improving the accuracy of calculations of electronic excitation energies of molecular systems. A detailed derivation of the frequency-dependent second-order Bethe-Salpeter correlation kernel is given using many-body Green-function theory. Preliminary tests of this range-separated TDDFT method are presented for the calculation of excitation energies of four small molecules: N2, CO2, H2CO, and C2H4. The results suggest that the addition of the long-range second-order Bethe-Salpeter correlation kernel overall slightly improves the excitation energies.
Time-Dependent Transport in Nanoscale Devices
Institute of Scientific and Technical Information of China (English)
CHEN Zhi-Dong; ZHANG Jin-Yu; YU Zhi-Ping
2009-01-01
A method for simulating ballistic time-dependent device transport,which solves the time-dependent SchrSdinger equation using the finite difference time domain (FDTD) method together with Poisson's equation,is described in detail The effective mass SchrSdinger equation is solved. The continuous energy spectrum of the system is discretized using adaptive mesh,resulting in energy levels that sample the density-of-states.By calculating time evolution of wavefunctions at sampled energies,time-dependent transport characteristics such as current and charge density distributions are obtained.Simulation results in a uanowire and a coaxially gated carbon nanotube field-effect transistor (CNTFET) are presented.Transient effects,e.g.,finite rising time,are investigated in these devices.
Energy Technology Data Exchange (ETDEWEB)
Govind, Niranjan; De Jong, Wibe A.
2014-02-21
We report simulations of the X-ray absorption near edge structure (XANES) at the Cl K-edge of actinide hexahalides MCl62- (M = U, Np, Pu) and the UOCl5- complex using linear-response time-dependent density functional theory (LR-TDDFT) extended for core excitations. To the best of our knowledge, these are the first calculations of the Cl K-edge spectra of NpCl62- and PuCl62-. In addition, the spectra are simulated with and without the environmental effects of the host crystal as well as ab initio molecular dynamics (AIMD) to capture the dynamical effects due to atomic motion. The calculated spectra are compared with experimental results, where available and the observed trends are discussed.
Energy Technology Data Exchange (ETDEWEB)
Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan
2015-11-09
Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a power- ful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with con- ventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We con- sider seven low- and high-spin model complexes involving chromium, manganese and iron transition metal centers. Our results are in good agreement with experiment.
Energy Technology Data Exchange (ETDEWEB)
Lee, Sang Uck [Univ. of Ulsan, Ulsan (Korea, Republic of)
2013-08-15
The accurate prediction of vertical excitation energies is very important for the development of new materials in the dye and pigment industry. A time-dependent density functional theory (TD-DFT) approach coupled with 22 different exchange-correlation functionals was used for the prediction of vertical excitation energies in the halogenated copper phthalocyanine molecules in order to find the most appropriate functional and to determine the accuracy of the prediction of the absorption wavelength and observed spectral shifts. Among the tested functional, B3LYP functional provides much more accurate vertical excitation energies and UV-vis spectra. Our results clearly provide a benchmark calibration of the TD-DFT method for phthalocyanine based dyes and pigments used in industry.
Tsuchimochi, Takashi; Kobayashi, Masato; Nakata, Ayako; Imamura, Yutaka; Nakai, Hiromi
2008-11-15
The Sakurai-Sugiura projection (SS) method was implemented and numerically assessed for diagonalization of the Hamiltonian in time-dependent density functional theory (TDDFT). Since the SS method can be used to specify the range in which the eigenvalues are computed, it may be an efficient tool for use with eigenvalues in a particular range. In this article, the SS method is applied to core excited calculations for which the eigenvalues are located within a particular range, since the eigenvalues are unique to atomic species in molecules. The numerical assessment of formaldehyde molecule by TDDFT with core-valence Becke's three-parameter exchange (B3) plus Lee-Yang-Parr (LYP) correlation (CV-B3LYP) functional demonstrates that the SS method can be used to selectively obtain highly accurate eigenvalues and eigenvectors. Thus, the SS method is a new and powerful alternative for calculating core-excitation energies without high computation costs.
Mennucci, Benedetta; Cappelli, Chiara; Guido, Ciro Achille; Cammi, Roberto; Tomasi, Jacopo
2009-04-02
This paper provides an overview of recent research activities concerning the quantum-mechanical description of structures and properties of electronically excited chromophores in solution. The focus of the paper is on a specific approach to include solvent effects, namely the polarizable continuum model (PCM). Such a method represents an efficient strategy if coupled to proper quantum-mechanical descriptions such as the time-dependent density functional theory (TDDFT). As a result, the description of molecules in the condensed phase can be extended to excited states still maintaining the computational efficiency and the physical reliability of the ground-state calculations. The most important theoretical and computational aspects of the coupling between PCM and TDDFT are presented and discussed together with an example of application to the study of the low-lying electronic excited states of push-pull chromophores in different solvents.
Energy Technology Data Exchange (ETDEWEB)
Carrasquilla, Rafael J; Neira, Oscar L, E-mail: rjcarrasquilla@yahoo.com [Grupo de Espectroscopia Optica y Laser, Universidad Popular del Cesar, Valledupar (Colombia)
2011-01-01
Time dependent density functional (TD-DFT) calculations were performed on 1,3-benzoxazole and substituted benzoxazoles using the B3LYP functional and the 6-31+G(d) basis sets. The geometry of the S{sub 0} and S{sub 1} singlet ground and excited states were optimized in gas phase, toluene and methanol using B3LYP/6-31+G(d) y CIS/6-31+G(d) methods, respectively, and the vertical {pi} {yields} {pi}{sup *} absorption largest wavelength transitions were determined. Several global molecular descriptors were considered such as the hardness, chemical potential, electronegativity and the dipole moment for each molecule and was determined the influence that has, about the values of these descriptors, the alteration of the main molecular chain of an initial structure (1,3 not substituted Benzoxazole). Generally, the predicted spectra are in agreement with the experimental data.
Kanno, Shohei; Imamura, Yutaka; Hada, Masahiko
2016-05-25
We explore spin-forbidden transitions for a Ru dye with an N3 skeleton and an Fe dye with a DX1 skeleton by time-dependent density functional theory with spin-orbit interaction. The modified N3-based Ru dye with iodine anions has an absorption edge in the long wavelength region which is not observed in the original N3 dye. The long wavelength absorption edge originates from the spin-orbit interaction with iodine. Although the Fe dye has a small spin-orbit interaction, because of less spin-orbit interaction from the light metal, spin-forbidden transitions also occur for DX1-based Fe dye systems with iodine anions. This result indicates that the introduction of iodine can strengthen the spin-orbit interaction for a dye sensitizer and offers a new approach for designing spin-forbidden transitions.
Petit, Laurence; Maldivi, Pascale; Adamo, Carlo
2005-09-01
The calculation of the absorption spectra of four families of transition-metal complexes (Ni(CO)4, MnO4(-), MF6 (M = Cr, Mo, W) and CpM(CO)2 (M = Rh, Ir)) has been undertaken to unravel the influence of basis sets onto excitation energies, oscillator strengths, and assignments. Three among the most common pseudopotentials, with the corresponding valence basis sets, and two all-electron basis sets have been used for the metal center description in the framework of the time dependent Density Functional Theory (TD-DFT). Our results show that this approach does not particularly depend on the basis set used on the metal atoms. Furthermore, the chosen functional PBE0 provides transitions in good agreement with experiments, and it provides an accuracy of about 0.3 eV, comparable to that of refined post-Hartree-Fock methods.
Zhang, Yahong; Duan, Yuping; Liu, Jin
2017-01-01
A theoretical study was carried out to study the excited-state of hydrogen-bonding characteristics of polyaniline (PANI) in aqueous environment. The hydrogen-bonded PANI-H2O complexes were studied using first-principles calculations based on density functional theory (DFT). The electronic excitation energies and the corresponding oscillator strengths of the low-lying electronically excited states for hydrogen-bonded complexes were calculated by time-dependent density functional theory (TDDFT). The ground-state geometric structures were optimized, and it is observed that the intermolecular hydrogen bonds Csbnd N ⋯ Hsbnd O and Nsbnd H ⋯ Osbnd H were formed in PANI-H2O complexes. The formed hydrogen bonds influenced the bond lengths, the charge distribution, as well as the spectral characters of the groups involved. It was concluded that all the hydrogen-bonded PANI-H2O complexes were primarily excited to the S1 states with the largest oscillator strength. In addition, the orbital transition from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) involved intramolecular charge redistribution resulting to increase the electron density of the quinonoid rings.
Energy Technology Data Exchange (ETDEWEB)
Menouar, Salah; Maamache, Mustapha [Laboratoire de Physique Quantique et Systemes Dynamiques, Departement de Physique, Faculte des Sciences, Universite Ferhat Abbas de Setif, Setif 19000 (Algeria); Choi, Jeong Ryeol, E-mail: menouar_salah@yahoo.f, E-mail: choiardor@hanmail.ne [Department of Radiologic Technology, Daegu Health College, Taejeon 1-dong, Buk-gu, Daegu 702-722 (Korea, Republic of)
2010-12-15
The dynamics of the time-dependent coupled oscillator model for the motion of a charged particle subjected to a time-dependent external magnetic field is investigated. We use the canonical transformation approach for the classical treatment of the system, whereas the unitary transformation approach is used in managing the system in the framework of quantum mechanics. For both approaches, the original system is transformed into a much more simple system that is the sum of two independent harmonic oscillators with time-dependent frequencies. We therefore easily identify the wavefunctions in the transformed system with the help of an invariant operator of the system. The full wavefunctions in the original system are derived from the inverse unitary transformation of the wavefunctions associated with the transformed system.
Numerical analysis and field study of time dependent exergy-energy of a gas-steam combined cycle
Directory of Open Access Journals (Sweden)
Barari Bamdad
2012-01-01
Full Text Available In this study, time dependent exergy analysis of the Fars Combined Power Plant Cycle has been investigated. Exergy analysis has been used for investigating each part of actual combined cycle by considering irreversibility from Apr 2006 to Oct 2010. Performance analysis has been done for each part by evaluating exergy destruction in each month. By using of exergy analysis, aging of each part has been evaluated respect to time duration. In addition, the rate of lost work for each month has been calculated and variation of this parameter has been considered as a function of aging rate. Finally, effects of exergy destruction of each part have been investigated on exergy destruction of whole cycle. Entire analysis has been done for Unit 3 and 4 of gas turbine cycle which combined by Unit B of steam cycle in Fars Combined Power Plant Cycle located in Fars province in Iran.
Energy Technology Data Exchange (ETDEWEB)
Silverstein, Daniel W.; Govind, Niranjan; van Dam, Hubertus J. J.; Jensen, Lasse
2013-12-10
A parallel implementation of analytical time-dependent density functional theory gradients is presented for the quantum chemistry program NWChem. The implementation is based on the Lagrangian approach developed by Furche and Ahlrichs. To validate our implementation, we first calculate the Stokes shifts for a range of organic dye molecules using a diverse set of exchange-correlation functionals (traditional density functionals, global hybrids, and range-separated hybrids) followed by simulations of the one-photon absorption and resonance Raman scattering spectrum of the phenoxyl radical, the well-studied dye molecule rhodamine 6G, and a molecular host–guest complex (TTFcCBPQT^{4+}). The study of organic dye molecules illustrates that B3LYP and CAM-B3LYP generally give the best agreement with experimentally determined Stokes shifts unless the excited state is a charge transfer state. Absorption, resonance Raman, and fluorescence simulations for the phenoxyl radical indicate that explicit solvation may be required for accurate characterization. For the host–guest complex and rhodamine 6G, it is demonstrated that absorption spectra can be simulated in good agreement with experimental data for most exchange-correlation functionals. Finally, however, because one-photon absorption spectra generally lack well-resolved vibrational features, resonance Raman simulations are necessary to evaluate the accuracy of the exchange-correlation functional for describing a potential energy surface.
Xie, Hang; Jiang, Feng; Tian, Heng; Zheng, Xiao; Kwok, Yanho; Chen, Shuguang; Yam, ChiYung; Yan, YiJing; Chen, Guanhua
2012-07-28
Basing on our hierarchical equations of motion for time-dependent quantum transport [X. Zheng, G. H. Chen, Y. Mo, S. K. Koo, H. Tian, C. Y. Yam, and Y. J. Yan, J. Chem. Phys. 133, 114101 (2010)], we develop an efficient and accurate numerical algorithm to solve the Liouville-von-Neumann equation. We solve the real-time evolution of the reduced single-electron density matrix at the tight-binding level. Calculations are carried out to simulate the transient current through a linear chain of atoms, with each represented by a single orbital. The self-energy matrix is expanded in terms of multiple Lorentzian functions, and the Fermi distribution function is evaluated via the Padè spectrum decomposition. This Lorentzian-Padè decomposition scheme is employed to simulate the transient current. With sufficient Lorentzian functions used to fit the self-energy matrices, we show that the lead spectral function and the dynamics response can be treated accurately. Compared to the conventional master equation approaches, our method is much more efficient as the computational time scales cubically with the system size and linearly with the simulation time. As a result, the simulations of the transient currents through systems containing up to one hundred of atoms have been carried out. As density functional theory is also an effective one-particle theory, the Lorentzian-Padè decomposition scheme developed here can be generalized for first-principles simulation of realistic systems.
Institute of Scientific and Technical Information of China (English)
WANG Han-Lu; WANG Xue-Ye; WANG Ling; WANG Heng-Liang; LIU Ai-Hong
2007-01-01
Electronic properties, such as HOMO and LUMO energies, band gaps, ionization potential (IP) and electron affinity (EA) of 2,7- and 3,6-linked carbazole trimers, two conjugated oligomers with different linkages of carbazole, were studied by the density functional theory with Becke-Lee-Young-Parr composite exchange correlation functional (B3LYP). The absorption spectra of these compounds were also investigated by time-dependent density functional theory (TD-DFT) with 6-31G* basis set. The calculated results indicated that the HOMO and LUMO of the 2,7- and 3,6-linked carbazole trimers are both slightly destabilized on going from methyl substitution to sec-butyl substitution. Both IP and EA exhibit their good hole-transporting but poor electron-accepting ability. The presence of alkyl groups on the nitrogen atoms does not affect the intra-chain electronic delocalization along the molecular frame. Thus no significant effect on the band gap and absorption spectra of compounds has been found.
Sato, Shunsuke A.; Taniguchi, Yasutaka; Shinohara, Yasushi; Yabana, Kazuhiro
2015-12-01
We develop methods to calculate electron dynamics in crystalline solids in real-time time-dependent density functional theory employing exchange-correlation potentials which reproduce band gap energies of dielectrics; a meta-generalized gradient approximation was proposed by Tran and Blaha [Phys. Rev. Lett. 102, 226401 (2009)] (TBm-BJ) and a hybrid functional was proposed by Heyd, Scuseria, and Ernzerhof [J. Chem. Phys. 118, 8207 (2003)] (HSE). In time evolution calculations employing the TB-mBJ potential, we have found it necessary to adopt the predictor-corrector step for a stable time evolution. We have developed a method to evaluate electronic excitation energy without referring to the energy functional which is unknown for the TB-mBJ potential. For the HSE functional, we have developed a method for the operation of the Fock-like term in Fourier space to facilitate efficient use of massive parallel computers equipped with graphic processing units. We compare electronic excitations in silicon and germanium induced by femtosecond laser pulses using the TB-mBJ, HSE, and a simple local density approximation (LDA). At low laser intensities, electronic excitations are found to be sensitive to the band gap energy: they are close to each other using TB-mBJ and HSE and are much smaller in LDA. At high laser intensities close to the damage threshold, electronic excitation energies do not differ much among the three cases.
Energy Technology Data Exchange (ETDEWEB)
Sato, Shunsuke A. [Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571 (Japan); Taniguchi, Yasutaka [Center for Computational Science, University of Tsukuba, Tsukuba 305-8571 (Japan); Department of Medical and General Sciences, Nihon Institute of Medical Science, 1276 Shimogawara, Moroyama-Machi, Iruma-Gun, Saitama 350-0435 (Japan); Shinohara, Yasushi [Max Planck Institute of Microstructure Physics, 06120 Halle (Germany); Yabana, Kazuhiro [Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571 (Japan); Center for Computational Science, University of Tsukuba, Tsukuba 305-8571 (Japan)
2015-12-14
We develop methods to calculate electron dynamics in crystalline solids in real-time time-dependent density functional theory employing exchange-correlation potentials which reproduce band gap energies of dielectrics; a meta-generalized gradient approximation was proposed by Tran and Blaha [Phys. Rev. Lett. 102, 226401 (2009)] (TBm-BJ) and a hybrid functional was proposed by Heyd, Scuseria, and Ernzerhof [J. Chem. Phys. 118, 8207 (2003)] (HSE). In time evolution calculations employing the TB-mBJ potential, we have found it necessary to adopt the predictor-corrector step for a stable time evolution. We have developed a method to evaluate electronic excitation energy without referring to the energy functional which is unknown for the TB-mBJ potential. For the HSE functional, we have developed a method for the operation of the Fock-like term in Fourier space to facilitate efficient use of massive parallel computers equipped with graphic processing units. We compare electronic excitations in silicon and germanium induced by femtosecond laser pulses using the TB-mBJ, HSE, and a simple local density approximation (LDA). At low laser intensities, electronic excitations are found to be sensitive to the band gap energy: they are close to each other using TB-mBJ and HSE and are much smaller in LDA. At high laser intensities close to the damage threshold, electronic excitation energies do not differ much among the three cases.
Institute of Scientific and Technical Information of China (English)
LIU Dan-Dan; ZHANG Hong
2010-01-01
@@ The photoabsorption spectra of (SiO2)n (n= 2-5) clusters[including isomers (D3h,D2d) structures of (SiO2)3 and (C2v,D2h,D4h ) structures of (SiO2)4]are calculated by using time-dependent density-function theory.The equilibrium geometries,the binding energy,the gap between the highest occupied and lowest unoccupied molecular orbitals and vertical ionization potential for corresponding structures are computed using several methods with different types of the basis functions.It is found that the polarizability functions are necessary for the basis functions when optimize the structures of silicon oxide clusters.For different geometries of various clusters and the related isomers,their spectra are very different.Meanwhile,the comparison between using local-density generalized-gradient approximations for exchange-correlation potentials shows that both the calculated spectra present the same spectral feature.We suggest that the calculated photoabsorption spectra could be taken as a tool to elucidate the isomers and clusters structure.
Neugebauer, Johannes; Gritsenko, Oleg; Baerends, Evert Jan
2006-06-01
The failure of the time-dependent density-functional theory to describe long-range charge-transfer (CT) excitations correctly is a serious problem for calculations of electronic transitions in large systems, especially if they are composed of several weakly interacting units. The problem is particularly severe for molecules in solution, either modeled by periodic boundary calculations with large box sizes or by cluster calculations employing extended solvent shells. In the present study we describe the implementation and assessment of a simple physically motivated correction to the exchange-correlation kernel suggested in a previous study [O. Gritsenko and E. J. Baerends J. Chem. Phys. 121, 655 (2004)]. It introduces the required divergence in the kernel when the transition density goes to zero due to a large spatial distance between the "electron" (in the virtual orbital) and the "hole" (in the occupied orbital). A major benefit arises for solvated molecules, for which many CT excitations occur from solvent to solute or vice versa. In these cases, the correction of the exchange-correlation kernel can be used to automatically "clean up" the spectrum and significantly reduce the computational effort to determine low-lying transitions of the solute. This correction uses a phenomenological parameter, which is needed to identify a CT excitation in terms of the orbital density overlap of the occupied and virtual orbitals involved. Another quantity needed in this approach is the magnitude of the correction in the asymptotic limit. Although this can, in principle, be calculated rigorously for a given CT transition, we assess a simple approximation to it that can automatically be applied to a number of low-energy CT excitations without additional computational effort. We show that the method is robust and correctly shifts long-range CT excitations, while other excitations remain unaffected. We discuss problems arising from a strong delocalization of orbitals, which leads
Neugebauer, Johannes; Gritsenko, Oleg; Baerends, Evert Jan
2006-06-07
The failure of the time-dependent density-functional theory to describe long-range charge-transfer (CT) excitations correctly is a serious problem for calculations of electronic transitions in large systems, especially if they are composed of several weakly interacting units. The problem is particularly severe for molecules in solution, either modeled by periodic boundary calculations with large box sizes or by cluster calculations employing extended solvent shells. In the present study we describe the implementation and assessment of a simple physically motivated correction to the exchange-correlation kernel suggested in a previous study [O. Gritsenko and E. J. Baerends J. Chem. Phys. 121, 655 (2004)]. It introduces the required divergence in the kernel when the transition density goes to zero due to a large spatial distance between the "electron" (in the virtual orbital) and the "hole" (in the occupied orbital). A major benefit arises for solvated molecules, for which many CT excitations occur from solvent to solute or vice versa. In these cases, the correction of the exchange-correlation kernel can be used to automatically "clean up" the spectrum and significantly reduce the computational effort to determine low-lying transitions of the solute. This correction uses a phenomenological parameter, which is needed to identify a CT excitation in terms of the orbital density overlap of the occupied and virtual orbitals involved. Another quantity needed in this approach is the magnitude of the correction in the asymptotic limit. Although this can, in principle, be calculated rigorously for a given CT transition, we assess a simple approximation to it that can automatically be applied to a number of low-energy CT excitations without additional computational effort. We show that the method is robust and correctly shifts long-range CT excitations, while other excitations remain unaffected. We discuss problems arising from a strong delocalization of orbitals, which leads
Energy Technology Data Exchange (ETDEWEB)
Javier Ortensi; Abderrafi M Ougouag
2009-07-01
The Doppler feedback mechanism is a major contributor to the passive safety of gas-cooled, graphite-moderated high temperature reactors that use fuel based on Tristructural-Isotropic coated particles. It follows that the correct prediction of the magnitude and time-dependence of this feedback effect is essential to the conduct of safety analyses for these reactors. We present a fuel conduction model for obtaining better estimates of the temperature feedback during moderate and fast transients. The fuel model has been incorporated in the CYNOD-THERMIX-KONVEK suite of coupled codes as a single TRISO particle within each calculation cell. The heat generation rate is scaled down from the neutronic solution and a Dirichlet boundary condition is imposed as the bulk graphite temperature from the thermal-hydraulic solution. This simplified approach yields similar results to those obtained with more complex methods, requiring multi-TRISO calculations within one control volume, but with much less computational effort. We provide an analysis of the hypothetical total control ejection event in the PBMR-400 design that clearly depicts the improvement in the predictions of the fuel temperature.
Cao, Yixiang; Hughes, Thomas; Giesen, Dave; Halls, Mathew D; Goldberg, Alexander; Vadicherla, Tati Reddy; Sastry, Madhavi; Patel, Bhargav; Sherman, Woody; Weisman, Andrew L; Friesner, Richard A
2016-06-15
We have developed and implemented pseudospectral time-dependent density-functional theory (TDDFT) in the quantum mechanics package Jaguar to calculate restricted singlet and restricted triplet, as well as unrestricted excitation energies with either full linear response (FLR) or the Tamm-Dancoff approximation (TDA) with the pseudospectral length scales, pseudospectral atomic corrections, and pseudospectral multigrid strategy included in the implementations to improve the chemical accuracy and to speed the pseudospectral calculations. The calculations based on pseudospectral time-dependent density-functional theory with full linear response (PS-FLR-TDDFT) and within the Tamm-Dancoff approximation (PS-TDA-TDDFT) for G2 set molecules using B3LYP/6-31G*(*) show mean and maximum absolute deviations of 0.0015 eV and 0.0081 eV, 0.0007 eV and 0.0064 eV, 0.0004 eV and 0.0022 eV for restricted singlet excitation energies, restricted triplet excitation energies, and unrestricted excitation energies, respectively; compared with the results calculated from the conventional spectral method. The application of PS-FLR-TDDFT to OLED molecules and organic dyes, as well as the comparisons for results calculated from PS-FLR-TDDFT and best estimations demonstrate that the accuracy of both PS-FLR-TDDFT and PS-TDA-TDDFT. Calculations for a set of medium-sized molecules, including Cn fullerenes and nanotubes, using the B3LYP functional and 6-31G(**) basis set show PS-TDA-TDDFT provides 19- to 34-fold speedups for Cn fullerenes with 450-1470 basis functions, 11- to 32-fold speedups for nanotubes with 660-3180 basis functions, and 9- to 16-fold speedups for organic molecules with 540-1340 basis functions compared to fully analytic calculations without sacrificing chemical accuracy. The calculations on a set of larger molecules, including the antibiotic drug Ramoplanin, the 46-residue crambin protein, fullerenes up to C540 and nanotubes up to 14×(6,6), using the B3LYP functional and 6-31G
Energy Technology Data Exchange (ETDEWEB)
Claesson, J.; Probert, T. [Lund Univ. (Sweden). Dept. of Building Physics and Mathematical Physics
1996-01-01
The temperature field in rock due to a large rectangular grid of heat releasing canisters containing nuclear waste is studied. The solution is by superposition divided into different parts. There is a global temperature field due to the large rectangular canister area, while a local field accounts for the remaining heat source problem. The global field is reduced to a single integral. The local field is also solved analytically using solutions for a finite line heat source and for an infinite grid of point sources. The local solution is reduced to three parts, each of which depends on two spatial coordinates only. The temperatures at the envelope of a canister are given by a single thermal resistance, which is given by an explicit formula. The results are illustrated by a few numerical examples dealing with the KBS-3 concept for storage of nuclear waste. 8 refs.
