Lowe, John P
1993-01-01
Praised for its appealing writing style and clear pedagogy, Lowe's Quantum Chemistry is now available in its Second Edition as a text for senior undergraduate- and graduate-level chemistry students. The book assumes little mathematical or physical sophistication and emphasizes an understanding of the techniques and results of quantum chemistry, thus enabling students to comprehend much of the current chemical literature in which quantum chemical methods or concepts are used as tools. The book begins with a six-chapter introduction of standard one-dimensional systems, the hydrogen atom,
Sabin, John R
2013-01-01
Advances in Quantum Chemistry presents surveys of current topics in this rapidly developing field that has emerged at the cross section of the historically established areas of mathematics, physics, chemistry, and biology. It features detailed reviews written by leading international researchers. This volume focuses on the theory of heavy ion physics in medicine.Advances in Quantum Chemistry presents surveys of current topics in this rapidly developing field that has emerged at the cross section of the historically established areas of mathematics, physics, chemistry, and biology. It features
Principles of quantum chemistry
George, David V
2013-01-01
Principles of Quantum Chemistry focuses on the application of quantum mechanics in physical models and experiments of chemical systems.This book describes chemical bonding and its two specific problems - bonding in complexes and in conjugated organic molecules. The very basic theory of spectroscopy is also considered. Other topics include the early development of quantum theory; particle-in-a-box; general formulation of the theory of quantum mechanics; and treatment of angular momentum in quantum mechanics. The examples of solutions of Schroedinger equations; approximation methods in quantum c
Quantum mechanics in chemistry
Schatz, George C
2002-01-01
Intended for graduate and advanced undergraduate students, this text explores quantum mechanical techniques from the viewpoint of chemistry and materials science. Dynamics, symmetry, and formalism are emphasized. An initial review of basic concepts from introductory quantum mechanics is followed by chapters examining symmetry, rotations, and angular momentum addition. Chapter 4 introduces the basic formalism of time-dependent quantum mechanics, emphasizing time-dependent perturbation theory and Fermi's golden rule. Chapter 5 sees this formalism applied to the interaction of radiation and matt
Quantum chemistry an introduction
Kauzmann, Walter
2013-01-01
Quantum Chemistry: An Introduction provides information pertinent to the fundamental aspects of quantum mechanics. This book presents the theory of partial differentiation equations by using the classical theory of vibrations as a means of developing physical insight into this essential branch of mathematics.Organized into five parts encompassing 16 chapters, this book begins with an overview of how quantum mechanical deductions are made. This text then describes the achievements and limitations of the application of quantum mechanics to chemical problems. Other chapters provide a brief survey
Fundamentals of quantum chemistry
House, J E
2004-01-01
An introduction to the principles of quantum mechanics needed in physical chemistry. Mathematical tools are presented and developed as needed and only basic calculus, chemistry, and physics is assumed. Applications include atomic and molecular structure, spectroscopy, alpha decay, tunneling, and superconductivity. New edition includes sections on perturbation theory, orbital symmetry of diatomic molecules, the Huckel MO method and Woodward/Hoffman rules as well as a new chapter on SCF and Hartree-Fock methods. * This revised text clearly presents basic q
Handbook of relativistic quantum chemistry
Energy Technology Data Exchange (ETDEWEB)
Liu, Wenjian (ed.) [Peking Univ., Beijing (China). Center for Computational Science and Engineering
2017-03-01
This handbook focuses on the foundations of relativistic quantum mechanics and addresses a number of fundamental issues never covered before in a book. For instance: How can many-body theory be combined with quantum electrodynamics? How can quantum electrodynamics be interfaced with relativistic quantum chemistry? What is the most appropriate relativistic many-electron Hamiltonian? How can we achieve relativistic explicit correlation? How can we formulate relativistic properties? - just to name a few. Since relativistic quantum chemistry is an integral component of computational chemistry, this handbook also supplements the ''Handbook of Computational Chemistry''. Generally speaking, it aims to establish the 'big picture' of relativistic molecular quantum mechanics as the union of quantum electrodynamics and relativistic quantum chemistry. Accordingly, it provides an accessible introduction for readers new to the field, presents advanced methodologies for experts, and discusses possible future perspectives, helping readers understand when/how to apply/develop the methodologies.
Quantum Computing for Quantum Chemistry
2010-09-01
This three-year project consisted on the development and application of quantum computer algorithms for chemical applications. In particular, we developed algorithms for chemical reaction dynamics, electronic structure and protein folding. The first quantum computing for
Pilar, Frank L
2003-01-01
Useful introductory course and reference covers origins of quantum theory, Schrödinger wave equation, quantum mechanics of simple systems, electron spin, quantum states of atoms, Hartree-Fock self-consistent field method, more. 1990 edition.
Relativistic quantum chemistry on quantum computers
DEFF Research Database (Denmark)
Veis, L.; Visnak, J.; Fleig, T.
2012-01-01
The past few years have witnessed a remarkable interest in the application of quantum computing for solving problems in quantum chemistry more efficiently than classical computers allow. Very recently, proof-of-principle experimental realizations have been reported. However, so far only...... the nonrelativistic regime (i.e., the Schrodinger equation) has been explored, while it is well known that relativistic effects can be very important in chemistry. We present a quantum algorithm for relativistic computations of molecular energies. We show how to efficiently solve the eigenproblem of the Dirac......-Coulomb Hamiltonian on a quantum computer and demonstrate the functionality of the proposed procedure by numerical simulations of computations of the spin-orbit splitting in the SbH molecule. Finally, we propose quantum circuits with three qubits and nine or ten controlled-NOT (CNOT) gates, which implement a proof...
Bradlyn, Barry; Elcoro, L.; Cano, Jennifer; Vergniory, M. G.; Wang, Zhijun; Felser, C.; Aroyo, M. I.; Bernevig, B. Andrei
2017-07-01
Since the discovery of topological insulators and semimetals, there has been much research into predicting and experimentally discovering distinct classes of these materials, in which the topology of electronic states leads to robust surface states and electromagnetic responses. This apparent success, however, masks a fundamental shortcoming: topological insulators represent only a few hundred of the 200,000 stoichiometric compounds in material databases. However, it is unclear whether this low number is indicative of the esoteric nature of topological insulators or of a fundamental problem with the current approaches to finding them. Here we propose a complete electronic band theory, which builds on the conventional band theory of electrons, highlighting the link between the topology and local chemical bonding. This theory of topological quantum chemistry provides a description of the universal (across materials), global properties of all possible band structures and (weakly correlated) materials, consisting of a graph-theoretic description of momentum (reciprocal) space and a complementary group-theoretic description in real space. For all 230 crystal symmetry groups, we classify the possible band structures that arise from local atomic orbitals, and show which are topologically non-trivial. Our electronic band theory sheds new light on known topological insulators, and can be used to predict many more.
Introducing Relativity into Quantum Chemistry
Li, Wai-Kee; Blinder, S. M.
2011-01-01
It is not often realized by chemists that the special theory of relativity is behind several aspects of quantum chemistry. The Schrdinger equation itself is based on relations between space-time and energy-momentum four vectors. Electron spin is, of course, the most obvious manifestation of relativity. The chemistry of some heavy elements is…
Remedial Mathematics for Quantum Chemistry
Koopman, Lodewijk; Brouwer, Natasa; Heck, Andre; Buma, Wybren Jan
2008-01-01
Proper mathematical skills are important for every science course and mathematics-intensive chemistry courses rely on a sound mathematical pre-knowledge. In the first-year quantum chemistry course at this university, it was noticed that many students lack basic mathematical knowledge. To tackle the mathematics problem, a remedial mathematics…
Introducing Relativity into Quantum Chemistry
Li, Wai-Kee; Blinder, S. M.