Liu, Yufang; Ding, Junxia; Liu, Ruiqiong; Shi, Deheng; Sun, Jinfeng
2009-12-01
The geometric structures and infrared (IR) spectra in the electronically excited state of a novel doubly hydrogen-bonded complex formed by fluorenone and alcohols, which has been observed by IR spectra in experimental study, are investigated by the time-dependent density functional theory (TDDFT) method. The geometric structures and IR spectra in both ground state and the S(1) state of this doubly hydrogen-bonded FN-2MeOH complex are calculated using the DFT and TDDFT methods, respectively. Two intermolecular hydrogen bonds are formed between FN and methanol molecules in the doubly hydrogen-bonded FN-2MeOH complex. Moreover, the formation of the second intermolecular hydrogen bond can make the first intermolecular hydrogen bond become slightly weak. Furthermore, it is confirmed that the spectral shoulder at around 1700 cm(-1) observed in the IR spectra should be assigned as the doubly hydrogen-bonded FN-2MeOH complex from our calculated results. The electronic excited-state hydrogen bonding dynamics is also studied by monitoring some vibraitonal modes related to the formation of hydrogen bonds in different electronic states. As a result, both the two intermolecular hydrogen bonds are significantly strengthened in the S(1) state of the doubly hydrogen-bonded FN-2MeOH complex. The hydrogen bond strengthening in the electronically excited state is similar to the previous study on the singly hydrogen-bonded FN-MeOH complex and play important role on the photophysics of fluorenone in solutions.
Su, Xiaoxing; Jiang, Lan; Wang, Feng; Su, Gaoshi; Qu, Liangti; Lu, Yongfeng
2017-07-01
In this study, we adopted time-dependent density functional theory to investigate the optical properties of monolayer MoS2 and the effect of intense few-cycle femtosecond laser pulses on these properties. The electron dynamics of monolayer MoS2 under few-cycle and multi-cycle laser irradiation were described. The polarization direction of the laser had a marked effect on the energy absorption and electronic excitation of monolayer MoS2 because of anisotropy. Change in the polarization direction of few-cycle pulse changed the absorbed energy by a factor over 4000. Few-cycle pulse showed a higher sensitivity to the electronic property of material than multi-cycle pulse. The modulation of the dielectric properties of the material was observed on the femtosecond time scale. The negative divergence appeared in the real part of the function at low frequencies and photoinduced blue shift occurred due to Burstein-Moss effect. The irradiation of femtosecond laser caused the dielectric response within the infrared region and introduced anisotropy to the in-plane optical properties. Laser-based engineering of optical properties through controlling transient electron dynamics expands the functionality of MoS2 and has potential applications in direction-dependent optoelectronic devices.
Kornobis, Karina; Wong, Bryan M; Lodowski, Piotr; Jaworska, Maria; Andruniów, Tadeusz; Rudd, Kenneth; Kozlowski, Pawel M; 10.1021/jp110914y
2011-01-01
Time-dependent density functional theory (TD-DFT) and correlated ab initio methods have been applied to the electronically excited states of vitamin B12 (cyanocobalamin or CNCbl). Different experimental techniques have been used to probe the excited states of CNCbl, revealing many issues that remain poorly understood from an electronic structure point of view. Due to its efficient scaling with size, TD-DFT emerges as one of the most practical tools that can be used to predict the electronic properties of these fairly complex molecules. However, the description of excited states is strongly dependent on the type of functional used in the calculations. In the present contribution, the choice of a proper functional for vitamin B12 was evaluated in terms of its agreement with both experimental results and correlated ab initio calculations. Three different functionals, i.e. B3LYP, BP86, and LC-BLYP, were tested. In addition, the effect of relative contributions of DFT and HF to the exchange-correlation functional ...
Gelabert, Ricard; Moreno, Miquel; Lluch, José M
2006-01-26
The hybrid configuration interaction singles/time dependent density functional theory approach of Dreuw and Head-Gordon [Dreuw, A.; Head-Gordon, M. J. Am. Chem. Soc. 2004, 126, 4007] has been applied to study the potential energy landscape and accessibility of the charge-transfer pipi* excited state in the dimer of 7-azaindole, which has been traditionally considered a model for DNA base pairing. It is found that the charge-transfer pipi* excited state preferentially stabilizes the product of a single proton transfer. In this situation, the crossing between this state and the photoactive electronic state of the dimer is accessible. It is found that the charge-transfer pipi* excited state has a very steep potential energy profile with respect to any single proton-transfer coordinate and, in contrast, an extremely flat potential energy profile with respect to the stretch of the single proton-transfer complex. This is predicted to bring about a pair of rare fragments of the 7-azaindole dimer, physically separated and hence having very long lifetimes. This could have implications in the DNA base pairs of which the system is an analogue, in the form of replication errors.
Guthmuller, Julien; Champagne, Benoît
2007-10-28
The absorption and resonance Raman spectra have been investigated for the first excited state of the julolidinemalononitrile push-pull chromophore in cyclohexane, dichloromethane, and acetonitrile by means of time dependent density functional theory calculations. The effect of nonlocal exchange has been considered by using three different hybrid exchange-correlation functionals containing 20%, 35%, and 50% of exact Hartree-Fock exchange. The interactions with the solvent have been described by the polarizable continuum model. The short-time approximation expression has been used to evaluate the resonance Raman intensities, while the vibronic theory of resonance Raman spectroscopy has been employed to determine both the intensities and the excitation profiles. It is shown that a consistent description of the vibronic structure of the excited state and resonance Raman spectra can be obtained provided that an adequate amount, close to 35%, of exact exchange is included in the exchange-correlation functional. The effect of increasing the polarity of the solvent is well represented by the polarizable continuum model, both for the absorption spectra and resonance Raman intensities. In particular, these simulations can reproduce the observed variations of the 1560 cm(-1) band intensity and attribute them to elongations of a CC double bond upon electronic excitation. Moreover, the short-time approximation has been found sufficient to reproduce most of the results of the more evolved vibronic theory of resonance Raman spectroscopy, which includes summations over vibrational excited states, for both the spectral signatures and their solvent dependencies.
Guido, Ciro A; Knecht, Stefan; Kongsted, Jacob; Mennucci, Benedetta
2013-05-14
We analyze potentials and limits of the Time-Dependent Density Functional Theory (TD-DFT) approach for the determination of excited-state geometries of organic molecules in gas-phase and in solution. Three very popular DFT exchange-correlation functionals, two hybrids (B3LYP and PBE0) and one long-range corrected (CAM-B3LYP), are here investigated, and the results are compared to the correlated RI-CC2 wave function approach. Solvent effects are further analyzed by means of a polarizable continuum model. A total of 15 organic chromophores (including both small molecules and larger push-pull systems) are considered as prototypes of n → π* and π → π* singlet excitations. Our analysis allows to point out specific correlations between the accuracy of the various functionals and the type of excitation and/or the type of chemical bonds involved. We find that while the best ground-state geometries are obtained with PBE0 and B3LYP, CAM-B3LYP yields the most accurate description of electronic and geometrical characteristics of excited states, both in gas-phase and in solution.
Ii, Barry Moore; Autschbach, Jochen
2013-11-12
The lowest-energy/longest-wavelength electronic singlet excitation energies of linear cyanine dyes are examined, using time-dependent density functional theory (TDDFT) and selected wave function methods in comparison with literature data. Variations of the bond-length alternation obtained with different optimized structures produce small differences of the excitation energy in the limit of an infinite chain. Hybrid functionals with range-separated exchange are optimally 'tuned', which is shown to minimize the delocalization error (DE) in the cyanine π systems. Much unlike the case of charge-transfer excitations, small DEs are not strongly correlated with better performance. A representative cyanine is analyzed in detail. Compared with accurate benchmark data, TDDFT with 'pure' local functionals gives too high singlet excitation energies for all systems, but DFT-based ΔSCF calculations with a local functional severely underestimates the energies. TDDFT strongly overestimates the difference between singlet and triplet excitation energies. An analysis points to systematically much too small magnitudes of integrals from the DFT components of the exchange-correlation response kernel as the likely culprit. The findings support previous suggestions that the differential correlation energy between the ground and excited state is not correctly produced by TDDFT with most functionals.
Nakata, Ayako; Tsuneda, Takao; Hirao, Kimihiko
2011-12-14
A long-range corrected (LC) time-dependent density functional theory (TDDFT) incorporating relativistic effects with spin-orbit couplings is presented. The relativistic effects are based on the two-component zeroth-order regular approximation Hamiltonian. Before calculating the electronic excitations, we calculated the ionization potentials (IPs) of alkaline metal, alkaline-earth metal, group 12 transition metal, and rare gas atoms as the minus orbital (spinor) energies on the basis of Koopmans' theorem. We found that both long-range exchange and spin-orbit coupling effects are required to obtain Koopmans' IPs, i.e., the orbital (spinor) energies, quantitatively in DFT calculations even for first-row transition metals and systems containing large short-range exchange effects. We then calculated the valence excitations of group 12 transition metal atoms and the Rydberg excitations of rare gas atoms using spin-orbit relativistic LC-TDDFT. We found that the long-range exchange and spin-orbit coupling effects significantly contribute to the electronic spectra of even light atoms if the atoms have low-lying excitations between orbital spinors of quite different electron distributions.
Energy Technology Data Exchange (ETDEWEB)
Zuehlsdorff, T. J., E-mail: tjz21@cam.ac.uk; Payne, M. C. [Cavendish Laboratory, J. J. Thomson Avenue, Cambridge CB3 0HE (United Kingdom); Hine, N. D. M. [Department of Physics, University of Warwick, Coventry CV4 7AL (United Kingdom); Haynes, P. D. [Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Department of Physics, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Thomas Young Centre for Theory and Simulation of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom)
2015-11-28
We present a solution of the full time-dependent density-functional theory (TDDFT) eigenvalue equation in the linear response formalism exhibiting a linear-scaling computational complexity with system size, without relying on the simplifying Tamm-Dancoff approximation (TDA). The implementation relies on representing the occupied and unoccupied subspaces with two different sets of in situ optimised localised functions, yielding a very compact and efficient representation of the transition density matrix of the excitation with the accuracy associated with a systematic basis set. The TDDFT eigenvalue equation is solved using a preconditioned conjugate gradient algorithm that is very memory-efficient. The algorithm is validated on a small test molecule and a good agreement with results obtained from standard quantum chemistry packages is found, with the preconditioner yielding a significant improvement in convergence rates. The method developed in this work is then used to reproduce experimental results of the absorption spectrum of bacteriochlorophyll in an organic solvent, where it is demonstrated that the TDA fails to reproduce the main features of the low energy spectrum, while the full TDDFT equation yields results in good qualitative agreement with experimental data. Furthermore, the need for explicitly including parts of the solvent into the TDDFT calculations is highlighted, making the treatment of large system sizes necessary that are well within reach of the capabilities of the algorithm introduced here. Finally, the linear-scaling properties of the algorithm are demonstrated by computing the lowest excitation energy of bacteriochlorophyll in solution. The largest systems considered in this work are of the same order of magnitude as a variety of widely studied pigment-protein complexes, opening up the possibility of studying their properties without having to resort to any semiclassical approximations to parts of the protein environment.
Gritsenko, Oleg; Baerends, Evert Jan
2004-07-08
Time-dependent density functional theory (TDDFT) calculations of charge-transfer excitation energies omegaCT are significantly in error when the adiabatic local density approximation (ALDA) is employed for the exchange-correlation kernel fxc. We relate the error to the physical meaning of the orbital energy of the Kohn-Sham lowest unoccupied molecular orbital (LUMO). The LUMO orbital energy in Kohn-Sham DFT--in contrast to the Hartree-Fock model--approximates an excited electron, which is correct for excitations in compact molecules. In CT transitions the energy of the LUMO of the acceptor molecule should instead describe an added electron, i.e., approximate the electron affinity. To obtain a contribution that compensates for the difference, a specific divergence of fxc is required in rigorous TDDFT, and a suitable asymptotically correct form of the kernel fxc(asymp) is proposed. The importance of the asymptotic correction of fxc is demonstrated with the calculation of omegaCT(R) for the prototype diatomic system HeBe at various separations R(He-Be). The TDDFT-ALDA curve omegaCT(R) roughly resembles the benchmark ab initio curve omegaCT CISD(R) of a configuration interaction calculation with single and double excitations in the region R=1-1.5 A, where a sizable He-Be interaction exists, but exhibits the wrong behavior omegaCT(R)
Zuehlsdorff, T. J.; Hine, N. D. M.; Payne, M. C.; Haynes, P. D.
2015-11-01
We present a solution of the full time-dependent density-functional theory (TDDFT) eigenvalue equation in the linear response formalism exhibiting a linear-scaling computational complexity with system size, without relying on the simplifying Tamm-Dancoff approximation (TDA). The implementation relies on representing the occupied and unoccupied subspaces with two different sets of in situ optimised localised functions, yielding a very compact and efficient representation of the transition density matrix of the excitation with the accuracy associated with a systematic basis set. The TDDFT eigenvalue equation is solved using a preconditioned conjugate gradient algorithm that is very memory-efficient. The algorithm is validated on a small test molecule and a good agreement with results obtained from standard quantum chemistry packages is found, with the preconditioner yielding a significant improvement in convergence rates. The method developed in this work is then used to reproduce experimental results of the absorption spectrum of bacteriochlorophyll in an organic solvent, where it is demonstrated that the TDA fails to reproduce the main features of the low energy spectrum, while the full TDDFT equation yields results in good qualitative agreement with experimental data. Furthermore, the need for explicitly including parts of the solvent into the TDDFT calculations is highlighted, making the treatment of large system sizes necessary that are well within reach of the capabilities of the algorithm introduced here. Finally, the linear-scaling properties of the algorithm are demonstrated by computing the lowest excitation energy of bacteriochlorophyll in solution. The largest systems considered in this work are of the same order of magnitude as a variety of widely studied pigment-protein complexes, opening up the possibility of studying their properties without having to resort to any semiclassical approximations to parts of the protein environment.
Haxhimali, Tomorr; Belof, Jonathan; Benedict, Lorin
2015-06-01
Phase-field models have become popular in last two decades to describe a host of free-boundary problems. The strength of the method relies on implicitly describing the dynamics of surfaces and interfaces by continuous scalar field that enter in the global grand free energy functional of the system. We adapt this method in order to describe shock-induced phase transition. To this end we make use of the Multiphase Field Theory (MFT) to account for the existence of multiple phases during the transition. In this talk I will initially describe the constitutive equations that couple the dynamic of the phase field with that of the thermodynamic fields like T, P, c etc. I will then give details on developing a thermodynamically consistent phase-field interpolation function for multiple-phase system in the context of shock-induced phase-transition. At the end I will briefly comment on relating the dynamics of the interfaces in the shock/ramp compression to the Kardar-Parisi-Zhang equation. This work is performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
Time-dependent, non-monotonic response of warm convective cloud fields to changes in aerosol loading
Dagan, Guy; Koren, Ilan; Altaratz, Orit; Heiblum, Reuven H.
2017-06-01
Large eddy simulations (LESs) with bin microphysics are used here to study cloud fields' sensitivity to changes in aerosol loading and the time evolution of this response. Similarly to the known response of a single cloud, we show that the mean field properties change in a non-monotonic trend, with an optimum aerosol concentration for which the field reaches its maximal water mass or rain yield. This trend is a result of competition between processes that encourage cloud development versus those that suppress it. However, another layer of complexity is added when considering clouds' impact on the field's thermodynamic properties and how this is dependent on aerosol loading. Under polluted conditions, rain is suppressed and the non-precipitating clouds act to increase atmospheric instability. This results in warming of the lower part of the cloudy layer (in which there is net condensation) and cooling of the upper part (net evaporation). Evaporation at the upper part of the cloudy layer in the polluted simulations raises humidity at these levels and thus amplifies the development of the next generation of clouds (preconditioning effect). On the other hand, under clean conditions, the precipitating clouds drive net warming of the cloudy layer and net cooling of the sub-cloud layer due to rain evaporation. These two effects act to stabilize the atmospheric boundary layer with time (consumption of the instability). The evolution of the field's thermodynamic properties affects the cloud properties in return, as shown by the migration of the optimal aerosol concentration toward higher values.
Li, Zhendong; Liu, Wenjian
2016-06-14
Compared with closed-shell systems, open-shell systems place three additional challenges to time-dependent density functional theory (TD-DFT) for electronically excited states: (a) the spin-contamination problem is a serious issue; (b) the exchange-correlation (XC) kernel may be numerically instable; and (c) the single-determinant description of open-shell ground states readily becomes energetically instable. Confined to flip-up single excitations, the spin-contamination problem can largely be avoided by using the spin-flip TD-DFT (SF-TD-DFT) formalism, provided that a noncollinear XC kernel is employed. As for the numerical instabilities associated with such a kernel, only an ad hoc scheme has been proposed so far, viz., the ALDA0 kernel, which amounts to setting the divergent components (arising from density gradients and kinetic energy density) simply to zero. The ground-state instability problem can effectively be avoided by introducing the Tamm-Dancoff approximation (TDA) to TD-DFT. Therefore, on a general basis, the SF-TDA/ALDA0 Ansatz is so far the only promising means within the TD-DFT framework for flip-up single excitations of open-shell systems. To assess systematically the performance of SF-TDA/ALDA0, in total 61 low-lying quartet excited states of the benchmark set of 11 small radicals [J. Chem. Theory Comput. 2016, 12, 238] are investigated with various XC functionals. Taking the MRCISD+Q (multireference configuration interaction with singles and doubles plus the Davidson correction) results as benchmark, it is found that the mean absolute errors of SF-TDA/ALDA0 with the SAOP (statistical averaging of model orbital potentials), global hybrid, and range-separated hybrid functionals are in the range of 0.2-0.4 eV. This is in line not only with the typical accuracy of TD-DFT for singlet and triplet excited states of closed-shell systems but also with the gross accuracy of spin-adapted TD-DFT for spin-conserving excited states of open-shell systems.
Institute of Scientific and Technical Information of China (English)
Etienne Wamba; Timoléon C. Kofané; Alidou Mohamadou
2012-01-01
We construct,through a further extension of the tanh-function method,the matter-wave solutions of Bose-Einstein condensates (BECs) with a three-body interaction.The BECs are trapped in a potential comprising the linear magnetic and the time-dependent laser fields.The exact solutions obtained include soliton solutions,such as kink and antikink as well as bright,dark,multisolitonic modulated waves.We realize that the motion and the shape of the solitary wave can be manipulated by controlling the strengths of the fields.
Dapp, Wolf B.; Müser, Martin H.
2013-01-01
Force fields uniquely assign interatomic forces for a given set of atomic coordinates. The underlying assumption is that electrons are in their quantum-mechanical ground state or in thermal equilibrium. However, there is an abundance of cases where this is unjustified because the system is only locally in equilibrium. In particular, the fractional charges of atoms, clusters, or solids tend to not only depend on atomic positions but also on how the system reached its state. For example, the ch...
McDonald, Kirk T.
1997-11-01
The expressions of Jefimenko, which have received much recent attention in this Journal, are contained in Sec. 14.3 of the book Classical Electricity and Magnetism by Panofsky and Phillips. The latter develop these expressions further into a form that gives greater emphasis to the radiation fields. This article presents a derivation of the various expressions and discusses an apparent paradox in applying Panofsky and Phillips's result to static situations.
Kalita, Dhruba Jyoti; Gupta, Ashish K
2010-10-01
A study of the multiphoton dissociation of H(2)(+) in intense laser field using the smooth exterior scaling method to calculate resonance states is presented. This method is very attractive as it does not disturb the interaction region. The wave functions calculated with this method provide indisputable proof in support of the mechanisms of the different phenomena happening during photodissociation. Wave functions corresponding to the "vibrationally trapped" (bond-hardening) states are found. A unequivocal mechanism for "bond-softening" is provided. It is observed that with an increase in intensity, the lifetime of low vibrational level increases. The mechanism for this novel phenomenon is also explained.
Energy Technology Data Exchange (ETDEWEB)
Vatansever, Erol [Dokuz Eylül University, Graduate School of Natural and Applied Sciences, TR-35160 Izmir (Turkey); Polat, Hamza, E-mail: hamza.polat@deu.edu.tr [Department of Physics, Dokuz Eylül University, TR-35160 Izmir (Turkey)
2015-10-15
Nonequilibrium phase transition properties of a mixed Ising ferrimagnetic model consisting of spin-1/2 and spin-3/2 on a square lattice under the existence of a time dependent oscillating magnetic field have been investigated by making use of Monte Carlo simulations with a single-spin flip Metropolis algorithm. A complete picture of dynamic phase boundary and magnetization profiles have been illustrated and the conditions of a dynamic compensation behavior have been discussed in detail. According to our simulation results, the considered system does not point out a dynamic compensation behavior, when it only includes the nearest-neighbor interaction, single-ion anisotropy and an oscillating magnetic field source. As the next-nearest-neighbor interaction between the spins-1/2 takes into account and exceeds a characteristic value which sensitively depends upon values of single-ion anisotropy and only of amplitude of external magnetic field, a dynamic compensation behavior occurs in the system. Finally, it is reported that it has not been found any evidence of dynamically first-order phase transition between dynamically ordered and disordered phases, which conflicts with the recently published molecular field investigation, for a wide range of selected system parameters. - Highlights: • Spin-1/2 and spin-3/2 Ising ferrimagnetic model is examined. • The system is exposed to time-dependent magnetic field. • Kinetic Monte Carlo simulation technique is used. • Any evidence of first-order phase transition has not been found.
Energy Technology Data Exchange (ETDEWEB)
Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, N.; Schoenlein, R. W.; Govind, Niranjan; Khalil, Munira
2013-05-01
Ruthenium L2,3-edge X-ray absorption (XA) spectroscopy probes transitions from core 2p orbitals to the 4d levels of the atom and is a powerful tool for interrogating the local electronic and molecular structure around the metal atom. However, a molecular-level interpretation of the Ru L2,3-edge spectral lineshapes is often complicated by spin–orbit coupling (SOC) and multiplet effects. In this study, we develop spin-free time-dependent density functional theory (TDDFT) as a viable and predictive tool to simulate the Ru L3-edge spectra. We successfully simulate and analyze the ground state Ru L3-edge XA spectra of a series of RuII and RuIII complexes: [Ru(NH3)6]2+/3+, [Ru(CN)6]4-/3-, [RuCl6]4-/3-, and the ground (1A1) and photoexcited (3MLCT) transient states of [Ru(bpy)3]2+ and Ru(dcbpy)2(NCS)2 (termed N3). The TDDFT simulations reproduce all the experimentally observed features in Ru L3-edge XA spectra. The advantage of using TDDFT to assign complicated Ru L3-edge spectra is illustrated by its ability to identify ligand specific charge transfer features in complex molecules. We conclude that the B3LYP functional is the most reliable functional for accurately predicting the location of charge transfer features in these spectra. Experimental and simulated Ru L3-edge XA spectra are presented for the transition metal mixed-valence dimers [(NC)5MII-CN-RuIII(NH3)5]- (where M = Fe or Ru) dissolved in water. We explore the spectral signatures of electron delocalization in Ru L3-edge XA spectroscopy and our simulations reveal that the inclusion of explicit solvent molecules is crucial for reproducing the experimentally determined valencies, highlighting the importance of the role of the solvent in transition metal charge transfer chemistry.