2011-01-01
It is not often realized by chemists that the special theory of relativity is behind several aspects of quantum chemistry. The Schrdinger equation itself is based on relations between space-time and energy-momentum four vectors. Electron spin is, of course, the most obvious manifestation of relativity. The chemistry of some heavy elements is…
Problems in Quantum Chemistry and Spectroscopy
DEFF Research Database (Denmark)
Spanget-Larsen, Jens
2015-01-01
A collection of 22 introductory exercise problems for the course "Quantum Chemistry and Spectroscopy (QCS)".......A collection of 22 introductory exercise problems for the course "Quantum Chemistry and Spectroscopy (QCS)"....
Handbook of computational quantum chemistry
Cook, David B
2005-01-01
Quantum chemistry forms the basis of molecular modeling, a tool widely used to obtain important chemical information and visual images of molecular systems. Recent advances in computing have resulted in considerable developments in molecular modeling, and these developments have led to significant achievements in the design and synthesis of drugs and catalysts. This comprehensive text provides upper-level undergraduates and graduate students with an introduction to the implementation of quantum ideas in molecular modeling, exploring practical applications alongside theoretical explanations.Wri
Quantum Chemistry via the Periodic Law.
Blinder, S. M.
1981-01-01
Describes an approach to quantum mechanics exploiting the periodic structure of the elements as a foundation for the quantum theory of matter. Indicates that a quantum chemistry course can be developed using this approach. (SK)
Haag, Moritz P
2012-01-01
Significant progress in the development of efficient and fast algorithms for quantum chemical calculations has been made in the past two decades. The main focus has always been the desire to be able to treat ever larger molecules or molecular assemblies---especially linear and sub-linear scaling techniques are devoted to the accomplishment of this goal. However, as many chemical reactions are rather local, they usually involve only a limited number of atoms so that models of about two hundred (or even less) atoms embedded in a suitable environment are sufficient to study their mechanisms. Thus, the system size does not need to be enlarged, but remains constant for reactions of this type that can be described by less than two hundred atoms. The question then arises how fast one can obtain the quantum chemical results. This question is not directly answered by linear-scaling techniques. In fact, ideas such as haptic quantum chemistry or interactive quantum chemistry require an immediate provision of quantum che...
Computing protein infrared spectroscopy with quantum chemistry.
Besley, Nicholas A
2007-12-15
Quantum chemistry is a field of science that has undergone unprecedented advances in the last 50 years. From the pioneering work of Boys in the 1950s, quantum chemistry has evolved from being regarded as a specialized and esoteric discipline to a widely used tool that underpins much of the current research in chemistry today. This achievement was recognized with the award of the 1998 Nobel Prize in Chemistry to John Pople and Walter Kohn. As the new millennium unfolds, quantum chemistry stands at the forefront of an exciting new era. Quantitative calculations on systems of the magnitude of proteins are becoming a realistic possibility, an achievement that would have been unimaginable to the early pioneers of quantum chemistry. In this article we will describe ongoing work towards this goal, focusing on the calculation of protein infrared amide bands directly with quantum chemical methods.
Quantum Nanobiology and Biophysical Chemistry
DEFF Research Database (Denmark)
2013-01-01
An introduction was provided in the first issue by way of an Editorial to this special two issue volume of Current Physical Chemistry – “Quantum Nanobiology and Biophysical Chemistry” [1]. The Guest Editors would like to thank all the authors and referees who have contributed to this second issue....... demonstrate extremely low detection performance of acyl-homoserine lactone in a biologically relevant system using surface enhanced Raman spectroscopy. Sugihara and Bondar evaluate the influence of methyl-groups and the protein environment on retinal geometries in rhodopsin and bacteriorhodopsin, two...
Exploiting Locality in Quantum Computation for Quantum Chemistry.
McClean, Jarrod R; Babbush, Ryan; Love, Peter J; Aspuru-Guzik, Alán
2014-12-18
Accurate prediction of chemical and material properties from first-principles quantum chemistry is a challenging task on traditional computers. Recent developments in quantum computation offer a route toward highly accurate solutions with polynomial cost; however, this solution still carries a large overhead. In this Perspective, we aim to bring together known results about the locality of physical interactions from quantum chemistry with ideas from quantum computation. We show that the utilization of spatial locality combined with the Bravyi-Kitaev transformation offers an improvement in the scaling of known quantum algorithms for quantum chemistry and provides numerical examples to help illustrate this point. We combine these developments to improve the outlook for the future of quantum chemistry on quantum computers.
Understanding Quantum Numbers in General Chemistry Textbooks
Niaz, Mansoor; Fernandez, Ramon
2008-01-01
Quantum numbers and electron configurations form an important part of the general chemistry curriculum and textbooks. The objectives of this study are: (1) Elaboration of a framework based on the following aspects: (a) Origin of the quantum hypothesis, (b) Alternative interpretations of quantum mechanics, (c) Differentiation between an orbital and…
Understanding Quantum Numbers in General Chemistry Textbooks
Niaz, Mansoor; Fernandez, Ramon
2008-01-01
Quantum numbers and electron configurations form an important part of the general chemistry curriculum and textbooks. The objectives of this study are: (1) Elaboration of a framework based on the following aspects: (a) Origin of the quantum hypothesis, (b) Alternative interpretations of quantum mechanics, (c) Differentiation between an orbital and…
A Quantum Chemistry Concept Inventory for Physical Chemistry Classes
Dick-Perez, Marilu; Luxford, Cynthia J.; Windus, Theresa L.; Holme, Thomas
2016-01-01
A 14-item, multiple-choice diagnostic assessment tool, the quantum chemistry concept inventory or QCCI, is presented. Items were developed based on published student misconceptions and content coverage and then piloted and used in advanced physical chemistry undergraduate courses. In addition to the instrument itself, data from both a pretest,…
A Quantum Chemistry Concept Inventory for Physical Chemistry Classes
Dick-Perez, Marilu; Luxford, Cynthia J.; Windus, Theresa L.; Holme, Thomas
2016-01-01
A 14-item, multiple-choice diagnostic assessment tool, the quantum chemistry concept inventory or QCCI, is presented. Items were developed based on published student misconceptions and content coverage and then piloted and used in advanced physical chemistry undergraduate courses. In addition to the instrument itself, data from both a pretest,…
Quantum chemistry simulation on quantum computers: theories and experiments.
Lu, Dawei; Xu, Boruo; Xu, Nanyang; Li, Zhaokai; Chen, Hongwei; Peng, Xinhua; Xu, Ruixue; Du, Jiangfeng
2012-07-14
It has been claimed that quantum computers can mimic quantum systems efficiently in the polynomial scale. Traditionally, those simulations are carried out numerically on classical computers, which are inevitably confronted with the exponential growth of required resources, with the increasing size of quantum systems. Quantum computers avoid this problem, and thus provide a possible solution for large quantum systems. In this paper, we first discuss the ideas of quantum simulation, the background of quantum simulators, their categories, and the development in both theories and experiments. We then present a brief introduction to quantum chemistry evaluated via classical computers followed by typical procedures of quantum simulation towards quantum chemistry. Reviewed are not only theoretical proposals but also proof-of-principle experimental implementations, via a small quantum computer, which include the evaluation of the static molecular eigenenergy and the simulation of chemical reaction dynamics. Although the experimental development is still behind the theory, we give prospects and suggestions for future experiments. We anticipate that in the near future quantum simulation will become a powerful tool for quantum chemistry over classical computations.
Density functional theory in quantum chemistry
Tsuneda, Takao
2014-01-01
This book examines density functional theory based on the foundation of quantum chemistry. Unconventional in approach, it reviews basic concepts, then describes the physical meanings of state-of-the-art exchange-correlation functionals and their corrections.