Energy Technology Data Exchange (ETDEWEB)
Valsson, Omar [Department of Chemistry and Applied Biosciences, ETH Zurich and Facoltà di Informatica, Instituto di Scienze Computationali, Università della Svizzera italiana, Via Giuseppe Buffi 13, CH-6900 Lugano (Switzerland); Filippi, Claudia, E-mail: c.filippi@utwente.nl [MESA+ Institute for Nanotechnology, University of Twente, P.O. Box 217, 7500 AE Enschede (Netherlands); Casida, Mark E., E-mail: mark.casida@ujf-grenoble.fr [Laboratoire de Chimie Théorique, Département de Chimie Moléculaire (DCM), Institut de Chimie Moléculaire de Grenoble (ICMG), Université Joseph Fourier, Grenoble I, F-3801 Grenoble (France)
2015-04-14
The excited-state relaxation of retinal protonated Schiff bases (PSBs) is an important test case for biological applications of time-dependent (TD) density-functional theory (DFT). While well-known shortcomings of approximate TD-DFT might seem discouraging for application to PSB relaxation, progress continues to be made in the development of new functionals and of criteria allowing problematic excitations to be identified within the framework of TD-DFT itself. Furthermore, experimental and theoretical ab initio advances have recently lead to a revised understanding of retinal PSB photochemistry, calling for a reappraisal of the performance of TD-DFT in describing this prototypical photoactive system. Here, we re-investigate the performance of functionals in (TD-)DFT calculations in light of these new benchmark results, which we extend to larger PSB models. We focus on the ability of the functionals to describe primarily the early skeletal relaxation of the chromophore and investigate how far along the out-of-plane pathways these functionals are able to describe the subsequent rotation around formal single and double bonds. Conventional global hybrid and range-separated hybrid functionals are investigated as the presence of Hartree-Fock exchange reduces problems with charge-transfer excitations as determined by the Peach-Benfield-Helgaker-Tozer Λ criterion and by comparison with multi-reference perturbation theory results. While we confirm that most functionals cannot render the complex photobehavior of the retinal PSB, do we also observe that LC-BLYP gives the best description of the initial part of the photoreaction.
Valsson, Omar; Filippi, Claudia; Casida, Mark E.
2015-04-01
The excited-state relaxation of retinal protonated Schiff bases (PSBs) is an important test case for biological applications of time-dependent (TD) density-functional theory (DFT). While well-known shortcomings of approximate TD-DFT might seem discouraging for application to PSB relaxation, progress continues to be made in the development of new functionals and of criteria allowing problematic excitations to be identified within the framework of TD-DFT itself. Furthermore, experimental and theoretical ab initio advances have recently lead to a revised understanding of retinal PSB photochemistry, calling for a reappraisal of the performance of TD-DFT in describing this prototypical photoactive system. Here, we re-investigate the performance of functionals in (TD-)DFT calculations in light of these new benchmark results, which we extend to larger PSB models. We focus on the ability of the functionals to describe primarily the early skeletal relaxation of the chromophore and investigate how far along the out-of-plane pathways these functionals are able to describe the subsequent rotation around formal single and double bonds. Conventional global hybrid and range-separated hybrid functionals are investigated as the presence of Hartree-Fock exchange reduces problems with charge-transfer excitations as determined by the Peach-Benfield-Helgaker-Tozer Λ criterion and by comparison with multi-reference perturbation theory results. While we confirm that most functionals cannot render the complex photobehavior of the retinal PSB, do we also observe that LC-BLYP gives the best description of the initial part of the photoreaction.
Tateyama, Yoshitaka; Oyama, Norihisa; Ohno, Takahisa; Miyamoto, Yoshiyuki
2006-03-01
Mechanism of the ring-opening transformation in the photoexcited crystalline benzene is investigated on the femtosecond scale by a computational method based on the real-time propagation (RTP) time-dependent density functional theory (TDDFT). The excited-state dynamics of the benzene molecule is also examined not only for the distinction between the intrinsic properties of molecule and the intermolecular interaction but for the first validation using the vibration frequencies for the RTP-TDDFT approach. It is found that the vibration frequencies of the excited and ground states in the molecule are well reproduced. This demonstrates that the present method of time evolution using the Suzuki-Trotter-type split operator technique starting with the Franck-Condon state approximated by the occupation change of the Kohn-Sham orbitals is adequately accurate. For the crystalline benzene, we carried out the RTP-TDDFT simulations for two typical pressures. At both pressures, large swing of the C-H bonds and subsequent twist of the carbon ring occurs, leading to tetrahedral (sp3-like) C-H bonding. The ν4 and ν16 out-of-plane vibration modes of the benzene molecule are found mostly responsible for these motions, which is different from the mechanism proposed for the thermal ring-opening transformation occurring at higher pressure. Comparing the results between different pressures, we conclude that a certain increase of the intermolecular interaction is necessary to make seeds of the ring opening (e.g., radical site formation and breaking of the molecular character) even with the photoexcitation, while the hydrogen migration to fix them requires more free volume, which is consistent with the experimental observation that the transformation substantially proceeds on the decompression.
Marino, I.-G.; Razzetti, C.; Lottici, P. P.
2007-03-01
We have investigated by wide field polariscopy the behaviour of photoinduced birefringence (PIB) in sol-gel hybrid disperse red 1 (DR1) doped films. This technique allows the mapping of the local values of a bell-shaped pump beam irradiance and those of the corresponding photoinduced birefringence. By means of a point-to-point correlation of these maps, we have tracked the dependence of PIB, simultaneously and continuously, on exposure times and pump irradiances. We have then applied some of the available theoretical models, representing birefringence as an analytical function of irradiance and time, to interpolate the experimental PIB data. As compared to the usual PIB measurements, which neglect the spatial distribution of the pump irradiance, our results provide a more detailed and reliable empirical basis on which models of the orientational mechanisms of the photoisomerizable molecules can be developed.
Casida, Mark E.; Salahub, Dennis R.
2000-11-01
The time-dependent density functional theory (TD-DFT) calculation of excitation spectra places certain demands on the DFT exchange-correlation potential, vxc, that are not met by the functionals normally used in molecular calculations. In particular, for high-lying excitations, it is crucial that the asymptotic behavior of vxc be correct. In a previous paper, we introduced a novel asymptotic-correction approach which we used with the local density approximation (LDA) to yield an asymptotically corrected LDA (AC-LDA) potential [Casida, Casida, and Salahub, Int. J. Quantum Chem. 70, 933 (1998)]. The present paper details the theory underlying this asymptotic correction approach, which involves a constant shift to incorporate the effect of the derivative discontinuity (DD) in the bulk region of finite systems, and a spliced asymptotic correction in the large r region. This is done without introducing any adjustable parameters. We emphasize that correcting the asymptotic behavior of vxc is not by itself sufficient to improve the overall form of the potential unless the effect of the derivative discontinuity is taken into account. The approach could be used to correct vxc from any of the commonly used gradient-corrected functionals. It is here applied to the LDA, using the asymptotically correct potential of van Leeuwen and Baerends (LB94) in the large r region. The performance of our AC-LDA vxc is assessed for the calculation of TD-DFT excitation energies for a large number of excitations, including both valence and Rydberg states, for each of four small molecules: N2, CO, CH2O, and C2H4. The results show a significant improvement over those from either the LB94 or the LDA functionals. This confirms that the DD is indeed an important element in the design of functionals. The quality of TDLDA/LB94 and TDLDA/AC-LDA oscillator strengths were also assessed in what we believe to be the first rigorous assessment of TD-DFT molecular oscillator strengths in comparison with
Energy Technology Data Exchange (ETDEWEB)
Strobel, Eckhard, E-mail: eckhard.strobel@irap-phd.eu [ICRANet, Piazzale della Repubblica 10, 65122 Pescara (Italy); Dipartimento di Fisica, Università di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome (Italy); Université de Nice Sophia Antipolis, 28 Avenue de Valrose, 06103 Nice Cedex 2 (France); Xue, She-Sheng, E-mail: xue@icra.it [ICRANet, Piazzale della Repubblica 10, 65122 Pescara (Italy); Dipartimento di Fisica, Università di Roma “La Sapienza”, Piazzale Aldo Moro 5, 00185 Rome (Italy)
2014-09-15
We present an analytic calculation of the semiclassical electron–positron pair creation rate by time-dependent electrical fields. We use two methods, first the imaginary time method in the WKB-approximation and second the world-line instanton approach. The analytic tools for both methods are generalized to time-dependent electric fields with more than one component. For the WKB method an expansion of the momentum spectrum of produced pairs around the canonical momentum P{sup →}=0 is presented which simplifies the computation of the pair creation rate. We argue that the world-line instanton method of [1] implicitly performs this expansion of the momentum spectrum around P{sup →}=0. Accordingly, the generalization to more than one component is shown to agree with the WKB result obtained via this expansion. However the expansion is only a good approximation for the cases where the momentum spectrum is peaked around P{sup →}=0. Thus the expanded WKB result and the world-line instanton method of [1] as well as the generalized method presented here are only applicable in these cases. We study the two-component case of a rotating electric field and find a new analytic closed form for the momentum spectrum using the generalized WKB method. The momentum spectrum for this field is not peaked around P{sup →}=0.
Institute of Scientific and Technical Information of China (English)
Yue Da-Guang; Zheng Xiao-Yun; Liu Hao; Wang Chun-Xing; Meng Qing-Tian
2009-01-01
This paper reports that the(2+1)resonance enhanced multi-photon ionization spectra of SH radical in external fields are simulated using the split-operator scheme of time-dependent wave-packet method.Two ionic states.i.e.α1△ and b1∑+,are involved in the simulation.It gives the simulated photoelectron spectra,the population in each electronic state,as well as the projection of the wave-packet in each electronic state on different vibrational states.These results show that the so-called four-state model can represent the experimental results well.
Casida, Mark E; Huix-Rotllant, Miquel
2016-01-01
In their famous paper, Kohn and Sham formulated a formally exact density-functional theory (DFT) for the ground-state energy and density of a system of N interacting electrons, albeit limited at the time by certain troubling representability questions. As no practical exact form of the exchange-correlation (xc) energy functional was known, the xc-functional had to be approximated, ideally by a local or semilocal functional. Nowadays, however, the realization that Nature is not always so nearsighted has driven us up Perdew's Jacob's ladder to find increasingly nonlocal density/wavefunction hybrid functionals. Time-dependent (TD-) DFT is a younger development which allows DFT concepts to be used to describe the temporal evolution of the density in the presence of a perturbing field. Linear response (LR) theory then allows spectra and other information about excited states to be extracted from TD-DFT. Once again the exact TD-DFT xc-functional must be approximated in practical calculations and this has historically been done using the TD-DFT adiabatic approximation (AA) which is to TD-DFT very similar to what the local density approximation (LDA) is to conventional ground-state DFT. Although some of the recent advances in TD-DFT focus on what can be done within the AA, others explore ways around the AA. After giving an overview of DFT, TD-DFT, and LR-TD-DFT, this chapter focuses on many-body corrections to LR-TD-DFT as one way to build hybrid density-functional/wavefunction methodology for incorporating aspects of nonlocality in time not present in the AA.
Birke, Ronald L; Znamenskiy, Vasiliy; Lombardi, John R
2010-06-07
Vibrational frequency calculations were made for a Ag(10)-pyridine vertex complex with density functional theory (DFT) for static simulated spectra and with time-dependent DFT (TD-DFT) for preresonance and resonance simulated spectra using both B3LYP/LANL2DZ and BP86/TZP methodologies. In addition, 40 excited states of the complex were calculated and assigned symmetry based on a C(2v) symmetry of the optimized complex found with B3LYP/LANL2DZ. Molecular orbital isosurfaces show that the excited states involve both Ag(10) intercluster excitations and charge-transfer (CT) excitations between the Ag nanocluster and the pyridine molecule. An excitation around 500 nm involving CT from the Ag cluster to pyridine was found in both calculations. For free pyridine, the relative average deviations between unscaled calculated and experimental results were 1.5 cm(-1) for BP86 and 3.1 cm(-1) for the B3LYP calculations. For the complex, simulated spectra at a variety of excitation wavelengths were calculated. In the case of 514 nm excitation, the simulated Raman cross section from the TD-DFT calculations (near the CT resonance) was plotted versus Raman shift frequency and compared with an experimental surface enhanced Raman scattering (SERS) spectrum obtained on an oxidation-reduction cycle, ORC roughened Ag electrode. The BP86 TD-DFT calculation with finite damping term showed a better fit to experimental spectrum with respect to both relative intensities and frequencies. The average deviation of the unscaled BP86 calculations for 16 bands in the experimental spectrum was 13.0 cm(-1). The calculated spectrum in both cases shows many contributions from nontotally symmetric as well as totally symmetric modes, indicating the contribution of Herzberg-Teller (HT) scattering. The simulated intensities of the Raman modes of different symmetry from Ag(10)-pyridine can be correlated with HT intensity borrowing from excited states of given symmetry and decent oscillator strength. These
Minasian, Stefan G; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Kozimor, Stosh A; Martin, Richard L; Shuh, David K; Tyliszczak, Tolek; Vernon, Louis J
2013-10-01
Metal-carbon covalence in (C5H5)2MCl2 (M = Ti, Zr, Hf) has been evaluated using carbon K-edge X-ray absorption spectroscopy (XAS) as well as ground-state and time-dependent hybrid density functional theory (DFT and TDDFT). Differences in orbital mixing were determined experimentally using transmission XAS of thin crystalline material with a scanning transmission X-ray microscope (STXM). Moving down the periodic table (Ti to Hf) has a marked effect on the experimental transition intensities associated with the low-lying antibonding 1a1* and 1b2* orbitals. The peak intensities, which are directly related to the M-(C5H5) orbital mixing coefficients, increase from 0.08(1) and 0.26(3) for (C5H5)2TiCl2 to 0.31(3) and 0.75(8) for (C5H5)2ZrCl2, and finally to 0.54(5) and 0.83(8) for (C5H5)2HfCl2. The experimental trend toward increased peak intensity for transitions associated with 1a1* and 1b2* orbitals agrees with the calculated TDDFT oscillator strengths [0.10 and 0.21, (C5H5)2TiCl2; 0.21 and 0.73, (C5H5)2ZrCl2; 0.35 and 0.69, (C5H5)2HfCl2] and with the amount of C 2p character obtained from the Mulliken populations for the antibonding 1a1* and 1b2* orbitals [8.2 and 23.4%, (C5H5)2TiCl2; 15.3 and 39.7%, (C5H5)2ZrCl2; 20.1 and 50.9%, (C5H5)2HfCl2]. The excellent agreement between experiment, theory, and recent Cl K-edge XAS and DFT measurements shows that C 2p orbital mixing is enhanced for the diffuse Hf (5d) and Zr (4d) atomic orbitals in relation to the more localized Ti (3d) orbitals. These results provide insight into how changes in M-Cl orbital mixing within the metallocene wedge are correlated with periodic trends in covalent bonding between the metal and the cyclopentadienide ancillary ligands.
Sato, Takeshi; Ishikawa, Kenichi L.; Březinová, Iva; Lackner, Fabian; Nagele, Stefan; Burgdörfer, Joachim
2016-08-01
We present a numerical implementation of the time-dependent complete-active-space self-consistent-field (TD-CASSCF) method [Phys. Rev. A 88, 023402 (2013), 10.1103/PhysRevA.88.023402] for atoms driven by a strong linearly polarized laser pulse. The present implementation treats the problem in its full dimensionality and introduces a gauge-invariant frozen-core approximation, an efficient evaluation of the Coulomb mean field scaling linearly with the number of basis functions, and a split-operator method specifically designed for stable propagation of stiff spatial derivative operators. We apply this method to high-harmonic generation in helium, beryllium, and neon and explore the role of electron correlations.
Herbert, John M; Zhang, Xing; Morrison, Adrian F; Liu, Jie
2016-05-17
Single-excitation methods, namely, configuration interaction singles and time-dependent density functional theory (TDDFT), along with semiempirical versions thereof, represent the most computationally affordable electronic structure methods for describing electronically excited states, scaling as [Formula: see text] absent further approximations. This relatively low cost, combined with a treatment of electron correlation, has made TDDFT the most widely used excited-state quantum chemistry method over the past 20+ years. Nevertheless, certain inherent problems (beyond just the accuracy of this or that exchange-correlation functional) limit the utility of traditional TDDFT. For one, it affords potential energy surfaces whose topology is incorrect in the vicinity of any conical intersection (CI) that involves the ground state. Since CIs are the conduits for transitions between electronic states, the TDDFT description of photochemistry (internal conversion and intersystem crossing) is therefore suspect. Second, the [Formula: see text] cost can become prohibitive in large systems, especially those that involve multiple electronically coupled chromophores, for example, the antennae structures of light-harvesting complexes or the conjugated polymers used in organic photovoltaics. In such cases, the smallest realistic mimics might already be quite large from the standpoint of ab initio quantum chemistry. This Account describes several new computational methods that address these problems. Topology around a CI can be rigorously corrected using a "spin-flip" version of TDDFT, which involves an α → β spin-flipping transition in addition to occupied → virtual excitation of one electron. Within this formalism, singlet states are generated via excitation from a high-spin triplet reference state, doublets from a quartet, etc. This provides a more balanced treatment of electron correlation between ground and excited states. Spin contamination is problematic away from the
Sepehry-Fard, F.; Coulthard, Maurice H.
1995-01-01
The process of predicting the values of maintenance time dependent variable parameters such as mean time between failures (MTBF) over time must be one that will not in turn introduce uncontrolled deviation in the results of the ILS analysis such as life cycle costs, spares calculation, etc. A minor deviation in the values of the maintenance time dependent variable parameters such as MTBF over time will have a significant impact on the logistics resources demands, International Space Station availability and maintenance support costs. There are two types of parameters in the logistics and maintenance world: a. Fixed; b. Variable Fixed parameters, such as cost per man hour, are relatively easy to predict and forecast. These parameters normally follow a linear path and they do not change randomly. However, the variable parameters subject to the study in this report such as MTBF do not follow a linear path and they normally fall within the distribution curves which are discussed in this publication. The very challenging task then becomes the utilization of statistical techniques to accurately forecast the future non-linear time dependent variable arisings and events with a high confidence level. This, in turn, shall translate in tremendous cost savings and improved availability all around.
Sepehry-Fard, F.; Coulthard, Maurice H.
1995-01-01
The process of predicting the values of maintenance time dependent variable parameters such as mean time between failures (MTBF) over time must be one that will not in turn introduce uncontrolled deviation in the results of the ILS analysis such as life cycle costs, spares calculation, etc. A minor deviation in the values of the maintenance time dependent variable parameters such as MTBF over time will have a significant impact on the logistics resources demands, International Space Station availability and maintenance support costs. There are two types of parameters in the logistics and maintenance world: a. Fixed; b. Variable Fixed parameters, such as cost per man hour, are relatively easy to predict and forecast. These parameters normally follow a linear path and they do not change randomly. However, the variable parameters subject to the study in this report such as MTBF do not follow a linear path and they normally fall within the distribution curves which are discussed in this publication. The very challenging task then becomes the utilization of statistical techniques to accurately forecast the future non-linear time dependent variable arisings and events with a high confidence level. This, in turn, shall translate in tremendous cost savings and improved availability all around.
Feigl, K. L.; Ali, S. T.; Akerley, J.; Baluyut, E.; Cardiff, M. A.; Davatzes, N. C.; Foxall, W.; Fratta, D.; Kreemer, C.; Mellors, R. J.; Lopeman, J.; Spielman, P.; Wang, H. F.
2015-12-01
To measure time-dependent deformation at the Brady Hot Springs geothermal field in western Nevada, we analyze interferometric synthetic aperture radar (InSAR) data acquired between 2004 and 2014 by five satellite missions, including: ERS-2, Envisat, ALOS, TerraSAR-X, and TanDEM-X. The resulting maps of deformation show an elliptical subsiding area that is ~4 km by ~1.5 km. Its long axis coincides with the strike of the dominant normal-fault system at Brady. Within this bowl of subsidence, the interference pattern shows several smaller features with length scales of the order of ~1 km. This signature occurs consistently in all of the well-correlated interferometric pairs spanning several months. Results from inverse modeling suggest that the deformation is a result of volumetric contraction in shallow units, no deeper than 600 m, that are probably associated with damaged regions where faults interact via thermal (T), hydrological (H), mechanical (M), and chemical (C) processes. Such damaged zones are expected to extend downward along steeply dipping fault planes, providing high-permeability conduits to the production wells. Using time series analysis, we test the hypothesis that geothermal production drives the observed deformation. We find a good correlation between the observed deformation rate and the rate of production in the shallow wells. We explore first-order models to calculate the time-dependent deformation fields produced by coupled processes, including: thermal contraction of rock (T-M coupling), decline in pore pressure (H-M coupling), and dissolution of minerals over time (H-C-M coupling). These processes are related to the heterogeneity of hydro-geological and material properties at the site. This work is part of a project entitled "Poroelastic Tomography by Adjoint Inverse Modeling of Data from Seismology, Geodesy, and Hydrology" (PoroTomo) http://geoscience.wisc.edu/feigl/porotomo.
Reiche, S
2000-01-01
For shorter bunches and narrower undulator gaps the interaction between the electrons in the bunch and the wake fields becomes so large that the FEL amplification is affected. For a typical vacuum chamber of an X-ray or VUV Free Electron Laser three major sources of wake fields exist: a resistance of the beam pipe, a change in the geometric aperture and the surface roughness of the beam pipe. The generated wake fields, which move along with the electrons, change the electron energy and momentum, depending on the electron longitudinal and transverse position. In particular, the accumulated energy modulation shifts the electrons away from the resonance condition. Based on an analytic model the energy loss by the wake fields has been incorporated into the time-dependent FEL simulation code GENESIS 1.3. For the parameters of the TESLA Test Facility the influence of the bunch length, beam pipe diameter and surface roughness has been studied. The results are presented in this paper.
Energy Technology Data Exchange (ETDEWEB)
Shvetsov-Shilovski, N.I., E-mail: nikolay.shvetsov@tut.fi; Räsänen, E., E-mail: erasanen@tut.fi
2014-12-15
One-dimensional model systems have a particular role in strong-field physics when gaining physical insight by computing data over a large range of parameters, or when performing numerous time propagations within, e.g., optimal control theory. Here we derive a scheme that removes a singularity in the one-dimensional Schrödinger equation in momentum space for a particle in the commonly used soft-core Coulomb potential. By using this scheme we develop two numerical approaches to the time-dependent Schrödinger equation in momentum space. The first approach employs the expansion of the momentum-space wave function over the eigenstates of the field-free Hamiltonian, and it is shown to be more efficient for laser parameters usual in strong field physics. The second approach employs the Crank–Nicolson scheme or the method of lines for time-propagation. The both methods are readily applicable for large-scale numerical simulations in one-dimensional model systems.
Directory of Open Access Journals (Sweden)
Y. Liu
2012-09-01
Full Text Available This paper is devoted on the application of the computational method for calculating the transient electromagnetic (EM near-field (NF radiated by electronic structures from the frequency-dependent data for the arbitrary wave form perturbations i(t. The method proposed is based on the fast Fourier transform (FFT. The different steps illustrating the principle of the method is described. It is composed of three successive steps: the synchronization of the input excitation spectrum I(f and the given frequency data H0(f, the convolution of the two inputs data and then, the determination of the time-domain emissions H(t. The feasibility of the method is verified with standard EM 3D simulations. In addition to this method, an extraction technique of the time-dependent z-transversal EM NF component Xz(t from the frequency-dependent x- and y- longitudinal components Hx(f and Hy(f is also presented. This technique is based on the conjugation of the plane wave spectrum (PWS transform and FFT. The feasibility of the method is verified with a set of dipole radiations. The method introduced in this paper is particularly useful for the investigation of time-domain emissions for EMC applications by considering transient EM interferences (EMIs.
Sharma, Divya; Paterson, Martin J
2014-11-01
DFT and MP2 calculations are performed to obtain optimized ground state geometries and binding energies of the cage and the prism conformers of water W6 clusters and Bz-W6 clusters using the aug-cc-pVDZ basis set. The cage conformer of Bz-W6 system is found to be more stable than prism conformer for all range of DFT functionals and MP2. Time dependent-DFT is then used to study UV spectroscopy of Bz, water W6 clusters and Bz-W6 clusters at both the MP2 and wB97XD optimized ground state geometries using the B3LYP, CAM-B3LYP and M06-2X functionals with 6-31++G(d,p) and aug-cc-pVTZ basis sets. Our results predict minor differences in the UV spectroscopy of cage and prism conformers W6 and Bz-W6 clusters that may be observable with high-resolution spectroscopy. The M06-2X and CAM-B3LYP functionals perform consistently with each other. Benzene-mediated excitations of the water W6 cluster towards longer wavelengths above 170 nm are noticed in both the cage and prism geometries of Bz-W6. Benzene is found to be influenced after interacting with the cage and prism W6 geometries, and is seen to undergo a red shift in the main π→π* electronic transition, in which the degeneracy is slightly broken. Charge transfer (CT) states and diffuse Rydberg-type states are also found to play an important role in the spectroscopy of such systems.
Basak, Sucharita; Rajak, Kajal Krishna
2008-10-06
The oxorhenium(V) complexes [Re (V)O(L A)Cl 2] bearing the (N-2-pyridylmethyl) of l-valine (HL A (1)), l-leucine (HL A (2)), and l-phenylalanine (HL A (3)) and [Re (V)O(L B)Cl] containing the {(N-2pyridylmethyl)-(N-(5-nitro-2-hydroxybenzyl)} of l-valine (H 2L B (1)), l-leucine (H 2L B (2)), and l-phenylalanine (H 2L B (3)) are presented in this article. The complexes are isolated in enantiomeric pure form examined from X-ray structure determination. The complexes are characterized by spectroscopic and electrochemical methods. The molecular structures observed in the solid state are grossly preserved in solution ( (1)H, (13)C, and circular dichroism spectra). Gas-phase geometry optimization and the electronic structures of [Re (V)O(L A (1))Cl 2], [Re (V)O(L A (2))Cl 2], and [Re (V)O(L B (2))Cl] have been investigated with the framework of density functional theory. The absorption and circular dichroism spectra of the complexes were also calculated applying time-dependent density functional theory (TDDFT) using the conductor-like polarizable continuum solvent model to understand the origin of the electronic excitations. The chemical shift ( (1)H and (13)C) as well as (1)H- (1)H spin-spin coupling constant were also computed by the gauge-independent atomic orbital method, and the computed values are consistent with the experimental data.
Energy Technology Data Exchange (ETDEWEB)
Zhang Long [College of Mathematics and System Sciences, Xinjiang University, Urumqi 830046 (China)], E-mail: longzhang_xj@sohu.com; Teng Zhidong [College of Mathematics and System Sciences, Xinjiang University, Urumqi 830046 (China)], E-mail: zhidong@xju.edu.cn
2008-05-15
In this paper, we study two species predator-prey Lotka-Volterra type dispersal system with periodic coefficients, in which the prey species can disperse among n patches, while the density-independent predator species is confined to one of the patches and cannot disperse. Sufficient conditions on the boundedness, permanence and existence of positive periodic solution for this system are established. The theoretical results are confirmed by a special example and numerical simulations.
Tawfik, Sherif A.; El-Sheikh, S. M.; Salem, N. M.
2016-09-01
Recently we have become aware that the description of the quantum wave functions in Sec. 2.1 is incorrect. In the published version of the paper, we have stated that the states are expanded in terms of plane waves. However, the correct description of the quantum states in the context of the real space implementation (using the Octopus code) is that states are represented by discrete points in a real space grid.
Energy Technology Data Exchange (ETDEWEB)
Welch, E. C.; Zhang, P.; He, Z.-H. [Department of Nuclear Engineering and Radiological Sciences, University of Michigan, Ann Arbor, Michigan 48109-2104 (United States); Dollar, F. [JILA, University of Colorado, Boulder, Colorado 80309 (United States); Krushelnick, K.; Thomas, A. G. R., E-mail: agrt@umich.edu [Department of Nuclear Engineering and Radiological Sciences, University of Michigan, Ann Arbor, Michigan 48109-2104 (United States); Center for Ultrafast Optical Science, University of Michigan, Ann Arbor, Michigan 48109-2104 (United States)
2015-05-15
High order harmonic generation from solid targets is a compelling route to generating intense attosecond or even zeptosecond pulses. However, the effects of ion motion on the generation of harmonics have only recently started to be considered. Here, we study the effects of ion motion in harmonics production at ultrahigh laser intensities interacting with solid density plasma. Using particle-in-cell simulations, we find that there is an optimum density for harmonic production that depends on laser intensity, which scales linearly with a{sub 0} with no ion motion but with a reduced scaling if ion motion is included. We derive a scaling for this optimum density with ion motion and also find that the background ion motion induces Doppler red-shifts in the harmonic structures of the reflected pulse. The temporal structure of the Doppler shifts is correlated to the envelope of the incident laser pulse. We demonstrate that by introducing a frequency chirp in the incident pulse we are able to eliminate these Doppler shifts almost completely.
Threshold electric field in unconventional density waves
Dóra, Balázs; Virosztek, Attila; Maki, Kazumi
2001-07-01
As it is well known most charge-density waves (CDW's) and spin-density waves exhibit nonlinear transport with well-defined threshold electric field ET. Here we study theoretically the threshold electric field of unconventional density waves. We find that the threshold field increases monotonically with temperature without divergent behavior at Tc, unlike the one in conventional CDW. The present result in the three-dimensional weak pinning limit appears to describe rather well the threshold electric field observed recently in the low-temperature phase of α-(BEDT-TTF)2KHg(SCN)4.
Energy Technology Data Exchange (ETDEWEB)
Keim, M.
2005-07-01
In the present thesis response effects in interatomic collisions with two active electrons are studied in the range of non-relativistic collision energies. The starting point is the mapping of the time-dependent interacting many-electron sytem on an effective one-particle picture on the base of the time-dependent density functional theory (TDDFT). By means of the basis generator method the one-particle equations aring in the framework of the TDDFT concept are solved in a finite-dimensional model space. In the study of ionization cross section in the collisional systeem anti p+He it is shown that by response effects an essential diminuishing of the cross sections in comparison to the no-response case is reached. Analoguously the ionization cross sections for the collisional systems p-He, He{sup 2+}-He, Li{sup 3+}-He and p-Li{sup +} behave.
Zuehlsdorff, Tim J; Payne, Mike C; Haynes, Peter D
2015-01-01
We present a solution of the full TDDFT eigenvalue equation in the linear response formalism exhibiting a linear-scaling computational complexity with system size, without relying on the simplifying Tamm-Dancoff approximation (TDA). The implementation relies on representing the occupied and unoccupied subspace with two different sets of in situ optimised localised functions, yielding a very compact and efficient representation of the transition density matrix of the excitation with the accuracy associated with a systematic basis set. The TDDFT eigenvalue equation is solved using a preconditioned conjugate-gradients algorithm that is very memory-efficient. The algorithm is validated on a test molecule and a good agreement with results obtained from standard quantum chemistry packages is found, with the preconditioner yielding a significant improvement in convergence rates. The method developed in this work is then used to reproduce experimental results of the absorption spectrum of bacteriochlorophyll (BChl) i...
Mikhailov, Ivan A.; Tafur, Sergio; Masunov, Artëm E.
2008-01-01
The effect of static and dynamic electron correlation on the nature of excited states and state-to-state transition dipole moments is studied with a multideterminant wave function approach on the example of all-trans linear polyenes ( C4H6 , C6H8 , and C8H10 ). Symmetry-forbidden singlet nAg states were found to separate into three groups: purely single, mostly single, and mostly double excitations. The excited-state absorption spectrum is dominated by two bright transitions: 1Bu-2Ag and 1Bu-mAg , where mAg is the state, corresponding to two-electron excitation from the highest occupied to lowest unoccupied molecular orbital. The richness of the excited-state absorption spectra and strong mixing of the doubly excited determinants into lower- nAg states, reported previously at the complete active space self-consistent field level of theory, were found to be an artifact of the smaller active space, limited to π orbitals. When dynamic σ-π correlation is taken into account, single- and double-excited states become relatively well separated at least at the equilibrium geometry of the ground state. This electronic structure is closely reproduced within time-dependent density-functional theory (TD DFT), where double excitations appear in a second-order coupled electronic oscillator formalism and do not mix with the single excitations obtained within the linear response. An extension of TD DFT is proposed, where the Tamm-Dancoff approximation (TDA) is invoked after the linear response equations are solved (a posteriori TDA). The numerical performance of this extension is validated against multideterminant-wave-function and quadratic-response TD DFT results. It is recommended for use with a sum-over-states approach to predict the nonlinear optical properties of conjugated molecules.
Hamilton, H. B.; Strangas, E.
1980-01-01
The time dependent solution of the magnetic field is introduced as a method for accounting for the variation, in time, of the machine parameters in predicting and analyzing the performance of the electrical machines. The method of time dependent finite element was used in combination with an also time dependent construction of a grid for the air gap region. The Maxwell stress tensor was used to calculate the airgap torque from the magnetic vector potential distribution. Incremental inductances were defined and calculated as functions of time, depending on eddy currents and saturation. The currents in all the machine circuits were calculated in the time domain based on these inductances, which were continuously updated. The method was applied to a chopper controlled DC series motor used for electric vehicle drive, and to a salient pole sychronous motor with damper bars. Simulation results were compared to experimentally obtained ones.
Isegawa, Miho; Truhlar, Donald G.
2013-04-01
Time-dependent density functional theory (TDDFT) holds great promise for studying photochemistry because of its affordable cost for large systems and for repeated calculations as required for direct dynamics. The chief obstacle is uncertain accuracy. There have been many validation studies, but there are also many formulations, and there have been few studies where several formulations were applied systematically to the same problems. Another issue, when TDDFT is applied with only a single exchange-correlation functional, is that errors in the functional may mask successes or failures of the formulation. Here, to try to sort out some of the issues, we apply eight formulations of adiabatic TDDFT to the first valence excitations of ten molecules with 18 density functionals of diverse types. The formulations examined are linear response from the ground state (LR-TDDFT), linear response from the ground state with the Tamm-Dancoff approximation (TDDFT-TDA), the original collinear spin-flip approximation with the Tamm-Dancoff (TD) approximation (SF1-TDDFT-TDA), the original noncollinear spin-flip approximation with the TDA approximation (SF1-NC-TDDFT-TDA), combined self-consistent-field (SCF) and collinear spin-flip calculations in the original spin-projected form (SF2-TDDFT-TDA) or non-spin-projected (NSF2-TDDFT-TDA), and combined SCF and noncollinear spin-flip calculations (SF2-NC-TDDFT-TDA and NSF2-NC-TDDFT-TDA). Comparing LR-TDDFT to TDDFT-TDA, we observed that the excitation energy is raised by the TDA; this brings the excitation energies underestimated by full linear response closer to experiment, but sometimes it makes the results worse. For ethylene and butadiene, the excitation energies are underestimated by LR-TDDFT, and the error becomes smaller making the TDA. Neither SF1-TDDFT-TDA nor SF2-TDDFT-TDA provides a lower mean unsigned error than LR-TDDFT or TDDFT-TDA. The comparison between collinear and noncollinear kernels shows that the noncollinear kernel
Halasinski, Thomas M.; Weisman, Jennifer L.; Lee, Timothy J.; Salama, Farid; Head-Gordon, Martin; Kwak, Dochan (Technical Monitor)
2002-01-01
We present a full experimental and theoretical study of an interesting series of polycyclic aromatic hydrocarbons, the oligorylenes. The absorption spectra of perylene, terrylene and quaterrylene in neutral, cationic and anionic charge states are obtained by matrix-isolation spectroscopy in Ne. The experimental spectra are dominated by a bright state that red shifts with growing molecular size. Excitation energies and state symmetry assignments are supported by calculations using time dependent density functional theory methods. These calculations also provide new insight into the observed trends in oscillator strength and excitation energy for the bright states: the oscillator strength per unit mass of carbon increases along the series.
Yb、Ybo电子激发态的相对论含时密度泛函理论研究%Time-dependent relativistic density functional study of Yb and YbO
Institute of Scientific and Technical Information of China (English)
许文华; 张勇; 刘文剑
2009-01-01
The low-lying electronic states of Yb and YbO are investigated by using time-dependent relativistic density functional theory,which is based on the newly developed exact two-component Hamiltonian resulting from symmetrized elimination of the small component.The nature of the excited states is analyzed by using the fall molecular symmetry.The calculated results support the previous experimental assignment of the ground and excited states of YbO.%本文用基于精确二分量哈密顿(exact two-component Hamiltonian)的相对论含时密度泛函理论(time-dependent relativistic density functional theory)计算了Yb和YbO的电子激发态,并利用对称性、自然原子轨道对激发态性质和归属进行了详细分析,所得结果支持实验对YbO基态与激发态的指认.
Ioannidou, Theodora
2016-01-01
An extended version of the BPS Skyrme model that admits time-dependent solutions is discussed. Initially, by introducing a power law at the original potential term of the BPS Skyrme model the existence, stability and structure of the corresponding solutions is investigated. Then, the frequencies and half-lifes of the radial oscillations of the constructed time-dependent solutions are determined.
Magnetic fields and density functional theory
Energy Technology Data Exchange (ETDEWEB)
Salsbury Jr., Freddie [Univ. of California, Berkeley, CA (United States)
1999-02-01
A major focus of this dissertation is the development of functionals for the magnetic susceptibility and the chemical shielding within the context of magnetic field density functional theory (BDFT). These functionals depend on the electron density in the absence of the field, which is unlike any other treatment of these responses. There have been several advances made within this theory. The first of which is the development of local density functionals for chemical shieldings and magnetic susceptibilities. There are the first such functionals ever proposed. These parameters have been studied by constructing functionals for the current density and then using the Biot-Savart equations to obtain the responses. In order to examine the advantages and disadvantages of the local functionals, they were tested numerically on some small molecules.
Energy Technology Data Exchange (ETDEWEB)
Tao, Liang; Vanroose, Wim; Reps, Brian; Rescigno, Thomas N.; McCurdy, C. William
2009-09-08
We demonstrate that exterior complex scaling (ECS) can be used to impose outgoing wave boundary conditions exactly on solutions of the time-dependent Schrodinger equation for atoms in intense electromagnetic pulses using finite grid methods. The procedure is formally exact when applied in the appropriate gauge and is demonstrated in a calculation of high harmonic generation in which multiphoton resonances are seen for long pulse durations. However, we also demonstrate that while the application of ECS in this way is formally exact, numerical error can appear for long time propagations that can only be controlled by extending the finite grid. A mathematical analysis of the origins of that numerical error, illustrated with an analytically solvable model, is also given.
Energy Technology Data Exchange (ETDEWEB)
Guedj, C. [University Grenoble Alpes, F-38000 Grenoble (France); CEA, LETI, MINATEC Campus, F-38054 Grenoble (France); Hung, L.; Sottile, F. [LSI, CNRS, CEA, École Polytechnique, F-91128 Palaiseau (France); European Theoretical Spectroscopy Facility (ETSF) (France); Zobelli, A. [LPS, CNRS and University Paris Sud, F-91405 Orsay (France); Blaise, P. [University Grenoble Alpes, F-38000 Grenoble (France); CEA, LETI, MINATEC Campus, F-38054 Grenoble (France); European Theoretical Spectroscopy Facility (ETSF) (France); Olevano, V. [University Grenoble Alpes, F-38000 Grenoble (France); European Theoretical Spectroscopy Facility (ETSF) (France); CNRS, Institut Néel, F-38042 Grenoble (France)
2014-12-01
The effect of nanocrystal orientation on the energy loss spectra of monoclinic hafnia (m-HfO{sub 2}) is measured by high resolution transmission electron microscopy (HRTEM) and valence energy loss spectroscopy (VEELS) on high quality samples. For the same momentum-transfer directions, the dielectric properties are also calculated ab initio by time-dependent density-functional theory (TDDFT). Experiments and simulations evidence anisotropy in the dielectric properties of m-HfO{sub 2}, most notably with the direction-dependent oscillator strength of the main bulk plasmon. The anisotropic nature of m-HfO{sub 2} may contribute to the differences among VEELS spectra reported in literature. The good agreement between the complex dielectric permittivity extracted from VEELS with nanometer spatial resolution, TDDFT modeling, and past literature demonstrates that the present HRTEM-VEELS device-oriented methodology is a possible solution to the difficult nanocharacterization challenges given in the International Technology Roadmap for Semiconductors.
Guedj, C.; Hung, L.; Zobelli, A.; Blaise, P.; Sottile, F.; Olevano, V.
2014-12-01
The effect of nanocrystal orientation on the energy loss spectra of monoclinic hafnia (m-HfO2) is measured by high resolution transmission electron microscopy (HRTEM) and valence energy loss spectroscopy (VEELS) on high quality samples. For the same momentum-transfer directions, the dielectric properties are also calculated ab initio by time-dependent density-functional theory (TDDFT). Experiments and simulations evidence anisotropy in the dielectric properties of m-HfO2, most notably with the direction-dependent oscillator strength of the main bulk plasmon. The anisotropic nature of m-HfO2 may contribute to the differences among VEELS spectra reported in literature. The good agreement between the complex dielectric permittivity extracted from VEELS with nanometer spatial resolution, TDDFT modeling, and past literature demonstrates that the present HRTEM-VEELS device-oriented methodology is a possible solution to the difficult nanocharacterization challenges given in the International Technology Roadmap for Semiconductors.
On time dependent Ekman transports
National Research Council Canada - National Science Library
Roed, L.P
1973-01-01
One of the most cited papers in ocean current theories is the paper by Ekman (1905). Here we take his paper as a starting point for computing time dependent solutions for the integrated velocities or the transports.
Time-Dependent Lagrangian Biomechanics
Ivancevic, Tijana T
2009-01-01
In this paper we present the time-dependent generalization of an 'ordinary' autonomous human musculo-skeletal biomechanics. We start with the configuration manifold of human body, given as a set of its all active degrees of freedom (DOF). This is a Riemannian manifold with a material metric tensor given by the total mass-inertia matrix of the human body segments. This is the base manifold for standard autonomous biomechanics. To make its time-dependent generalization, we need to extend it with a real time axis. On this extended configuration space we develop time-dependent biomechanical Lagrangian dynamics, using derived jet spaces of velocities and accelerations, as well as the underlying geometric evolution of the mass-inertia matrix. Keywords: Human time-dependent biomechanics, configuration manifold, jet spaces, geometric evolution
Rabilloud, Franck
2014-10-14
Absorption spectra of Ag20 and Ag55(q) (q = +1, -3) nanoclusters are investigated in the framework of the time-dependent density functional theory in order to analyse the role of the d electrons in plasmon-like band of silver clusters. The description of the plasmon-like band from calculations using density functionals containing an amount of Hartree-Fock exchange at long range, namely, hybrid and range-separated hybrid (RSH) density functionals, is in good agreement with the classical interpretation of the plasmon-like structure as a collective excitation of valence s-electrons. In contrast, using local or semi-local exchange functionals (generalized gradient approximations (GGAs) or meta-GGAs) leads to a strong overestimation of the role of d electrons in the plasmon-like band. The semi-local asymptotically corrected model potentials also describe the plasmon as mainly associated to d electrons, though calculated spectra are in fairly good agreement with those calculated using the RSH scheme. Our analysis shows that a portion of non-local exchange modifies the description of the plasmon-like band.
Yüksel, Yusuf; Akıncı, Ümit
2016-12-01
Using Monte Carlo simulations, we have investigated the dynamic phase transition properties of magnetic nanoparticles with ferromagnetic core coated by an antiferromagnetic shell structure. Effects of field amplitude and frequency on the thermal dependence of magnetizations, magnetization reversal mechanisms during hysteresis cycles, as well as on the exchange bias and coercive fields have been examined, and the feasibility of applying dynamic magnetic fields on the particle have been discussed for technological and biomedical purposes.
Time-dependent Backgrounds Of String Theory
Maloney, A D
2003-01-01
This thesis is devoted to the study of time-dependent backgrounds in string theory. The first chapter contains a brief, non-technical introduction to the subject. In the second chapter quantum field theory in d-dimensional de Sitter space is studied, with an emphasis on the dS/CFT correspondence. We study a one-parameter family of dS-invariant vacua; this bulk vacuum dependence is dual to a deformation of the boundary CFT by a marginal operator. In odd spacetime dimensions the state with no particles on I- has no particles on I+ , implying the absence of particle production. In Kerr-dS, a thermal density matrix is found by tracing over causally inaccessible modes. Assuming Cardy's formula, the microscopic entropy of such a thermal state in the boundary CFT precisely equals the Bekenstein-Hawking value. Next, we construct de Sitter vacua of supercritical string theories in D > 10 dimensions. Compactifying D − 4 of these dimensions on a carefully constructed asymmetric orientifold projects out t...
Investigations of Low Temperature Time Dependent Cracking
Energy Technology Data Exchange (ETDEWEB)
Van der Sluys, W A; Robitz, E S; Young, B A; Bloom, J
2002-09-30
The objective of this project was to investigate metallurgical and mechanical phenomena associated with time dependent cracking of cold bent carbon steel piping at temperatures between 327 C and 360 C. Boiler piping failures have demonstrated that understanding the fundamental metallurgical and mechanical parameters controlling these failures is insufficient to eliminate it from the field. The results of the project consisted of the development of a testing methodology to reproduce low temperature time dependent cracking in laboratory specimens. This methodology was used to evaluate the cracking resistance of candidate heats in order to identify the factors that enhance cracking sensitivity. The resultant data was integrated into current available life prediction tools.
Time-Dependent Lagrangian Biomechanics
Ivancevic, Tijana T.
2009-01-01
In this paper we present the time-dependent generalization of an 'ordinary' autonomous human musculo-skeletal biomechanics. We start with the configuration manifold of human body, given as a set of its all active degrees of freedom (DOF). This is a Riemannian manifold with a material metric tensor given by the total mass-inertia matrix of the human body segments. This is the base manifold for standard autonomous biomechanics. To make its time-dependent generalization, we need to extend it wit...
Eulerian bias and the galaxy density field
Mann, B M; Heavens, A F; Mann, Bob; Peacock, John; Heavens, Alan
1997-01-01
We investigate the effects on cosmological clustering statistics of empirical biasing, where the galaxy distribution is a local transformation of the present-day Eulerian density field. The effects of the suppression of galaxy numbers in voids, and their enhancement in regions of high density, are considered, independently and in combination. We compare results from numerical simulations with the predictions of simple analytic models. We find that the bias is generally scale-dependent, so that the shape of the galaxy power spectrum differs from that of the underlying mass distribution. The degree of bias is always a monotonic function of scale, tending to an asymptotic value on scales where the density fluctuations are linear. The scale dependence is often rather weak, with many reasonable prescriptions giving a bias which is nearly independent of scale. We have investigated whether such an Eulerian bias can reconcile a range of theoretical power spectra with the twin requirements of fitting the galaxy power ...
Pulsar braking: Time dependent moment of inertia?
Urbanec, Martin
2017-08-01
Pulsars rotate with extremely stable rotational frequency enabling one to measure its first and second time derivatives. These observed values can be combined to the so-called braking index. However observed values of braking index differ from the theoretical value of 3 corresponding to braking by magnetic dipole radiation being the dominant theoretical model. Such a difference can be explained by contribution of other mechanism like pulsar wind or quadrupole radiation, or by time dependency of magnetic field or moment of inertia. In this presentation we focus on influence of time dependent moment of inertia on the braking index. We will also discuss possible physical models for time-dependence of moment of inertia.
Transformation of time dependence to linear algebra
Menšík, Miroslav
2005-10-01
Reduced density matrix and memory function in the Nakajima-Zwanzig equation are expanded in properly chosen basis of special functions. This trick completely transforms time dependence to linear algebra. Then, the master equation for memory function is constructed and expanded in the same basis functions. For the model of a simple harmonic oscillator it is shown that this trick introduces infinite partial summation of the memory function in the system-bath interaction.
Hunt, G. J.; Cowley, S. W. H.; Provan, G.; Bunce, E. J.; Belenkaya, E. S.; Alexeev, I. I.; Kalegaev, V. V.; Dougherty, M. K.; Coates, A. J.
2016-12-01
We examine and compare the magnetic field perturbations associated with field-aligned ionosphere-magnetosphere coupling currents at Saturn, observed by the Cassini spacecraft during two sequences of highly inclined orbits in 2006/7 and 2008 under late southern summer conditions. These sequences explore the southern currents in the dawn-noon and midnight sectors, respectively. This allows investigation of possible origins of the local time (LT) asymmetry in auroral Saturn kilometric radiation (SKR) emissions, which peak in power at 8 h LT in the dawn-noon sector. We first show that the dawn-noon field data generally have the same four-sheet current structure as found previously in the midnight data, and that both are similarly modulated by "planetary period oscillation" (PPO) currents, these being associated with the 10.7 h magnetic field oscillations observed throughout Saturn's magnetosphere. We then separate the averaged PPO-independent (e.g., subcorotation) and PPO-related currents for both LT sectors using the latter current system symmetry properties. Surprisingly, we find that the PPO-independent currents are essentially identical within uncertainties in the dawn-dusk and midnight sectors, thus providing no explanation for the LT dependence of the SKR emissions. The main PPO-related currents are, however, found to be slightly stronger and narrower in latitudinal width at dawn-noon than at midnight, leading to estimated precipitating electron powers, and hence emissions, that are on average a factor of 1.3 larger at dawn-noon than at midnight, inadequate to account for the observed LT asymmetry in SKR power by a factor of 2.7. Some other factor must also be involved, such as a LT asymmetry in the hot magnetospheric auroral source electron population.
Roper, Ian P E; Besley, Nicholas A
2016-03-21
The simulation of X-ray emission spectra of transition metal complexes with time-dependent density functional theory (TDDFT) is investigated. X-ray emission spectra can be computed within TDDFT in conjunction with the Tamm-Dancoff approximation by using a reference determinant with a vacancy in the relevant core orbital, and these calculations can be performed using the frozen orbital approximation or with the relaxation of the orbitals of the intermediate core-ionised state included. Both standard exchange-correlation functionals and functionals specifically designed for X-ray emission spectroscopy are studied, and it is shown that the computed spectral band profiles are sensitive to the exchange-correlation functional used. The computed intensities of the spectral bands can be rationalised by considering the metal p orbital character of the valence molecular orbitals. To compute X-ray emission spectra with the correct energy scale allowing a direct comparison with experiment requires the relaxation of the core-ionised state to be included and the use of specifically designed functionals with increased amounts of Hartree-Fock exchange in conjunction with high quality basis sets. A range-corrected functional with increased Hartree-Fock exchange in the short range provides transition energies close to experiment and spectral band profiles that have a similar accuracy to those from standard functionals.
Zeng, Qiao; Liu, Jie; Liang, WanZhen
2014-05-14
This work extends our previous works [J. Liu and W. Z. Liang, J. Chem. Phys. 135, 014113 (2011); J. Liu and W. Z. Liang, J. Chem. Phys. 135, 184111 (2011)] on analytical excited-state energy Hessian within the framework of time-dependent density functional theory (TDDFT) to couple with molecular mechanics (MM). The formalism, implementation, and applications of analytical first and second energy derivatives of TDDFT/MM excited state with respect to the nuclear and electric perturbations are presented. Their performances are demonstrated by the calculations of adiabatic excitation energies, and excited-state geometries, harmonic vibrational frequencies, and infrared intensities for a number of benchmark systems. The consistent results with the full quantum mechanical method and other hybrid theoretical methods indicate the reliability of the current numerical implementation of developed algorithms. The computational accuracy and efficiency of the current analytical approach are also checked and the computational efficient strategies are suggested to speed up the calculations of complex systems with many MM degrees of freedom. Finally, we apply the current analytical approach in TDDFT/MM to a realistic system, a red fluorescent protein chromophore together with part of its nearby protein matrix. The calculated results indicate that the rearrangement of the hydrogen bond interactions between the chromophore and the protein matrix is responsible for the large Stokes shift.
Time-dependent models of dense PDRs with complex molecules
Morata, O.; Herbst, E.
2008-01-01
We present a study of the chemistry of a dense photon-dominated region (PDR) using a time-dependent chemical model. Our major interest is to study the spatial distribution of complex molecules such as hydrocarbons and cyanopolyynes in the cool dense material bordering regions where star formation has taken place. Our standard model uses a homogeneous cloud of density 2x10e4 cm-3 and temperature T=40 K, which is irradiated by a far-ultraviolet radiation field of intermediate intensity, given b...
Gritsenko, Oleg V; Baerends, Evert Jan
2009-06-14
Time-dependent density functional (response) theory (TDDF(R)T) is applied almost exclusively in its adiabatic approximation (ATDDFT), which is restricted to predominantly single electronic excitations and neglects additional roots of the TDDFT eigenvalue problem stemming from the interaction between single and double excitations. We incorporate the effect of the latter interaction into a non-adiabatic frequency-dependent and spatially non-local Hartree-exchange-correlation (Hxc) kernel fCEDAHxc (r1, r2, omega), the explicit analytical expression of which is derived for interacting single and double excitations well separated from the other excitations, within the common energy denominator approximation (CEDA) for the Kohn-Sham (KS) and interacting density response functions, chis and chi, respectively. The kernel fCEDAHxc (r1, r2, omega) obtained from the direct analytical inverse of chiCEDAs and chiCEDA is a sum of the delta-function and non-local orbital-dependent spatial terms with frequency-dependent factors, with which fCEDAHxc acquires a modulated quadratic dependence on omega. The effective incorporation in fCEDAHxc of the complete manifold of excited states (through the delta function term) represents an extension of the kernel reported by Maitra, Zhang, Cave, and Burke [J. Chem. Phys., 2004, 120, 5932]. In the TDDFT eigenvalue equations considered in the diagonal approximation, fCEDAHxc generates two excitation energies omegaq and omegaq+1, which both correspond to the same single KS excitation omegasq, thus producing the effect of the single-double excitation interaction.
Sato, Yukio; Kono, Hirohiko; Koseki, Shiro; Fujimura, Yuichi
2003-07-02
We theoretically investigated the dynamics of structural deformations of CO(2) and its cations in near-infrared intense laser fields (approximately 10(15) W cm(-2)) by using the time-dependent adiabatic state approach. To obtain "field-following" adiabatic potentials for nuclear dynamics, the electronic Hamiltonian including the interaction with the instantaneous laser electric field is diagonalized by the multiconfiguration self-consistent-field molecular orbital method. In the CO(2) and CO(2+) stages, ionization occurs before the field intensity becomes high enough to deform the molecule. In the CO(2)(2+) stage, simultaneous symmetric two-bond stretching occurs as well as one-bond stretching. Two-bond stretching is induced by an intense field in the lowest time-dependent adiabatic state |1> of CO(2)(2+), and this two-bond stretching is followed by the occurrence of a large-amplitude bending motion mainly in the second-lowest adiabatic state |2> nonadiabatically created at large internuclear distances by the field from |1>. It is concluded that the experimentally observed stretched and bent structure of CO(2)(3+) just before Coulomb explosions originates from the structural deformation of CO(2)(2+). We also show in this report that the concept of "optical-cycle-averaged potential" is useful for designing schemes to control molecular (reaction) dynamics, such as dissociation dynamics of CO(2), in intense fields. The present approach is simple but has wide applicability for analysis and prediction of electronic and nuclear dynamics of polyatomic molecules in intense laser fields.
Time-dependent problems and difference methods
Gustafsson, Bertil; Oliger, Joseph
2013-01-01
Praise for the First Edition "". . . fills a considerable gap in the numerical analysis literature by providing a self-contained treatment . . . this is an important work written in a clear style . . . warmly recommended to any graduate student or researcher in the field of the numerical solution of partial differential equations."" -SIAM Review Time-Dependent Problems and Difference Methods, Second Edition continues to provide guidance for the analysis of difference methods for computing approximate solutions to partial differential equations for time-de
Jose, Linta; Seth, Michael; Ziegler, Tom
2012-02-23
We have applied time dependent density functional theory to study excited state structures of the tetroxo d(0) transition metal complexes MnO(4)(-), TcO(4)(-), RuO(4), and OsO(4). The excited state geometry optimization was based on a newly implemented scheme [Seth et al. Theor. Chem. Acc. 2011, 129, 331]. The first excited state has a C(3v) geometry for all investigated complexes and is due to a "charge transfer" transition from the oxygen based HOMO to the metal based LUMO. The second excited state can uniformly be characterized by "charge transfer" from the oxygen HOMO-1 to the metal LUMO with a D(2d) geometry for TcO(4)(-), RuO(4), and OsO(4) and two C(2v) geometries for MnO(4)(-). It is finally found that the third excited state of MnO(4)(-) representing the HOMO to metal based LUMO+1 orbital transition has a D(2d) geometry. On the basis of the calculated excited state structures and vibrational modes, the Franck-Condon method was used to simulate the vibronic structure of the absorption spectra for the tetroxo d(0) transition metal complexes. The Franck-Condon scheme seems to reproduce the salient features of the experimental spectra as well as the simulated vibronic structure for MnO(4)(-) generated from an alternative scheme [Neugebauer J. J. Phys. Chem. A 2005, 109, 1168] that does not apply the Franck-Condon approximation.
Energy Technology Data Exchange (ETDEWEB)
Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.; Bannan, Caitlin; Strader, Matthew L.; Cho, Hana; Huse, Nils; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira
2013-05-30
Ruthenium L3-edge X-ray absorption (XA) spectroscopy probes unoccupied 4d orbitals of the metal atom and is increasingly being used to investigate the local electronic structure in ground and excited electronic states of Ru complexes. The simultaneous development of computational tools for simulating Ru L3-edge spectra is crucial for interpreting the spectral features at a molecular level. This study demonstrates that time-dependent density functional theory (TDDFT) is a viable and predictive tool for simulating ruthenium L3-edge XA spectroscopy. We systematically investigate the effects of exchange correlation functional and implicit and explicit solvent interactions on a series of RuII and RuIII complexes in their ground and electronic excited states. The TDDFT simulations reproduce all of the experimentally observed features in Ru L3-edge XA spectra within the experimental resolution (0.4 eV). Our simulations identify ligand-specific charge transfer features in complicated Ru L3-edge spectra of [Ru(CN)6]4- and RuII polypyridyl complexes illustrating the advantage of using TDDFT in complex systems. We conclude that the B3LYP functional most accurately predicts the transition energies of charge transfer features in these systems. We use our TDDFT approach to simulate experimental Ru L3-edge XA spectra of transition metal mixed-valence dimers of the form [(NC)5MII-CN-RuIII(NH3)5] (where M = Fe or Ru) dissolved in water. Our study determines the spectral signatures of electron delocalization in Ru L3-edge XA spectra. We find that the inclusion of explicit solvent molecules is necessary for reproducing the spectral features and the experimentally determined valencies in these mixed-valence complexes. This study validates the use of TDDFT for simulating Ru 2p excitations using popular quantum chemistry codes and providing a powerful interpretive tool for equilibrium and ultrafast Ru L3-edge XA spectroscopy.
Farhi, Asaf
2016-01-01
An exact calculation of the local electric field ${\\bf E}({\\bf r})$ is described for the case of a time dependent point electric dipole ${\\bf p}e^{-i\\omega t}$ in the top layer of an $\\epsilon_2$, $\\epsilon_1$, $\\epsilon_2$ three parallel slabs composite structure, where the $\\epsilon_1$ layer has a finite thickness $2d$ but the $\\epsilon_2$ layers are infinitely thick. For this purpose we first calculate all the eigenstates of the full Maxwell equations for the case where $\\mu=1$ everywhere in the system. The eigenvalues appear as special, non-physical values of $\\epsilon_1$ when $\\epsilon_2$ is given. These eigenstates are then used to develop an exact expansion for the physical values of ${\\bf E}({\\bf r})$ in the system characterized by physical values of $\\epsilon_1(\\omega)$ and $\\epsilon_2(\\omega)$. Results are compared with those of a previous calculation of the local field of a time dependent point charge in the quasi-static regime. Numerical results are shown for the local electric field in practicall...
Time dependence of immersion freezing
Directory of Open Access Journals (Sweden)
A. Welti
2012-05-01
Full Text Available The time dependence of immersion freezing was studied for temperatures between 236 K and 243 K. Droplets with single immersed, size-selected 400 nm and 800 nm kaolinite particles were produced at 300 K, cooled down to supercooled temperatures typical for mixed-phase cloud conditions, and the fraction of frozen droplets with increasing residence time was detected. To simulate the conditions of immersion freezing in mixed-phase clouds we used the Zurich Ice Nucleation Chamber (ZINC and its vertical extension, the Immersion Mode Cooling chAmber (IMCA. We observed that the frozen fraction of droplets increased with increasing residence time in the chamber. This suggests that there is a time dependence of immersion freezing and supports the importance of a stochastic component in the ice nucleation process. The rate at which droplets freeze was observed to decrease towards higher temperatures and smaller particle sizes. Comparison of the laboratory data with four different ice nucleation models, three based on classical nucleation theory with different representations of the particle surface properties and one singular, suggest that the classical, stochastic approach combined with a distribution of contact angles is able to reproduce the ice nucleation observed in these experiments most accurately. Using the models to calculate the increase in frozen fraction at typical mixed-phase cloud temperatures over an extended period of time, yields an equivalent effect of −1 K temperature shift and an increase in time scale by a factor of ~10.
DEFF Research Database (Denmark)
Rotvig, J.; Smith, H.; Jauho, Antti-Pekka
1996-01-01
We present an analytical study of one-dimensional semiconductor superlattices in external electric fields, which may be time dependent. A number of general results for the (quasi)energies and eigenstates are derived. An equation of motion for the density matrix is obtained for a two-band model an....... 74, 1831 (1995)], where a set of numerical simulations was presented....
Time-dependent Cooling in Photoionized Plasma
Gnat, Orly
2017-02-01
I explore the thermal evolution and ionization states in gas cooling from an initially hot state in the presence of external photoionizing radiation. I compute the equilibrium and nonequilibrium cooling efficiencies, heating rates, and ion fractions for low-density gas cooling while exposed to the ionizing metagalactic background radiation at various redshifts (z = 0 ‑ 3), for a range of temperatures (108–104 K), densities (10‑7–103 cm‑3), and metallicities (10‑3–2 times solar). The results indicate the existence of a threshold ionization parameter, above which the cooling efficiencies are very close to those in photoionization equilibrium (so that departures from equilibrium may be neglected), and below which the cooling efficiencies resemble those in collisional time-dependent gas cooling with no external radiation (and are thus independent of density).
Dissipative time-dependent quantum transport theory.
Zhang, Yu; Yam, Chi Yung; Chen, GuanHua
2013-04-28
A dissipative time-dependent quantum transport theory is developed to treat the transient current through molecular or nanoscopic devices in presence of electron-phonon interaction. The dissipation via phonon is taken into account by introducing a self-energy for the electron-phonon coupling in addition to the self-energy caused by the electrodes. Based on this, a numerical method is proposed. For practical implementation, the lowest order expansion is employed for the weak electron-phonon coupling case and the wide-band limit approximation is adopted for device and electrodes coupling. The corresponding hierarchical equation of motion is derived, which leads to an efficient and accurate time-dependent treatment of inelastic effect on transport for the weak electron-phonon interaction. The resulting method is applied to a one-level model system and a gold wire described by tight-binding model to demonstrate its validity and the importance of electron-phonon interaction for the quantum transport. As it is based on the effective single-electron model, the method can be readily extended to time-dependent density functional theory.
Fraaije, JGEM; vanVlimmeren, BAC; Maurits, NM; Postma, M; Evers, OA; Hoffmann, C; Altevogt, P; GoldbeckWood, G
1997-01-01
In this paper we discuss a new generalized time-dependent Ginzburg-Landau theory for the numerical calculation of polymer phase separation kinetics in 3D. The thermodynamic forces are obtained by a mean-field density functional method, using a Gaussian chain as a molecular model. The method is
Institute of Scientific and Technical Information of China (English)
张红; 尹海峰; 张开彪; 林家和
2015-01-01
纳米粒子的局域表面等离激元(LSP)由于其新颖的光学特性成为目前国内外研究的热点之一。本文利用含时密度泛函理论(TDDFT)对金属团簇及石墨烯纳米结构中的等离激元激发及调制的物理本质进行了研究。和宏观大小的材料相比，由于纳米结构的尺寸和量子受限效应，纳米结构的等离激元具有一些不同的特征。在低能共振区，光谱线发生展宽，并且发生劈裂。由于纳米单体间的电磁耦合作用，使聚合的纳米结构表现出了与单体不同的光学性质。这些结果为等离激元的调控提供了坚实的理论指导。%Localized surface plasmon (LSP) of nanoparticles has become one of the world’s research hotspots due to its novel optical properties. Based on the time-dependent density functional theory (TDDFT), this paper studies the physical nature of plasmon excitation which is modulated in metal clusters and graphene nanostructures. Compared with the plasmon in the macroscopic material, the plasmon in nanostructures has some different properties due to the effects of the size and the dimensional confinement. In lower-energy resonance zone, the spectral band is greatly broadened, and the photoabsorption strength line splits. Because of the electromagnetic coupling between the nano-monomers, aggregated nanostructures exhibit different optical properties. For plasmon regulation and control, these results provide a solid theoretical guidance.
Time-dependent Dyson orbital theory.
Gritsenko, O V; Baerends, E J
2016-08-21
Although time-dependent density functional theory (TDDFT) has become the tool of choice for real-time propagation of the electron density ρ(N)(t) of N-electron systems, it also encounters problems in this application. The first problem is the neglect of memory effects stemming from the, in TDDFT virtually unavoidable, adiabatic approximation, the second problem is the reliable evaluation of the probabilities P(n)(t) of multiple photoinduced ionization, while the third problem (which TDDFT shares with other approaches) is the reliable description of continuum states of the electrons ejected in the process of ionization. In this paper time-dependent Dyson orbital theory (TDDOT) is proposed. Exact TDDOT equations of motion (EOMs) for time-dependent Dyson orbitals are derived, which are linear differential equations with just static, feasible potentials of the electron-electron interaction. No adiabatic approximation is used, which formally resolves the first TDDFT problem. TDDOT offers formally exact expressions for the complete evolution in time of the wavefunction of the outgoing electron. This leads to the correlated probability of single ionization P(1)(t) as well as the probabilities of no ionization (P(0)(t)) and multiple ionization of n electrons, P(n)(t), which formally solves the second problem of TDDFT. For two-electron systems a proper description of the required continuum states appears to be rather straightforward, and both P(1)(t) and P(2)(t) can be calculated. Because of the exact formulation, TDDOT is expected to reproduce a notorious memory effect, the "knee structure" of the non-sequential double ionization of the He atom.
Network-timing-dependent plasticity
Directory of Open Access Journals (Sweden)
Vincent eDelattre
2015-06-01
Full Text Available Bursts of activity in networks of neurons are thought to convey salient information and drive synaptic plasticity. Here we report that network bursts also exert a profound effect on Spike-Timing-Dependent Plasticity (STDP. In acute slices of juvenile rat somatosensory cortex we paired a network burst, which alone induced long-term depression (LTD, with STDP-induced long-term potentiation and depression (LTP and LTD. We observed that STDP-induced LTP was either unaffected, blocked or flipped into LTD by the network burst, and that STDP-induced LTD was either saturated or flipped into LTP, depending on the relative timing of the network burst with respect to spike coincidences of the STDP event. We hypothesized that network bursts flip STDP-induced LTP to LTD by depleting resources needed for LTP and therefore developed a resource-dependent STDP learning rule. In a model neural network under the influence of the proposed resource-dependent STDP rule, we found that excitatory synaptic coupling was homeostatically regulated to produce power law distributed burst amplitudes reflecting self-organized criticality, a state that ensures optimal information coding.
Network-timing-dependent plasticity.
Delattre, Vincent; Keller, Daniel; Perich, Matthew; Markram, Henry; Muller, Eilif B
2015-01-01
Bursts of activity in networks of neurons are thought to convey salient information and drive synaptic plasticity. Here we report that network bursts also exert a profound effect on Spike-Timing-Dependent Plasticity (STDP). In acute slices of juvenile rat somatosensory cortex we paired a network burst, which alone induced long-term depression (LTD), with STDP-induced long-term potentiation (LTP) and LTD. We observed that STDP-induced LTP was either unaffected, blocked or flipped into LTD by the network burst, and that STDP-induced LTD was either saturated or flipped into LTP, depending on the relative timing of the network burst with respect to spike coincidences of the STDP event. We hypothesized that network bursts flip STDP-induced LTP to LTD by depleting resources needed for LTP and therefore developed a resource-dependent STDP learning rule. In a model neural network under the influence of the proposed resource-dependent STDP rule, we found that excitatory synaptic coupling was homeostatically regulated to produce power law distributed burst amplitudes reflecting self-organized criticality, a state that ensures optimal information coding.
Propulsion Physics Under the Changing Density Field Model
Robertson, Glen A.
2011-01-01
To grow as a space faring race, future spaceflight systems will requires new propulsion physics. Specifically a propulsion physics model that does not require mass ejection without limiting the high thrust necessary to accelerate within or beyond our solar system and return within a normal work period or lifetime. In 2004 Khoury and Weltman produced a density dependent cosmology theory they called Chameleon Cosmology, as at its nature, it is hidden within known physics. This theory represents a scalar field within and about an object, even in the vacuum. Whereby, these scalar fields can be viewed as vacuum energy fields with definable densities that permeate all matter; having implications to dark matter/energy with universe acceleration properties; implying a new force mechanism for propulsion physics. Using Chameleon Cosmology, the author has developed a new propulsion physics model, called the Changing Density Field (CDF) Model. This model relates to density changes in these density fields, where the density field density changes are related to the acceleration of matter within an object. These density changes in turn change how an object couples to the surrounding density fields. Whereby, thrust is achieved by causing a differential in the coupling to these density fields about an object. Since the model indicates that the density of the density field in an object can be changed by internal mass acceleration, even without exhausting mass, the CDF model implies a new propellant-less propulsion physics model
McMahon, S.; Amirjalayer, S.; Buma, W.J.; Halpin, Y.; Long, C.; Rooney, A.D.; Woutersen, S.; Pryce, M.T.
2015-01-01
The photophysics and photochemistry of [(CO)(5)MC(OMe)Me] (M = Cr or W) were investigated using pico-second time-resolved infrared spectroscopy (M = Cr or W), low-temperature matrix isolation techniques (M = Cr), and time-dependent density functional calculations (M = Cr or W). These studies provide
The density field of the local Universe
Energy Technology Data Exchange (ETDEWEB)
Saunders, Will (Oxford Univ. (UK). Dept. of Astrophysics Queen Mary and Westfield Coll., London (UK). Astronomy Unit); Frenk, Carlos (Durham Univ. (UK). Dept. of Physics); Rowan-Robinson, Michael (Queen Mary and Westfield Coll., London (UK). Astronomy Unit) (and others)
1991-01-03
An all-sky redshift survey of galaxies detected by IRAS (the Infrared Astronomical Satellite) has been used to map the Universe out to 140h{sup -1} Mpc (the Hubble constant H{sub 0} identical to 100h km s{sup -1} Mpc{sup -1}). Well-known superclusters and voids are seen, as are others not previously identified. The inferred underlying distribution of density is found to be skewed to high densities (the voids are larger than the superclusters but depart less from the mean density); and there is more structure on large scales than is predicted by the standard cold dark matter theory of galaxy formation. (author).
Holographic Complexity for Time-Dependent Backgrounds
Momeni, Davood; Bahamonde, Sebastian; Myrzakulov, Ratbay
2016-01-01
In this paper, we will analyse the holographic complexity for time-dependent asymptotically $AdS$ geometries. We will first use a covariant zero mean curvature slicing of the time-dependent bulk geometries, and then use this co-dimension one spacelike slice of the bulk spacetime to define a co-dimension two minimal surface. The time-dependent holographic complexity will be defined using the volume enclosed by this minimal surface. This time-dependent holographic complexity will reduce to the usual holographic complexity for static geometries. We will analyse the time-dependence as a perturbation of the asymptotically $AdS$ geometries. Thus, we will obtain time-dependent asymptotically $AdS$ geometries, and we will calculate the holographic complexity for such a time-dependent geometries.
Acoustic Force Density Acting on Inhomogeneous Fluids in Acoustic Fields
DEFF Research Database (Denmark)
Karlsen, Jonas Tobias; Augustsson, Per; Bruus, Henrik
2016-01-01
We present a theory for the acoustic force density acting on inhomogeneous fluids in acoustic fields on time scales that are slow compared to the acoustic oscillation period. The acoustic force density depends on gradients in the density and compressibility of the fluid. For microfluidic systems...
Constitutive model with time-dependent deformations
DEFF Research Database (Denmark)
Krogsbøll, Anette
1998-01-01
are common in time as well as size. This problem is adressed by means of a new constitutive model for soils. It is able to describe the behavior of soils at different deformation rates. The model defines time-dependent and stress-related deformations separately. They are related to each other and they occur......In many geological and Engineering problems it is necessary to transform information from one scale to another. Data collected at laboratory scale are often used to evaluate field problems on a much larger scale. This is certainly true for geological problems where extreme scale differences...... simultanelously. The model is based on concepts from elasticity and viscoplasticity theories. In addition to Hooke's law for the elastic behavior, the framework for the viscoplastic behavior consists, in the general case (two-dimensional or three-dimensional), of a yield surface, an associated flow rule...
Sipkin, S.A.; Silver, P.G.
2003-01-01
We present a method for summing moment tensors derived from first-motion focal mechanisms to study temporal dependence in features of the subsurface regional strain field. Time-dependent processes are inferred by comparing mechanisms summed over differing time periods. We apply this methodology to seismogenic zones in central and southern California using focal mechanisms produced by the Northern and Southern California Seismograph Networks for events during 1980-1999. We find a consistent pattern in both the style of deformation (strike-slip versus compressional) and seismicity rate across the entire region. If these temporal variations are causally related, it suggests a temporal change in the regional-scale stress field. One change consistent with the observations is a rotation in the regional maximum horizontal compressive stress direction, followed by a reversal to the original direction. Depending upon the dominant style of deformation locally, this change in orientation of the regional stress will tend to either enhance or hinder deformation. The mode of enhanced deformation can range from increased microseismicity and creep to major earthquakes. We hypothesize that these temporal changes in the regional stress field are the result of subtle changes in apparent relative plate motion between the Pacific and North American plates, perhaps due to long-range postseismic stress diffusion. Others have hypothesized that small changes in plate motion over thousands of years, and/or over decades, are responsible for changes in the style of deformation in southern California. We propose that such changes, over the course of just a few years, also affect the style of deformation.
Three dimensional density cavities in guide field collisionless magnetic reconnection
Markidis, Stefano; Divin, Andrey; Goldman, Martin V; Newman, D; Andersson, Laila
2012-01-01
Particle-in-Cell simulations of collisionless magnetic reconnection with a guide field reveal for the first time the three dimensional features of the low density regions along the magnetic reconnection separatrices, the so-called "cavities". It is found that structures with further lower density develop within the cavities. Because their appearance is similar to the rib shape, these formations are here called "low density ribs". Their location remains approximately fixed in time and their density progressively decreases, as electron currents along the cavities evacuate them. They develop along the magnetic field lines and are supported by a strong perpendicular electric field that oscillates in space. In addition, bipolar parallel electric field structures form as isolated spheres between the cavities and the outflow plasma, along the direction of the low density ribs and of magnetic field lines.
Using Spatial Density to Characterize Volcanic Fields on Mars
Richardson, J. A.; Bleacher, J. E.; Connor, C. B.; Connor, L. J.
2012-01-01
We introduce a new tool to planetary geology for quantifying the spatial arrangement of vent fields and volcanic provinces using non parametric kernel density estimation. Unlike parametricmethods where spatial density, and thus the spatial arrangement of volcanic vents, is simplified to fit a standard statistical distribution, non parametric methods offer more objective and data driven techniques to characterize volcanic vent fields. This method is applied to Syria Planum volcanic vent catalog data as well as catalog data for a vent field south of Pavonis Mons. The spatial densities are compared to terrestrial volcanic fields.
Time-dependent models of dense PDRs with complex molecules
Morata, O
2008-01-01
We present a study of the chemistry of a dense photon-dominated region (PDR) using a time-dependent chemical model. Our major interest is to study the spatial distribution of complex molecules such as hydrocarbons and cyanopolyynes in the cool dense material bordering regions where star formation has taken place. Our standard model uses a homogeneous cloud of density 2x10e4 cm-3 and temperature T=40 K, which is irradiated by a far-ultraviolet radiation field of intermediate intensity, given by X=100. We find that over a range of times unsaturated hydrocarbons (e.g., C2H, C4H, C3H2) have relatively high fractional abundances in the more external layers of the PDR, whereas their abundances in the innermost layers are several orders of magnitudes lower. On the other hand, molecules that are typical of late-time chemistry are usually more abundant in the inner parts of the PDR. We also present results for models with different density, temperature, intensity of the radiation field and initial fractional abundance...
Energy Technology Data Exchange (ETDEWEB)
Koshelev, A. E.; Sadovskyy, I. A.; Phillips, C. L.; Glatz, A.
2016-02-29
Introducing nanoparticles into superconducting materials has emerged as an efficient route to enhance their current-carrying capability. We address the problem of optimizing vortex pinning landscape for randomly distributed metallic spherical inclusions using large-scale numerical simulations of time- dependent Ginzburg-Landau equations. We found the size and density of particles for which the highest critical current is realized in a fixed magnetic field. For each particle size and magnetic field, the critical current reaches a maximum value at a certain particle density, which typically corresponds to 15{23% of the total volume being replaced by nonsuperconducting material. For fixed diameter, this optimal particle density increases with the magnetic field. Moreover, we found that the optimal particle diameter slowly decreases with the magnetic field from 4.5 to 2.5 coherence lengths at a given temperature. This result shows that pinning landscapes have to be designed for specific applications taking into account relevant magnetic field scales.
Direct imaging of small scatterers using reduced time dependent data
Cakoni, Fioralba; Rezac, Jacob D.
2017-06-01
We introduce qualitative methods for locating small objects using time dependent acoustic near field waves. These methods have reduced data collection requirements compared to typical qualitative imaging techniques. In particular, we only collect scattered field data in a small region surrounding the location from which an incident field was transmitted. The new methods are partially theoretically justified and numerical simulations demonstrate their efficacy. We show that these reduced data techniques give comparable results to methods which require full multistatic data and that these time dependent methods require less scattered field data than their time harmonic analogs.
The Time-Dependent Chemistry of Cometary Debris in the Solar Corona
Pesnell, W. D.; Bryans, P.
2015-01-01
Recent improvements in solar observations have greatly progressed the study of sungrazing comets. They can now be imaged along the entirety of their perihelion passage through the solar atmosphere, revealing details of their composition and structure not measurable through previous observations in the less volatile region of the orbit further from the solar surface. Such comets are also unique probes of the solar atmosphere. The debris deposited by sungrazers is rapidly ionized and subsequently influenced by the ambient magnetic field. Measuring the spectral signature of the deposited material highlights the topology of the magnetic field and can reveal plasma parameters such as the electron temperature and density. Recovering these variables from the observable data requires a model of the interaction of the cometary species with the atmosphere through which they pass. The present paper offers such a model by considering the time-dependent chemistry of sublimated cometary species as they interact with the solar radiation field and coronal plasma. We expand on a previous simplified model by considering the fully time-dependent solutions of the emitting species' densities. To compare with observations, we consider a spherically symmetric expansion of the sublimated material into the corona and convert the time-dependent ion densities to radial profiles. Using emissivities from the CHIANTI database and plasma parameters derived from a magnetohydrodynamic simulation leads to a spatially dependent emission spectrum that can be directly compared with observations. We find our simulated spectra to be consistent with observation.
Bohr Hamiltonian with time-dependent potential
Naderi, L.; Hassanabadi, H.; Sobhani, H.
2016-04-01
In this paper, Bohr Hamiltonian has been studied with the time-dependent potential. Using the Lewis-Riesenfeld dynamical invariant method appropriate dynamical invariant for this Hamiltonian has been constructed and the exact time-dependent wave functions of such a system have been derived due to this dynamical invariant.
Competing risks and time-dependent covariates
DEFF Research Database (Denmark)
Cortese, Giuliana; Andersen, Per K
2010-01-01
Time-dependent covariates are frequently encountered in regression analysis for event history data and competing risks. They are often essential predictors, which cannot be substituted by time-fixed covariates. This study briefly recalls the different types of time-dependent covariates...
Perturbation Theory of the Cosmological Log-Density Field
Wang, Xin; Szapudi, István; Szalay, Alex; Chen, Xuelei; Lesgourgues, Julien; Riotto, Antonio; Sloth, Martin; 10.1088/0004-637X/735/1/32
2011-01-01
The matter density field exhibits a nearly lognormal probability density distribution (PDF) after entering into the nonlinear regime. Recently, it has been shown that the shape of the power spectrum of a logarithmically transformed density field is very close to the linear density power spectrum, motivating an analytic study of it. In this paper, we develop cosmological perturbation theory for the power spectrum of this field. Our formalism is developed in the context of renormalized perturbation theory, which helps to regulate the convergence behavior of the perturbation series, and of the Taylor- series expansion we use of the logarithmic mapping. This approach allows us to handle the critical issue of density smoothing in a straightforward way. We also compare our perturbative results with simulation measurements.
Density functional theory of the crystal field in dioxides
Diviš, M.; Kuriplach, J.; Richter, M.; Steinbeck, L.
1996-04-01
Presented are the results of ab-initio density functional calculations for PrO2 and UO2 using the general potential LAPW and optimized LCAO method in the local density approximation. The crystal field splitting of ionic Pr4+ and U4+ ground states was calculated and compared with predictions of a superposition model.
Nazemi, Sanaz; Pourfath, Mahdi; Soleimani, Ebrahim Asl; Kosina, Hans
2016-04-01
Due to their tunable properties, silicon nano-crystals (NC) are currently being investigated. Quantum confinement can generally be employed for size-dependent band-gap tuning at dimensions smaller than the Bohr radius (˜5 nm for silicon). At the nano-meter scale, however, increased surface-to-volume ratio makes the surface effects dominant. Specifically, in Si-SiO2 core-shell semiconductor NCs the interfacial transition layer causes peculiar electronic and optical properties, because of the co-existence of intermediate oxidation states of silicon (Sin+, n = 0-4). Due to the presence of the many factors involved, a comprehensive understanding of the optical properties of these NCs has not yet been achieved. In this work, Si-SiO2 NCs with a diameter of 1.1 nm and covered by amorphous oxide shells with thicknesses between 2.5 and 4.75 Å are comprehensively studied, employing density functional theory calculations. It is shown that with increased oxide shell thickness, the low-energy part of the optical transition spectrum of the NC is red shifted and attenuated. Moreover, the absorption coefficient is increased in the high-energy part of the spectrum which corresponds to SiO2 transitions. Structural examinations indicate a larger compressive stress on the central silicon cluster with a thicker oxide shell. Examination of the local density of states reveals the migration of frontier molecular orbitals from the oxide shell into the silicon core with the increase of silica shell thickness. The optical and electrical properties are explained through the analysis of the density of states and the spatial distribution of silicon sub-oxide species.
Time dependent friction in a free gas
Fanelli, Cristiano; Sisti, Francesco; Stagno, Gabriele V.
2016-03-01
We consider a body moving in a perfect gas, described by the mean-field approximation and interacting elastically with the body, we study the friction exerted by the gas on the body fixed at constant velocities. The time evolution of the body in this setting was studied in Caprino et al. [Math. Phys. 264, 167-189 (2006)], Caprino et al. [Math. Models Methods Appl. Sci. 17, 1369-1403 (2007)], and Cavallaro [Rend. Mat. Appl. 27, 123-145 (2007)] for object with simple shape; the first study where a simple kind of concavity was considered was in Sisti and Ricciuti [SIAM J. Math. Anal. 46, 3759-3611 (2014)], showing new features in the dynamic but not in the friction term. The case of more general shape of the body was left out for further difficulties, and we believe indeed that there are actually non-trivial issues to be faced for these more general cases. To show this and in the spirit of getting a more realistic perspective in the study of friction problems, in this paper, we focused our attention on the friction term itself, studying its behavior on a body with a more general kind of concavity and fixed at constant velocities. We derive the expression of the friction term for constant velocities, we show how it is time dependent, and we give its exact estimate in time. Finally, we use this result to show the absence of a constant velocity in the actual dynamic of such a body.
Enhancement of electric and magnetic wave fields at density gradients
Directory of Open Access Journals (Sweden)
A. Reiniusson
2006-03-01
Full Text Available We use Freja satellite data to investigate irregular small-scale density variations. The observations are made in the auroral region at about 1000-1700 km. The density variations are a few percent, and the structures are found to be spatial down to a scale length of a few ion gyroradii. Irregular density variations are often found in an environment of whistler mode/lower hybrid waves and we show that at the density gradients both the electric and magnetic wave fields are enhanced.
Proton Radiography as an electromagnetic field and density perturbation diagnostic
Energy Technology Data Exchange (ETDEWEB)
Mackinnon, A; Patel, P; Town, R; Edwards, M; Phillips, T; Lerner, S; Price, D; Hicks, D; Key, M; Hatchett, S; Wilks, S; King, J; Snavely, R; Freeman, R; Boehlly, T; Koenig, M; Martinolli, E; Lepape, S; Benuzzi-Mounaix, A; Audebert, P; Gauthier, J; Borghesi, M; Romagnani, L; Toncian, T; Pretzler, G; Willi, O
2004-04-15
Laser driven proton beams have been used to diagnose transient fields and density perturbations in laser produced plasmas. Grid deflectometry techniques have been applied to proton radiography to obtain precise measurements of proton beam angles caused by electromagnetic fields in laser produced plasmas. Application of proton radiography to laser driven implosions has demonstrated that density conditions in compressed media can be diagnosed with MeV protons. This data has shown that proton radiography can provide unique insight into transient electromagnetic fields in super critical density plasmas and provide a density perturbation diagnostics in compressed matter . PACS numbers: 52.50.Jm, 52.40.Nk, 52.40.Mj, 52.70.Kz
Vikas, Hash(0xb7f6e60)
2012-01-01
Hydrogen molecule in a strong ultrashort magnetic field is investigated through a current-density functional theory (CDFT) and quantum fluid dynamics (QFD) based approach employing current-density dependent vector exchange-correlation potential and energy density functional derived with a vorticity variable. The numerical computations through the CDFT based approach are performed for the H2 molecule, starting initially from its field-free ground state, in a parallel internuclear axis and magnetic field-axis configuration with the internuclear separation R ranging from 0.1 a.u. to 14.0 a.u., and the strength of the time-dependent (TD) magnetic field varying between 0-1011 G over a few femtoseconds. The numerical results are compared with that obtained using an approach based on the current-density independent approximation under similar computational constraints but employing only scalar exchange-correlation potential dependent on the electronic charge-density alone. The current-density based approach yields exchange- and correlation energy as well as electronic charge-density of the H2 molecule drastically different from that obtained using current-independent approach, in particular, at TD magnetic field-strengths >109 G during a typical time-period of the field when the magnetic-field had attained maximum applied field-strength and is switched to a decreasing ramp function. This nonadiabatic behavior of the TD electronic charge-density is traced to the TD vorticity-dependent vector exchange-correlation potential of the CDFT based approach. The interesting electron dynamics of the H2 molecule in strong TD magnetic field is further elucidated by treating electronic charge-density as an `electron-fluid'. The present work also reveals interesting real-time dynamics on the attosecond time-scale in the electronic charge-density distribution of the hydrogen molecule.
ALCHEMIC: Advanced time-dependent chemical kinetics
Semenov, Dmitry A.
2017-08-01
ALCHEMIC solves chemical kinetics problems, including gas-grain interactions, surface reactions, deuterium fractionization, and transport phenomena and can model the time-dependent chemical evolution of molecular clouds, hot cores, corinos, and protoplanetary disks.
Estimating neuronal connectivity from axonal and dendritic density fields
van Pelt, Jaap; van Ooyen, Arjen
2013-01-01
Neurons innervate space by extending axonal and dendritic arborizations. When axons and dendrites come in close proximity of each other, synapses between neurons can be formed. Neurons vary greatly in their morphologies and synaptic connections with other neurons. The size and shape of the arborizations determine the way neurons innervate space. A neuron may therefore be characterized by the spatial distribution of its axonal and dendritic “mass.” A population mean “mass” density field of a particular neuron type can be obtained by averaging over the individual variations in neuron geometries. Connectivity in terms of candidate synaptic contacts between neurons can be determined directly on the basis of their arborizations but also indirectly on the basis of their density fields. To decide when a candidate synapse can be formed, we previously developed a criterion defining that axonal and dendritic line pieces should cross in 3D and have an orthogonal distance less than a threshold value. In this paper, we developed new methodology for applying this criterion to density fields. We show that estimates of the number of contacts between neuron pairs calculated from their density fields are fully consistent with the number of contacts calculated from the actual arborizations. However, the estimation of the connection probability and the expected number of contacts per connection cannot be calculated directly from density fields, because density fields do not carry anymore the correlative structure in the spatial distribution of synaptic contacts. Alternatively, these two connectivity measures can be estimated from the expected number of contacts by using empirical mapping functions. The neurons used for the validation studies were generated by our neuron simulator NETMORPH. An example is given of the estimation of average connectivity and Euclidean pre- and postsynaptic distance distributions in a network of neurons represented by their population mean density
Generating time dependent conformally coupled Einstein-scalar solutions
Sultana, Joseph
2015-07-01
Using the correspondence between a minimally coupled scalar field and an effective stiff perfect fluid with or without a cosmological constant, we present a simple method for generating time dependent Einstein-scalar solutions with a conformally coupled scalar field that has vanishing or non-vanishing potential. This is done by using Bekenstein's transformation on Einstein-scalar solutions with minimally coupled massless scalar fields, and its later generalization by Abreu et al. to massive fields. In particular we obtain two new spherically symmetric time dependent solutions to the coupled system of Einstein's and the conformal scalar field equations, with one of the solutions having a Higgs' type potential for the scalar field, and we study their properties.
Time-dependent stabilization in AdS/CFT
Auzzi, Roberto; Gudnason, Sven Bjarke; Rabinovici, Eliezer
2012-01-01
We consider theories with time-dependent Hamiltonians which alternate between being bounded and unbounded from below. For appropriate frequencies dynamical stabilization can occur rendering the effective potential of the system stable. We first study a free field theory on a torus with a time-dependent mass term, finding that the stability regions are described in terms of the phase diagram of the Mathieu equation. Using number theory we have found a compactification scheme such as to avoid resonances for all momentum modes in the theory. We further consider the gravity dual of a conformal field theory on a sphere in three spacetime dimensions, deformed by a doubletrace operator. The gravity dual of the theory with a constant unbounded potential develops big crunch singularities; we study when such singularities can be cured by dynamical stabilization. We numerically solve the Einstein-scalar equations of motion in the case of a time-dependent doubletrace deformation and find that for sufficiently high freque...
Dependence of the critical current density on the first matching field density
Energy Technology Data Exchange (ETDEWEB)
Obaidat, I.M. [Department of Physics, United Arab Emirates University, Al-Ain 17551 (United Arab Emirates)], E-mail: iobaidat@uaeu.ac.ae; Benkraouda, M.; Khawaja, U. Al [Department of Physics, United Arab Emirates University, Al-Ain 17551 (United Arab Emirates)
2008-10-01
Molecular dynamic simulations were carried out to investigate the properties of the critical depinning force in high temperature superconductors at several vortex densities at the first matching field. The study was conducted on samples with periodic square arrays of vortices and pinning sites. The variables in the simulations were the vortex density, the pinning sites density, the temperature, the pinning strength, the size of pinning sites. The critical depinning force is found to decrease with temperature for all first matching field densities. The rate of this decrease was found to be slower as the pinning strength and size of pinning site gets larger. At low temperatures and for large pinning strengths, the critical depinning force was found to decrease with increasing the first matching field density. But very interesting results were obtained at moderate temperatures where the critical depinning force was found to increase as the first matching field density increases. The same behavior of the critical depinning force was found at low temperatures, for small pinning strengths. These unexpected results were attributed to a vortex structural phase transition from a disordered state to an ordered state.
Rf Gun with High-Current Density Field Emission Cathode
Energy Technology Data Exchange (ETDEWEB)
Jay L. Hirshfield
2005-12-19
High current-density field emission from an array of carbon nanotubes, with field-emission-transistor control, and with secondary electron channel multiplication in a ceramic facing structure, have been combined in a cold cathode for rf guns and diode guns. Electrodynamic and space-charge flow simulations were conducted to specify the cathode configuration and range of emission current density from the field emission cold cathode. Design of this cathode has been made for installation and testing in an existing S-band 2-1/2 cell rf gun. With emission control and modulation, and with current density in the range of 0.1-1 kA/cm2, this cathode could provide performance and long-life not enjoyed by other currently-available cathodes
Classical and quantum time dependent solutions in string theory
Mart'inez-Prieto, C; Socorro, J
2004-01-01
Using the ontological interpretation of quantum mechanics in a particular sense, we obtain the classical behaviour of the scale factor and two scalar fields, derived from a string effective action for the FRW time dependent model. Besides, the Wheeler-DeWitt equation is solved exactly. We speculate that the same procedure could also be applied to S-branes.
Finite baryon density effects on gauge field dynamics
Bödeker, Dietrich
2001-01-01
We discuss the effective action for QCD gauge fields at finite temperatures and densities, obtained after integrating out the hardest momentum scales from the system. We show that a non-vanishing baryon density induces a charge conjugation (C) odd operator to the gauge field action, proportional to the chemical potential. Even though it is parametrically smaller than the leading C even operator, it could have an important effect on C odd observables. The same operator appears to be produced by classical kinetic theory, allowing in principle for a non-perturbative study of such processes.
Large Scale Magnetic Fields: Density Power Spectrum in Redshift Space
Indian Academy of Sciences (India)
Rajesh Gopal; Shiv K. Sethi
2003-09-01
We compute the density redshift-space power spectrum in the presence of tangled magnetic fields and compare it with existing observations. Our analysis shows that if these magnetic fields originated in the early universe then it is possible to construct models for which the shape of the power spectrum agrees with the large scale slope of the observed power spectrum. However requiring compatibility with observed CMBR anisotropies, the normalization of the power spectrum is too low for magnetic fields to have significant impact on the large scale structure at present. Magnetic fields of a more recent origin generically give density power spectrum ∝ 4 which doesn’t agree with the shape of the observed power spectrum at any scale. Magnetic fields generate curl modes of the velocity field which increase both the quadrupole and hexadecapole of the redshift space power spectrum. For curl modes, the hexadecapole dominates over quadrupole. So the presence of curl modes could be indicated by an anomalously large hexadecapole, which has not yet been computed from observation. It appears difficult to construct models in which tangled magnetic fields could have played a major role in shaping the large scale structure in the present epoch. However if they did, one of the best ways to infer their presence would be from the redshift space effects in the density power spectrum.
Jet Methods in Time-Dependent Lagrangian Biomechanics
Ivancevic, Tijana T
2009-01-01
In this paper we propose the time-dependent generalization of an `ordinary' autonomous human biomechanics, in which total mechanical + biochemical energy is not conserved. We introduce a general framework for time-dependent biomechanics in terms of jet manifolds associated to the extended musculo-skeletal configuration manifold, called the configuration bundle. We start with an ordinary configuration manifold of human body motion, given as a set of its all active degrees of freedom (DOF) for a particular movement. This is a Riemannian manifold with a material metric tensor given by the total mass-inertia matrix of the human body segments. This is the base manifold for standard autonomous biomechanics. To make its time-dependent generalization, we need to extend it with a real time axis. By this extension, using techniques from fibre bundles, we defined the biomechanical configuration bundle. On the biomechanical bundle we define vector-fields, differential forms and affine connections, as well as the associat...
A 3D radiative transfer framework. IX. Time dependence
Jack, D.; Hauschildt, P. H.; Baron, E.
2012-10-01
Context. Time-dependent, 3D radiation transfer calculations are important for the modeling of a variety of objects, from supernovae and novae to simulations of stellar variability and activity. Furthermore, time-dependent calculations can be used to obtain a 3D radiative equilibrium model structure via relaxation in time. Aims: We extend our 3D radiative transfer framework to include direct time dependence of the radiation field; i.e., the ∂I/∂t terms are fully considered in the solution of radiative transfer problems. Methods: We build on the framework that we have described in previous papers in this series and develop a subvoxel method for the ∂I/∂t terms. Results: We test the implementation by comparing the 3D results to our well tested 1D time dependent radiative transfer code in spherical symmetry. A simple 3D test model is also presented. Conclusions: The 3D time dependent radiative transfer method is now included in our 3D RT framework and in PHOENIX/3D.
A 3D radiative transfer framework IX. Time dependence
Jack, D; Baron, E
2012-01-01
Context. Time-dependent, 3D radiation transfer calculations are important for the modeling of a variety of objects, from supernovae and novae to simulations of stellar variability and activity. Furthermore, time-dependent calculations can be used to obtain a 3D radiative equilibrium model structure via relaxation in time. Aims. We extend our 3D radiative transfer framework to include direct time dependence of the radiation field; i.e., the $\\partial I/ \\partial t$ terms are fully considered in the solution of radiative transfer problems. Methods. We build on the framework that we have described in previous papers in this series and develop a subvoxel method for the $\\partial I/\\partial t$ terms. Results. We test the implementation by comparing the 3D results to our well tested 1D time dependent radiative transfer code in spherical symmetry. A simple 3D test model is also presented. Conclusions. The 3D time dependent radiative transfer method is now included in our 3D RT framework and in PHOENIX/3D.
Noncommutative quantum mechanics in a time-dependent background
Dey, Sanjib; Fring, Andreas
2014-10-01
We investigate a quantum mechanical system on a noncommutative space for which the structure constant is explicitly time dependent. Any autonomous Hamiltonian on such a space acquires a time-dependent form in terms of the conventional canonical variables. We employ the Lewis-Riesenfeld method of invariants to construct explicit analytical solutions for the corresponding time-dependent Schrödinger equation. The eigenfunctions are expressed in terms of the solutions of variants of the nonlinear Ermakov-Pinney equation and discussed in detail for various types of background fields. We utilize the solutions to verify a generalized version of Heisenberg's uncertainty relations for which the lower bound becomes a time-dependent function of the background fields. We study the variance for various states, including standard Glauber coherent states with their squeezed versions and Gaussian Klauder coherent states resembling a quasiclassical behavior. No type of coherent state appears to be optimal in general with regard to achieving minimal uncertainties, as this feature turns out to be background field dependent.
Differential Geometry of Time-Dependent Mechanics
Giachetta, G; Sardanashvily, G
1997-01-01
The usual formulations of time-dependent mechanics start from a given splitting $Y=R\\times M$ of the coordinate bundle $Y\\to R$. From physical viewpoint, this splitting means that a reference frame has been chosen. Obviously, such a splitting is broken under reference frame transformations and time-dependent canonical transformations. Our goal is to formulate time-dependent mechanics in gauge-invariant form, i.e., independently of any reference frame. The main ingredient in this formulation is a connection on the bundle $Y\\to R$ which describes an arbitrary reference frame. We emphasize the following peculiarities of this approach to time-dependent mechanics. A phase space does not admit any canonical contact or presymplectic structure which would be preserved under reference frame transformations, whereas the canonical Poisson structure is degenerate. A Hamiltonian fails to be a function on a phase space. In particular, it can not participate in a Poisson bracket so that the evolution equation is not reduced...
Time-dependent current-density-functional theory for metals
Romaniello, Pina
2006-01-01
Materials have been used throughout history for their structural properties, e.g. ductility, elasticity, hardness etc., and later also for their physical properties, i.e., for their characteristic response to external perturbances. These last properties have been investigated in this thesis by using
Nuclear Level Density: Shell Model vs Mean Field
Sen'kov, Roman
2015-01-01
The knowledge of the nuclear level density is necessary for understanding various reactions including those in the stellar environment. Usually the combinatorics of Fermi-gas plus pairing is used for finding the level density. Recently a practical algorithm avoiding diagonalization of huge matrices was developed for calculating the density of many-body nuclear energy levels with certain quantum numbers for a full shell-model Hamiltonian. The underlying physics is that of quantum chaos and intrinsic thermalization in a closed system of interacting particles. We briefly explain this algorithm and, when possible, demonstrate the agreement of the results with those derived from exact diagonalization. The resulting level density is much smoother than that coming from the conventional mean-field combinatorics. We study the role of various components of residual interactions in the process of thermalization, stressing the influence of incoherent collision-like processes. The shell-model results for the traditionally...
Thermal state of the general time-dependent harmonic oscillator
Indian Academy of Sciences (India)
Jeong-Ryeol Choi
2003-07-01
Taking advantage of dynamical invariant operator, we derived quantum mechanical solution of general time-dependent harmonic oscillator. The uncertainty relation of the system is always larger than ħ=2 not only in number but also in the thermal state as expected. We used the diagonal elements of density operator satisfying Leouville–von Neumann equation to calculate various expectation values in the thermal state. We applied our theory to a special case which is the forced Caldirola–Kanai oscillator.
Superconducting toroidal field coil current densities for the TFCX
Energy Technology Data Exchange (ETDEWEB)
Kalsi, S.S.; Hooper, R.J.
1985-04-01
A major goal of the Tokamak Fusion Core Experiment (TFCX) study was to minimize the size of the device and achieve lowest cost. Two key factors influencing the size of the device employing superconducting magnets are toroidal field (TF) winding current density and its nuclear heat load withstand capability. Lower winding current density requires larger radial build of the winding pack. Likewise, lower allowable nuclear heating in the winding requires larger shield thickness between the plasma and coil. In order to achieve a low-cost device, it is essential to maximize the winding's current density and nuclear heating withhstand capability. To meet the above objective, the TFCX design specification adopted as goals a nominal winding current density of 3500 A/cm/sup 2/ with 10-T peak field at the winding and peak nuclear heat load limits of 1 MW/cm/sup 3/ for the nominal design and 50 MW/cm/sup 3/ for an advanced design. This study developed justification for these current density and nuclear heat load limits.
Eisenhart lifts and symmetries of time-dependent systems
Cariglia, M; Gibbons, G W; Horvathy, P A
2016-01-01
Certain dissipative systems, such as Caldirola and Kannai's damped simple harmonic oscillator, may be modelled by time-dependent Lagrangian and hence time dependent Hamiltonian systems with $n$ degrees of freedom. In this paper we treat these systems, their projective and conformal symmetries as well as their quantisation from the point of view of the Eisenhart lift to a Bargmann spacetime in $n+2$ dimensions, equipped with its covariantly constant null Killing vector field. Reparametrization of the time variable corresponds to conformal rescalings of the Bargmann metric. We show how the Arnold map lifts to Bargmann spacetime. We contrast the greater generality of the Caldirola-Kannai approach with that of Arnold and Bateman. At the level of quantum mechanics, we are able to show how the relevant Schr\\"odinger equation emerges naturally using the techniques of quantum field theory in curved spacetimes, since a covariantly constant null Killing vector field gives rise to well defined one particle Hilbert space...
Time-dependent species sensitivity distributions.
Fox, David R; Billoir, Elise
2013-02-01
Time is a central component of toxicity assessments. However, current ecotoxicological practice marginalizes time in concentration-response (C-R) modeling and species sensitivity distribution (SSD) analyses. For C-R models, time is invariably fixed, and toxicity measures are estimated from a function fitted to the data at that time. The estimated toxicity measures are used as inputs to the SSD modeling phase, which similarly avoids explicit recognition of the temporal component. The present study extends some commonly employed probability models for SSDs to derive theoretical results that characterize the time-dependent nature of hazardous concentration (HCx) values. The authors' results show that even from very simple assumptions, more complex patterns in the SSD time dependency can be revealed.
Time-Dependent Erosion of Ion Optics
Wirz, Richard E.; Anderson, John R.; Katz, Ira; Goebel, Dan M.
2008-01-01
The accurate prediction of thruster life requires time-dependent erosion estimates for the ion optics assembly. Such information is critical to end-of-life mechanisms such as electron backstreaming. CEX2D was recently modified to handle time-dependent erosion, double ions, and multiple throttle conditions in a single run. The modified code is called "CEX2D-t". Comparisons of CEX2D-t results with LDT and ELT post-tests results show good agreement for both screen and accel grid erosion including important erosion features such as chamfering of the downstream end of the accel grid and reduced rate of accel grid aperture enlargement with time.
Coasting cosmologies with time dependent cosmological constant
Pimentel, L O; Pimentel, Luis O.
1999-01-01
The effect of a time dependent cosmological constant is considered in a family of scalar tensor theories. Friedmann-Robertson-Walker cosmological models for vacumm and perfect fluid matter are found. They have a linear expansion factor, the so called coasting cosmology, the gravitational "constant" decreace inversely with time; this model satisfy the Dirac hipotesis. The cosmological "constant" decreace inversely with the square of time, therefore we can have a very small value for it at present time.
The Time Dependent CP Violation in Charm
Inguglia, Gianluca
2012-01-01
A model which describes the time-dependent CP formalism in $D^0$ decays has recently been proposed. There it has been highlighted a possible measurement of the angle $\\beta_c$, in the charm unitarity triangle, using the decays $D^0\\to K^+ K^-$ and $D^0\\to \\pi^+ \\pi^-$, and a measurement of the mixing phase $\\phi_{MIX}$. The same method can be used to measure the value of the parameter $x$, one of the two parameters defining charm mixing. We numerically evaluate the impact of a time-dependent analysis in terms of the possible outcomes from present and future experiments. We consider the scenarios of correlated $D^0$ mesons production at the center of mass energy of the $\\Psi(3770)$ at Super$B$, uncorrelated production at the center of mass energy of the $\\Upsilon(4S)$ at Super$B$ and Belle II, and LHCb. Recently a hint of direct CP violation in charm decays was reported by the LHCb collaboration, we estimate the rate of time-dependent asymmetry that could be achieved using their available data, and we generali...
Nuclear energy density functional inspired by an effective field theory
Papakonstantinou, Panagiota; Lim, Yeunhwan; Hyun, Chang Ho
2016-01-01
Inspired by an effective field theory (EFT) for Fermi systems, we write the nuclear energy density functional (EDF) as an expansion in powers of the Fermi momentum $k_F$, or the cubic root of the density $\\rho^{1/3}$. With the help of pseudodata from microscopic calculations we fit the coefficients of the functional within a wide range of densities relevant for nuclei and neutron stars. The functional already at low order can reproduce known or adopted values of nuclear matter near saturation, a range of existing microscopic results on asymmetric matter, and a neutron-star mass-radius relation consistent with observations. Our approach leads to a transparent expansion of Skyrme-type EDFs and opens up many possibilities for future explorations in nuclei and homogeneous matter.
Tensor classification of structure in smoothed particle hydrodynamics density fields
Forgan, Duncan; Lucas, William; Rice, Ken
2016-01-01
As hydrodynamic simulations increase in scale and resolution, identifying structures with non-trivial geometries or regions of general interest becomes increasingly challenging. There is a growing need for algorithms that identify a variety of different features in a simulation without requiring a "by-eye" search. We present tensor classification as such a technique for smoothed particle hydrodynamics (SPH). These methods have already been used to great effect in N-Body cosmological simulations, which require smoothing defined as an input free parameter. We show that tensor classification successfully identifies a wide range of structures in SPH density fields using its native smoothing, removing a free parameter from the analysis and preventing the need for tesselation of the density field, as required by some classification algorithms. As examples, we show that tensor classification using the tidal tensor and the velocity shear tensor successfully identifies filaments, shells and sheet structures in giant m...
Estimation of probability densities using scale-free field theories.
Kinney, Justin B
2014-07-01
The question of how best to estimate a continuous probability density from finite data is an intriguing open problem at the interface of statistics and physics. Previous work has argued that this problem can be addressed in a natural way using methods from statistical field theory. Here I describe results that allow this field-theoretic approach to be rapidly and deterministically computed in low dimensions, making it practical for use in day-to-day data analysis. Importantly, this approach does not impose a privileged length scale for smoothness of the inferred probability density, but rather learns a natural length scale from the data due to the tradeoff between goodness of fit and an Occam factor. Open source software implementing this method in one and two dimensions is provided.
Tensor classification of structure in smoothed particle hydrodynamics density fields
Forgan, Duncan; Bonnell, Ian; Lucas, William; Rice, Ken
2016-04-01
As hydrodynamic simulations increase in scale and resolution, identifying structures with non-trivial geometries or regions of general interest becomes increasingly challenging. There is a growing need for algorithms that identify a variety of different features in a simulation without requiring a `by eye' search. We present tensor classification as such a technique for smoothed particle hydrodynamics (SPH). These methods have already been used to great effect in N-Body cosmological simulations, which require smoothing defined as an input free parameter. We show that tensor classification successfully identifies a wide range of structures in SPH density fields using its native smoothing, removing a free parameter from the analysis and preventing the need for tessellation of the density field, as required by some classification algorithms. As examples, we show that tensor classification using the tidal tensor and the velocity shear tensor successfully identifies filaments, shells and sheet structures in giant molecular cloud simulations, as well as spiral arms in discs. The relationship between structures identified using different tensors illustrates how different forces compete and co-operate to produce the observed density field. We therefore advocate the use of multiple tensors to classify structure in SPH simulations, to shed light on the interplay of multiple physical processes.
Nonlinear density fluctuation field theory for large scale structure
Institute of Scientific and Technical Information of China (English)
Yang Zhang; Hai-Xing Miao
2009-01-01
We develop an effective field theory of density fluctuations for a Newtonian self-gravitating N-body system in quasi-equilibrium and apply it to a homogeneous uni-verse with small density fluctuations. Keeping the density fluctuations up to second or-der, we obtain the nonlinear field equation of 2-pt correlation ξ(r), which contains 3-pt correlation and formal ultra-violet divergences. By the Groth-Peebles hierarchical ansatz and mass renormalization, the equation becomes closed with two new terms beyond the Gaussian approximation, and their coefficients are taken as parameters. The analytic solu-tion is obtained in terms of the hypergeometric functions, which is checked numerically.With one single set of two fixed parameters, the correlation ξ(r) and the corresponding power spectrum P(k) simultaneously match the results from all the major surveys, such as APM, SDSS, 2dfGRS, and REFLEX. The model gives a unifying understanding of several seemingly unrelated features of large scale structure from a field-theoretical per-spective. The theory is worth extending to study the evolution effects in an expanding universe.
Tokamak power reactor ignition and time dependent fractional power operation
Energy Technology Data Exchange (ETDEWEB)
Vold, E.L.; Mau, T.K.; Conn, R.W.
1986-06-01
A flexible time-dependent and zero-dimensional plasma burn code with radial profiles was developed and employed to study the fractional power operation and the thermal burn control options for an INTOR-sized tokamak reactor. The code includes alpha thermalization and a time-dependent transport loss which can be represented by any one of several currently popular scaling laws for energy confinement time. Ignition parameters were found to vary widely in density-temperature (n-T) space for the range of scaling laws examined. Critical ignition issues were found to include the extent of confinement time degradation by alpha heating, the ratio of ion to electron transport power loss, and effect of auxiliary heating on confinement. Feedback control of the auxiliary power and ion fuel sources are shown to provide thermal stability near the ignition curve.
Form the density-of-states method to finite density quantum field theory
Langfeld, Kurt
2016-01-01
During the last 40 years, Monte Carlo calculations based upon Importance Sampling have matured into the most widely employed method for determinig first principle results in QCD. Nevertheless, Importance Sampling leads to spectacular failures in situations in which certain rare configurations play a non-secondary role as it is the case for Yang-Mills theories near a first order phase transition or quantum field theories at finite matter density when studied with the re-weighting method. The density-of-states method in its LLR formulation has the potential to solve such overlap or sign problems by means of an exponential error suppression. We here introduce the LLR approach and its generalisation to complex action systems. Applications include U(1), SU(2) and SU(3) gauge theories as well as the Z3 spin model at finite densities and heavy-dense QCD.
Magnetic field dependence of the threshold electric field in unconventional charge density waves
Dóra, Balázs; Virosztek, Attila; Maki, Kazumi
2002-04-01
Many experiments suggest that the unidentified low-temperature phase of α-(BEDT-TTF)2KHg(SCN)4 is most likely unconventional charge density wave (UCDW). To further extend this identification we present our theoretical study of the threshold electric field of UCDW in a magnetic field. The magnetic field-temperature phase diagram is very similar to those in a d-wave superconductor. The optical conductivity shows clear features characteristic to both UDW and magnetic field. We find a rather strong field dependence of the threshold electric field, which shows qualitatively good agreement with the experimental data.
Casarin, Maurizio; Finetti, Paola; Vittadini, Andrea; Wang, Fan; Ziegler, Tom
2007-06-21
Time-dependent density functional theory (TDDFT) coupled to the relativistic two-component zeroth-order regular approximation, both available in the last version of the ADF package, have been successfully used to simulate X-ray absorption spectra of TiCl4, Ti(eta5-C5H5)Cl3, and Ti(eta5-C5H5)2Cl2 in terms of their oscillator strength distributions. Besides allowing a first principle assignment of Ti 1s, Cl 1s, and Ti 2p (L2,3 edges) core excitation spectra, theoretical outcomes provide a rationale for deviations from the expected L3/L2 branching ratio.
McMahon, Suzanne; Amirjalayer, Saeed; Buma, Wybren J; Halpin, Yvonne; Long, Conor; Rooney, A Denise; Woutersen, Sander; Pryce, Mary T
2015-09-21
The photophysics and photochemistry of [(CO)5MC(OMe)Me] (M = Cr or W) were investigated using picosecond time-resolved infrared spectroscopy (M = Cr or W), low-temperature matrix isolation techniques (M = Cr), and time-dependent density functional calculations (M = Cr or W). These studies provide unambiguous evidence for the photochemical formation of a long-lived, 18-electron metallaketene species capable of acting as a synthetically useful intermediate. For the Cr complex, an intermediate metallacyclopropanone singlet excited state was detected on the reaction path to the metallaketene species. This metallacyclopropanone excited state species has a lifetime of less than 100 ps and a characteristic bridging carbonyl band at 1770 cm(-1). The tungsten ketene species was also detected but in contrast to the chromium system, this forms directly from a low-lying triplet excited state. The electrochemical release of CO showed a greater efficiency for the chromium complex when compared to the tungsten.
Eisenhart lifts and symmetries of time-dependent systems
Cariglia, M.; Duval, C.; Gibbons, G. W.; Horváthy, P. A.
2016-10-01
Certain dissipative systems, such as Caldirola and Kannai's damped simple harmonic oscillator, may be modelled by time-dependent Lagrangian and hence time dependent Hamiltonian systems with n degrees of freedom. In this paper we treat these systems, their projective and conformal symmetries as well as their quantisation from the point of view of the Eisenhart lift to a Bargmann spacetime in n + 2 dimensions, equipped with its covariantly constant null Killing vector field. Reparametrisation of the time variable corresponds to conformal rescalings of the Bargmann metric. We show how the Arnold map lifts to Bargmann spacetime. We contrast the greater generality of the Caldirola-Kannai approach with that of Arnold and Bateman. At the level of quantum mechanics, we are able to show how the relevant Schrödinger equation emerges naturally using the techniques of quantum field theory in curved spacetimes, since a covariantly constant null Killing vector field gives rise to well defined one particle Hilbert space. Time-dependent Lagrangians arise naturally also in cosmology and give rise to the phenomenon of Hubble friction. We provide an account of this for Friedmann-Lemaître and Bianchi cosmologies and how it fits in with our previous discussion in the non-relativistic limit.
Shock front field structure in low-density systems
Hua, Rui; Mucguffey, Christopher; Beg, Farhat; Sio, Hong; Ping, Yuan; Wilks, Scott; Heeter, Bob; Collins, Rip
2016-10-01
It is known that a shock front is not a simple discontinuity in density and temperature as depicted in commonly used hydro codes but also consists of self-generated fields associated with gradients in the electron pressure. A quasi-planar platform using broadband proton radiography has been developed to study this field structure at a shock front. The broad bandwidth offers energy-dependent measurements which quantitatively constrain both the potential and field width at the shock front. Experiments were conducted on the OMEGA EP, where three long pulse beams delivered 6 kJ in 2 ns for shock initiation in a tube filled with either pure Helium or mixture of Helium and Neon, and a short pulse of 850 J, 10 ps generated broadband protons for point-projection radiography. Simultaneous spatially resolved soft-x-ray spectroscopy provided shock velocity, particle velocity and thermal emission measurements, constraining density and temperature for the field generation. The data and modeling indicate that a multi-KeV potential was present at the shock front where a strong electron pressure gradient existed. This work was performed under DOE contract DE-AC52-07NA27344 with support from OFES Early Career program and LLNL LDRD program.
The time-dependent Gutzwiller approximation
Fabrizio, Michele
2015-03-01
The time-dependent Gutzwiller Approximation (t-GA) is shown to be capable of tracking the off-equilibrium evolution both of coherent quasiparticles and of incoherent Hubbard bands. The method is used to demonstrate that the sharp dynamical crossover observed by time-dependent DMFT in the quench-dynamics of a half-filled Hubbard model can be identified within the t-GA as a genuine dynamical transition separating two distinct physical phases. This result, strictly variational for lattices of infinite coordination number, is intriguing as it actually questions the occurrence of thermalization. Next, we shall present how t-GA works in a multi-band model for V2O3 that displays a first-order Mott transition. We shall show that a physically accessible excitation pathway is able to collapse the Mott gap down and drive off-equilibrium the insulator into a metastable metal phase. Work supported by the European Union, Seventh Framework Programme, under the project GO FAST, Grant Agreement No. 280555.
Time-dependent secular evolution in galaxies
Weinberg, M D
2004-01-01
Lynden-Bell & Kalnajs (1972) presented a useful formula for computing the long-range torque between spiral arms and the disk at large. The derivation uses second-order perturbation theory and assumes that the perturbation slowly grows over a very long time: the time-asymptotic limit. This formula has been widely used to predict the angular momentum transport between spiral arms and stellar bars between disks and dark-matter halos. However, this paper shows that the LBK time-asymptotic limit is not appropriate because the characteristic evolution time for galaxies is too close to the relevant dynamical times. We demonstrate that transients, not present in the time-asymptotic formula, can play a major role in the evolution for realistic astronomical time scales. A generalisation for arbitrary time dependence is presented and illustrated by the bar--halo and satellite--halo interaction. The natural time dependence in bar-driven halo evolution causes quantitative differences in the overall torque and qualitat...
Chandrasekaran, Suryanarayanan; Aghtar, Mortaza; Valleau, Stéphanie; Aspuru-Guzik, Alán; Kleinekathöfer, Ulrich
2015-08-06
Studies on light-harvesting (LH) systems have attracted much attention after the finding of long-lived quantum coherences in the exciton dynamics of the Fenna-Matthews-Olson (FMO) complex. In this complex, excitation energy transfer occurs between the bacteriochlorophyll a (BChl a) pigments. Two quantum mechanics/molecular mechanics (QM/MM) studies, each with a different force-field and quantum chemistry approach, reported different excitation energy distributions for the FMO complex. To understand the reasons for these differences in the predicted excitation energies, we have carried out a comparative study between the simulations using the CHARMM and AMBER force field and the Zerner intermediate neglect of differential orbital (ZINDO)/S and time-dependent density functional theory (TDDFT) quantum chemistry methods. The calculations using the CHARMM force field together with ZINDO/S or TDDFT always show a wider spread in the energy distribution compared to those using the AMBER force field. High- or low-energy tails in these energy distributions result in larger values for the spectral density at low frequencies. A detailed study on individual BChl a molecules in solution shows that without the environment, the density of states is the same for both force field sets. Including the environmental point charges, however, the excitation energy distribution gets broader and, depending on the applied methods, also asymmetric. The excitation energy distribution predicted using TDDFT together with the AMBER force field shows a symmetric, Gaussian-like distribution.
Time dependent deformation of Kilauea Volcano, Hawaii
Montgomery-Brown, Emily Kvietka Desmarais
to a decollement structure 8 km under the south flank, and the locations of the microearthquakes suggest that both occur on the same structure. In 2007, Episode 56 of the Pu'u 'O'o-Kupianaha eruption occurred. This episode was exciting both because it was the largest intrusion in the last decade, and because it occurred concurrently with a flank slow-slip event. The intrusion started on Father's day (June 17th), 2007 with increased seismicity and abrupt tilts at the summit and rift zones. Quasi-static models of the total deformation determined from GPS, tilt, and InSAR indicate that the intrusion occurred on two en echelon dike segments in the upper East Rift Zone along with deformation consistent with slow-slip in the same areas of previous events. The ˜ 2 m maximum opening occurred on the eastern segment near Makaopui crater. Unlike previous intrusions in 1997, 1999, and 2000, the dike model was not sufficient to explain deformation on the western flank. Additionally, a coastal tiltmeter installed in anticipation of a slow-slip event recorded tilts consistent with those observed during the 2005 slow-slip event. These observations led to the conclusion that a concurrent slow-slip event occurred. Geodetic models indicate a similar amount of decollement slip occurred as in previous slow-slip events. Sub-daily GPS positions were used to study the spatio-temporal distribution of the dike intrusion. The time-dependent intrusion model shows that the intrusion began on the western en echelon segment before jumping to the eastern segment, which accumulated the majority of the 2 m of opening. Sub-daily GPS positions limit the number of stations available since there are very few continuous stations north of the East Rift Zone, where coverage is critical for separating the intrusion from the slow-slip. However, an ENVISAT interferogram at 08:22 on June 18, 2007 provides additional spatial coverage of deformation up to that point. Combining this image with the GPS and tilt
Time-dependent tomographic reconstruction of the solar corona
Vibert, D.; Peillon, C.; Lamy, P.; Frazin, R. A.; Wojak, J.
2016-10-01
Solar rotational tomography (SRT) applied to white-light coronal images observed at multiple aspect angles has been the preferred approach for determining the three-dimensional (3D) electron density structure of the solar corona. However, it is seriously hampered by the restrictive assumption that the corona is time-invariant which introduces significant errors in the reconstruction. We first explore several methods to mitigate the temporal variation of the corona by decoupling the "fast-varying" inner corona from the "slow-moving" outer corona using multiple masking (either by juxtaposition or recursive combination) and radial weighting. Weighting with a radial exponential profile provides some improvement over a classical reconstruction but only beyond ≈ 3R⊙. We next consider a full time-dependent tomographic reconstruction involving spatio-temporal regularization and further introduce a co-rotating regularization aimed at preventing concentration of reconstructed density in the plane of the sky. Crucial to testing our procedure and properly tuning the regularization parameters is the introduction of a time-dependent MHD model of the corona based on observed magnetograms to build a time-series of synthetic images of the corona. Our procedure, which successfully reproduces the time-varying model corona, is finally applied to a set of 53 LASCO-C2 pB images roughly evenly spaced in time from 15 to 29 March 2009. Our procedure paves the way to a time-dependent tomographic reconstruction of the coronal electron density to the whole set of LASCO-C2 images presently spanning 20 years.
Time-dependent magnetohydrodynamic simulations of the inner heliosphere
Merkin, V. G.; Lyon, J. G.; Lario, D.; Arge, C. N.; Henney, C. J.
2016-04-01
This paper presents results from a simulation study exploring heliospheric consequences of time-dependent changes at the Sun. We selected a 2 month period in the beginning of year 2008 that was characterized by very low solar activity. The heliosphere in the equatorial region was dominated by two coronal holes whose changing structure created temporal variations distorting the classical steady state picture of the heliosphere. We used the Air Force Data Assimilate Photospheric Flux Transport (ADAPT) model to obtain daily updated photospheric magnetograms and drive the Wang-Sheeley-Arge (WSA) model of the corona. This leads to a formulation of a time-dependent boundary condition for our three-dimensional (3-D) magnetohydrodynamic (MHD) model, LFM-helio, which is the heliospheric adaptation of the Lyon-Fedder-Mobarry MHD simulation code. The time-dependent coronal conditions were propagated throughout the inner heliosphere, and the simulation results were compared with the spacecraft located near 1 astronomical unit (AU) heliocentric distance: Advanced Composition Explorer (ACE), Solar Terrestrial Relations Observatory (STEREO-A and STEREO-B), and the MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft that was in cruise phase measuring the heliospheric magnetic field between 0.35 and 0.6 AU. In addition, during the selected interval MESSENGER and ACE aligned radially allowing minimization of the effects of temporal variation at the Sun versus radial evolution of structures. Our simulations show that time-dependent simulationsreproduce the gross-scale structure of the heliosphere with higher fidelity, while on smaller spatial and faster time scales (e.g., 1 day) they provide important insights for interpretation of the data. The simulations suggest that moving boundaries of slow-fast wind transitions at 0.1 AU may result in the formation of inverted magnetic fields near pseudostreamers which is an intrinsically time-dependent process
Atomistic force field for alumina fit to density functional theory.
Sarsam, Joanne; Finnis, Michael W; Tangney, Paul
2013-11-28
We present a force field for bulk alumina (Al2O3), which has been parametrized by fitting the energies, forces, and stresses of a large database of reference configurations to those calculated with density functional theory (DFT). We use a functional form that is simpler and computationally more efficient than some existing models of alumina parametrized by a similar technique. Nevertheless, we demonstrate an accuracy of our potential that is comparable to those existing models and to DFT. We present calculations of crystal structures and energies, elastic constants, phonon spectra, thermal expansion, and point defect formation energies.
Energy and angular momentum densities of stationary gravity fields
Lynden-Bell, D; Bicak, Jiri; 10.1103/PhysRevD.75.024040
2009-01-01
We give physical explanations of explicit invariant expressions for the energy and angular momentum densities of gravitational fields in stationary space-times. These expressions involve non-locally defined conformal factors. In certain coordinates these become locally defined in terms of the metric. These results are derived via expressions for total gravitational potential energy from the difference between the total energy and the mechanical energy. The latter involves kinetic energy seen in the frame of static observers. When in the axially symmetric case we consider zero angular momentum observers (who move orthogonally to surfaces of constant time), we find that the angular momentum they attribute to the gravitational field is solely due to their motion.
Out of Equilibrium Fields in Inflationary Dynamics Density Fluctuations
Boyanovsky, D; De Vega, H J; Holman, R; Kumar, S P
1998-01-01
The energy and time scales during the inflationary stage of the universe calls for an out of equilibrium quantum field treatment. Moreover, the high energy densities involved make necessary the use of non-perturbative approaches as large N and Hartree methods. We start these lectures by introducing such non-perturbative out of equilibrium methods in cosmological universes. We discuss the renormalization procedure and the choice of initial conditions. We then study the nonlinear dynamics of quantum fields in matter and radiation dominated FRW and de Sitter universes. For a variety of initial conditions, we compute the evolution of the inflaton,its quantum fluctuations and the equation of state. We investigate the explosive particle production due to spinodal unstabilities and parametric amplification in FRW and de Sitter universes with and without symmetry breaking.We find that the particle production is sensitive to the expansion of the universe.For symmetry breaking scenarios, we determine generic late time ...
A collisional extension of time-dependent Hartree-Fock
Lacombe, L.; Reinhard, P.-G.; Dinh, P. M.; Suraud, E.
2016-12-01
We propose a collisional extension of time-dependent mean-field theories on the basis of a recently proposed stochastic extension of mean-field dynamics (stochastic time-dependent Hartree-Fock, STDHF). The latter theory is unfortunately too involved to envision practical applications in realistic systems in the near future and is thus bound to model systems. It is also hard to explore moderate to low energies with STDHF, because of vanishing transition probabilities that are impossible to sample properly. For such moderately excited situations covering small fluctuations, we compactify sampling by employing the same average mean field for all STDHF trajectories. The new approach, coined average STDHF (ASTDHF), ignores the fluctuations of the mean field but still accounts correctly for the collisional correlations responsible for dissipative features on top of mean-field dynamics. We detail the main features of the new approach in relation to existing equations, in particular quantum kinetic theories. The new theory is directly connected to STDHF, both formally and practically. We thus discuss in detail how the two approaches are related to each other. We apply the new scheme to illustrative examples taking as benchmark STDHF dynamics in 1D. ASTDHF provides results that are in remarkable agreement with the more elaborate STDHF. It makes it a promising approach to deal with dissipative dynamics in finite quantum systems, because of its moderate cost allowing applications in realistic systems and the possibility of exploring any excitation energy range where collisional correlations are expected to play a role.
The Space Density of Field Methane (``T") Dwarfs
Collinge, M. J.; Knapp, G. R.; Fan, X.; Lupton, R. H.; Narayanan, V.; Strauss, M. A.; Gunn, J. E.; Schlegel, D. J.; Ivezić, Ž.; Rockosi, C. M.; Geballe, T. R.; Leggett, S. K.; Golimowski, D.; Hawley, S. L.
2002-12-01
We describe a complete magnitude-limited sample of 11 field methane (T) dwarfs brighter than z ≈ 20.2 selected from the imaging data of the Sloan Digital Sky Survey (SDSS). We discuss the optical and near-infrared colors of these and other extremely red objects and show that T dwarfs occupy a unique region in optical color-color space. The area density of methane dwarfs in this sample is one per 140 square degrees, and the space density is about one per 160 pc3. We use simulations to show that this is consistent with an IMF that is slowly rising toward lower mass through the substellar regime (dn/dm m-α , where α < 1), in reasonable agreement with the results of many open cluster studies. The inferred mass density in substellar objects is about 10% of that in stars. Funding for the SDSS is provided by the Alfred P. Sloan Foundation, NASA, NSF, DoE, Monbukagakusho, the Max Planck Society and the member institutions. The SDSS web site is http://www.sdss.org/.
Aspects of renormalization in finite-density field theory
Energy Technology Data Exchange (ETDEWEB)
Fitzpatrick, A. Liam; Torroba, Gonzalo; Wang, Huajia
2015-05-26
We study the renormalization of the Fermi surface coupled to a massless boson near three spatial dimensions. For this, we set up a Wilsonian RG with independent decimation procedures for bosons and fermions, where the four-fermion interaction “Landau parameters” run already at tree level. Our explicit one-loop analysis resolves previously found obstacles in the renormalization of finite-density field theory, including logarithmic divergences in nonlocal interactions and the appearance of multilogarithms. The key aspects of the RG are the above tree-level running, and a UV-IR mixing between virtual bosons and fermions at the quantum level, which is responsible for the renormalization of the Fermi velocity. We apply this approach to the renormalization of 2 k F singularities, and to Fermi surface instabilities in a companion paper, showing how multilogarithms are properly renormalized. We end with some comments on the renormalization of finite-density field theory with the inclusion of Landau damping of the boson.
Vacuum energy density and pressure of a massive scalar field
Mera, Fernando Daniel; Fulling, S. A.
2015-06-01
With a view toward application of the Pauli-Villars regularization method to the Casimir energy of boundaries, we calculate the expectation values of the components of the stress tensor of a confined massive field in 1+1 space-time dimensions. Previous papers by Hays and Fulling are bridged and generalized. The Green function for the time-independent Schrödinger equation is constructed from the Green function for the whole line by the method of images; equivalently, the one-dimensional system is solved exactly in terms of closed classical paths and periodic orbits. Terms in the energy density and in the eigenvalue density attributable to the two boundaries individually and those attributable to the confinement of the field to a finite interval are distinguished so that their physical origins are clear. Then the pressure is found similarly from the cylinder kernel, the Green function associated most directly with an exponential frequency cutoff of the Fourier mode expansion. Finally, we discuss how the theory could be rendered finite by the Pauli-Villars method.
Vacuum energy density and pressure of a massive scalar field
Mera, Fernando Daniel
2014-01-01
With a view toward application of the Pauli-Villars regularization method to the Casimir energy of boundaries, we calculate the expectation values of the components of the stress tensor of a confined massive field in 1+1 space-time dimensions. Previous papers by Hays and Fulling are bridged and generalized. The Green function for the time-independent Schrodinger equation is constructed from the Green function for the whole line by the method of images; equivalently, the one-dimensional system is solved exactly in terms of closed classical paths and periodic orbits. Terms in the energy density and in the eigenvalue density attributable to the two boundaries individually and those attributable to the confinement of the field to a finite interval are distinguished so that their physical origins are clear. Then the pressure is found similarly from the cylinder kernel, the Green function associated most directly with an exponential frequency cutoff of the Fourier mode expansion. Finally, we discuss how the theory ...
Benchmarking mean-field approximations to level densities
Alhassid, Y; Gilbreth, C N; Nakada, H
2015-01-01
We assess the accuracy of finite-temperature mean-field theory using as a standard the Hamiltonian and model space of the shell model Monte Carlo calculations. Two examples are considered: the nucleus $^{162}$Dy, representing a heavy deformed nucleus, and $^{148}$Sm, representing a nearby heavy spherical nucleus with strong pairing correlations. The errors inherent in the finite-temperature Hartree-Fock and Hartree-Fock-Bogoliubov approximations are analyzed by comparing the entropies of the grand canonical and canonical ensembles, as well as the level density at the neutron resonance threshold, with shell model Monte Carlo (SMMC) calculations, which are accurate up to well-controlled statistical errors. The main weak points in the mean-field treatments are seen to be: (i) the extraction of number-projected densities from the grand canonical ensembles, and (ii) the symmetry breaking by deformation or by the pairing condensate. In the absence of a pairing condensate, we confirm that the usual saddle-point appr...
Saturation and time dependence of geodynamo models
Schrinner, M; Cameron, R; Hoyng, P
2009-01-01
In this study we address the question under which conditions a saturated velocity field stemming from geodynamo simulations leads to an exponential growth of the magnetic field in a corresponding kinematic calculation. We perform global self-consistent geodynamo simulations and calculate the evolution of a kinematically advanced tracer field. The self-consistent velocity field enters the induction equation in each time step, but the tracer field does not contribute to the Lorentz force. This experiment has been performed by Cattaneo & Tobias (2009) and is closely related to the test field method by Schrinner et al. (2005, 2007). We find two dynamo regimes in which the tracer field either grows exponentially or approaches a state aligned with the actual self-consistent magnetic field after an initial transition period. Both regimes can be distinguished by the Rossby number and coincide with the dipolar and multipolar dynamo regimes identified by Christensen & Aubert (2006). Dipolar dynamos with low Ros...
The time-dependent Aharonov–Casher effect
Directory of Open Access Journals (Sweden)
Douglas Singleton
2016-02-01
Full Text Available In this paper we give a covariant expression for Aharonov–Casher phase. This expression is a combination of the canonical electric field, Aharonov–Casher phase plus a magnetic field phase shift. We use this covariant expression for the Aharonov–Casher phase to investigate the case of a neutral particle with a non-zero magnetic moment moving in the time dependent electric and magnetic fields of a plane electromagnetic wave background. We focus on the case where the magnetic moment of the particle is oriented so that both the electric and magnetic fields lead to non-zero phases, and we look at the interplay between these electric and magnetic phases.
The time-dependent Aharonov-Casher effect
Singleton, Douglas
2015-01-01
In this paper we give a covariant expression for Aharonov-Casher phase. This expression is a combination of the canonical electric field, Aharonov-Casher phase plus a magnetic field phase shift. We use this covariant expression for the Aharonov-Casher phase to investigate the case of a neutral particle with a non-zero magnetic moment moving in the {\\it time dependent} electric and magnetic fields of a plane electromagnetic wave background. We focus on the case where the magnetic moment of the particle is oriented so that both the electric and magnetic field lead to non-zero phases, and we look at the interplay between these electric and magnetic phases.
The time-dependent Aharonov–Casher effect
Energy Technology Data Exchange (ETDEWEB)
Singleton, Douglas, E-mail: dougs@csufresno.edu [Department of Physics, California State University Fresno, Fresno, CA 93740-8031 (United States); ICTP South American Institute for Fundamental Research, UNESP – Univ. Estadual Paulista, Rua Dr. Bento T. Ferraz 271, 01140-070, São Paulo, SP (Brazil); Ulbricht, Jaryd, E-mail: julbrich@ucsc.edu [Physics Department, University of California Santa Cruz, Santa Cruz, CA 95064 (United States); Department of Physics, California State University Fresno, Fresno, CA 93740-8031 (United States)
2016-02-10
In this paper we give a covariant expression for Aharonov–Casher phase. This expression is a combination of the canonical electric field, Aharonov–Casher phase plus a magnetic field phase shift. We use this covariant expression for the Aharonov–Casher phase to investigate the case of a neutral particle with a non-zero magnetic moment moving in the time dependent electric and magnetic fields of a plane electromagnetic wave background. We focus on the case where the magnetic moment of the particle is oriented so that both the electric and magnetic fields lead to non-zero phases, and we look at the interplay between these electric and magnetic phases.
The time-dependent Aharonov-Casher effect
Singleton, Douglas; Ulbricht, Jaryd
2016-02-01
In this paper we give a covariant expression for Aharonov-Casher phase. This expression is a combination of the canonical electric field, Aharonov-Casher phase plus a magnetic field phase shift. We use this covariant expression for the Aharonov-Casher phase to investigate the case of a neutral particle with a non-zero magnetic moment moving in the time dependent electric and magnetic fields of a plane electromagnetic wave background. We focus on the case where the magnetic moment of the particle is oriented so that both the electric and magnetic fields lead to non-zero phases, and we look at the interplay between these electric and magnetic phases.
Time Dependence of Hawking Radiation Entropy
Page, Don N
2013-01-01
If a black hole starts in a pure quantum state and evaporates completely by a unitary process, the von Neumann entropy of the Hawking radiation initially increases and then decreases back to zero when the black hole has disappeared. Here numerical results are given for an approximation to the time dependence of the radiation entropy under an assumption of fast scrambling, for large nonrotating black holes that emit essentially only photons and gravitons. The maximum of the von Neumann entropy then occurs after about 53.81% of the evaporation time, when the black hole has lost about 40.25% of its original Bekenstein-Hawking (BH) entropy (an upper bound for its von Neumann entropy) and then has a BH entropy that equals the entropy in the radiation, which is about 59.75% of the original BH entropy 4 pi M_0^2, or about 7.509 M_0^2 \\approx 6.268\\times 10^{76}(M_0/M_\\odot)^2, using my 1976 calculations that the photon and graviton emission process into empty space gives about 1.4847 times the BH entropy loss of the...
Time-dependent correlations in electricity markets
Energy Technology Data Exchange (ETDEWEB)
Alvarez-Ramirez, Jose; Escarela-Perez, Rafael [Departamento de Energia, Universidad Autonoma Metropolitana, Mexico DF, 09340 (Mexico)
2010-03-15
In the last years, many electricity markets were subjected to deregulated operation where prices are set by the action of market participants. In this form, producers and consumers rely on demand and price forecasts to decide their bidding strategies, allocate assets, negotiate bilateral contracts, hedge risks, and plan facility investments. A basic feature of efficient market hypothesis is the absence of correlations between price increments over any time scale leading to random walk-type behavior of prices, so arbitrage is not possible. However, recent studies have suggested that this is not the case and correlations are present in the behavior of diverse electricity markets. In this paper, a temporal quantification of electricity market correlations is made by means of detrended fluctuation and Allan analyses. The approach is applied to two Canadian electricity markets, Ontario and Alberta. The results show the existence of correlations in both demand and prices, exhibiting complex time-dependent behavior with lower correlations in winter while higher in summer. Relatively steady annual cycles in demand but unstable cycles in prices are detected. On the other hand, the more significant nonlinear effects (measured in terms of a multifractality index) are found for winter months, while the converse behavior is displayed during the summer period. In terms of forecasting models, our results suggest that nonlinear recursive models (e.g., feedback NNs) should be used for accurate day-ahead price estimation. In contrast, linear models can suffice for demand forecasting purposes. (author)
Time-Dependent Tomographic Reconstruction of the Solar Corona
Vibert, Didier; Lamy, Philippe; Frazin, Richard A; Wojak, Julien
2016-01-01
Solar rotational tomography (SRT) applied to white-light coronal images observed at multiple aspect angles has been the preferred approach for determining the three-dimensional (3D) electron density structure of the solar corona. However, it is seriously hampered by the restrictive assumption that the corona is time-invariant which introduces significant errors in the reconstruction. We first explore several methods to mitigate the temporal variation of the corona by decoupling the "fast-varying" inner corona from the "slow-moving" outer corona using multiple masking (either by juxtaposition or recursive combination) and radial weighting. Weighting with a radial exponential profile provides some improvement over a classical reconstruction but only beyond 3 Rsun. We next consider a full time-dependent tomographic reconstruction involving spatio-temporal regularization and further introduce a co-rotating regularization aimed at preventing concentration of reconstructed density in the plane of the sky. Crucial t...
Khaneja, Mamta; Ghosh, Santanu; Gautam, Seema; Kumar, Prashant; Rawat, J S; Chaudhury, P K; Vankar, V D; Kumar, Vikram
2015-05-01
High field emission (FE) current density from carbon nanotube (CNT) arrays grown on lithographically patterned silicon substrates is reported. A typical patterned field emitter array consists of bundles of nanotubes separated by a fixed gap and spread over the entire emission area. Emission performance from such an array having randomly oriented nanotube growth within each bundle is reported for different bundle sizes and separations. One typical sample with aligned CNTs within the bundle is also examined for comparison. It is seen that the current density from an array having random nanotube growth within the bundles is appreciably higher as compared to its aligned counterpart. The influence of structure on FE current densities as revealed by Raman spectroscopy is also seen. It is also observed that current density depends on edge length and increases with the same for all samples under study. Highest current density of -100 mA cm(-2) at an applied field of 5 V/μm is achieved from the random growth patterned sample with a bundle size of 2 μm and spacing of 4 μm between the bundles.
Electric field diagnostics of the dynamics of equatorial density depletions
Laakso, H.; Maynard, N. C.; Pfaff, R. F.; Aggson, T. L.; Coley, W. R.; Janhunen, P.; Herrero, F. A.
1997-09-01
During its life of 10 months, the San Marco D satellite crossed a large number of plasma density depletion channels in the nightside F-region equatorial ionosphere. In-situ measurements of vector electric fields from San Marco D reveal convection velocity variations inside such channels and thus can be used as diagnostics of the dynamics of these plasma depleted regions. Furthermore, in some cases, the temporal evolution of the channel can be inferred from the measurements. In this paper the electric field data are converted to plasma drift velocities in order to illustrate cases where the plasma flow is directed upward or downward in the channel, the channel itself is oriented vertically upward or tilted eastward/westward, or the channel is experiencing a bifurcation or pinching-off process. Although the E × B plasma drift velocities within the depleted channels are commonly a few hundred m s-1, on some occasions electric fields corresponding to speeds as large as 2-3 km s-1 have been observed. The implications for such highly supersonic convection are discussed, including the possible constriction of such high-speed depletion channels at higher altitudes.
Xue, Yuting; Mishra, Brijes; Gao, Danqing
2017-09-01
Field observations have demonstrated that roof failure occurs spatially in a mine from the time of excavation. It is suspected that time-dependent deformation propagates failure in the rock mass. In this paper, the relaxation test is used to study variation in the time-dependent property of rock and the consequent effect on time-dependent roof failure. This investigation uses a numerical simulation in 3DEC. The relaxation equation is developed from Burgers model. Variations in the time-dependent property in the post-failure region show negligible variation and, therefore, are averaged to represent the time-dependent property of the failed rock. Finally, these parameters are used in the numerical simulation of underground excavations. Two groups of parameters are used to represent the time-dependent property for pre- and post-failure conditions. FISH functions within 3DEC are used to monitor the state of each zone. Once failure is detected, the parameters are changed to the values corresponding to failed rock. The results show that the new relaxation model accurately predicts the time-dependent propagation of the failure zone. The variation of the time-dependent parameters significantly affects the rock mass behavior and roof convergence.