The Application of SCC-DV-Xα Computational Method of Quantum Chemistry in Cement Chemistry
Institute of Scientific and Technical Information of China (English)
无
2001-01-01
It has been explored why quantum chemistry is applied to the research field of cement chemistry. The fundamental theory of SCC-DV-Xα computational method of quantum chemistry is synopsized. The results obtained by computational quantum chemistry method in recent years of valence-bond structures and hydration activity of some cement clinker minerals, mechanical strength and stabilization of some hydrates are summarized and evaluated. Finally the prospects of the future application of quantum chemistry to cement chemistry are depicted.
Simulating chemistry using quantum computers
Kassal, Ivan; Perdomo-Ortiz, Alejandro; Yung, Man-Hong; Aspuru-Guzik, Alán
2010-01-01
The difficulty of simulating quantum systems, well-known to quantum chemists, prompted the idea of quantum computation. One can avoid the steep scaling associated with the exact simulation of increasingly large quantum systems on conventional computers, by mapping the quantum system to another, more controllable one. In this review, we discuss to what extent the ideas in quantum computation, now a well-established field, have been applied to chemical problems. We describe algorithms that achieve significant advantages for the electronic-structure problem, the simulation of chemical dynamics, protein folding, and other tasks. Although theory is still ahead of experiment, we outline recent advances that have led to the first chemical calculations on small quantum information processors.
Simulating chemistry using quantum computers.
Kassal, Ivan; Whitfield, James D; Perdomo-Ortiz, Alejandro; Yung, Man-Hong; Aspuru-Guzik, Alán
2011-01-01
The difficulty of simulating quantum systems, well known to quantum chemists, prompted the idea of quantum computation. One can avoid the steep scaling associated with the exact simulation of increasingly large quantum systems on conventional computers, by mapping the quantum system to another, more controllable one. In this review, we discuss to what extent the ideas in quantum computation, now a well-established field, have been applied to chemical problems. We describe algorithms that achieve significant advantages for the electronic-structure problem, the simulation of chemical dynamics, protein folding, and other tasks. Although theory is still ahead of experiment, we outline recent advances that have led to the first chemical calculations on small quantum information processors.
Towards quantum chemistry on a quantum computer.
Lanyon, B P; Whitfield, J D; Gillett, G G; Goggin, M E; Almeida, M P; Kassal, I; Biamonte, J D; Mohseni, M; Powell, B J; Barbieri, M; Aspuru-Guzik, A; White, A G
2010-02-01
Exact first-principles calculations of molecular properties are currently intractable because their computational cost grows exponentially with both the number of atoms and basis set size. A solution is to move to a radically different model of computing by building a quantum computer, which is a device that uses quantum systems themselves to store and process data. Here we report the application of the latest photonic quantum computer technology to calculate properties of the smallest molecular system: the hydrogen molecule in a minimal basis. We calculate the complete energy spectrum to 20 bits of precision and discuss how the technique can be expanded to solve large-scale chemical problems that lie beyond the reach of modern supercomputers. These results represent an early practical step toward a powerful tool with a broad range of quantum-chemical applications.
Adiabatic quantum simulation of quantum chemistry.
Babbush, Ryan; Love, Peter J; Aspuru-Guzik, Alán
2014-10-13
We show how to apply the quantum adiabatic algorithm directly to the quantum computation of molecular properties. We describe a procedure to map electronic structure Hamiltonians to 2-body qubit Hamiltonians with a small set of physically realizable couplings. By combining the Bravyi-Kitaev construction to map fermions to qubits with perturbative gadgets to reduce the Hamiltonian to 2-body, we obtain precision requirements on the coupling strengths and a number of ancilla qubits that scale polynomially in the problem size. Hence our mapping is efficient. The required set of controllable interactions includes only two types of interaction beyond the Ising interactions required to apply the quantum adiabatic algorithm to combinatorial optimization problems. Our mapping may also be of interest to chemists directly as it defines a dictionary from electronic structure to spin Hamiltonians with physical interactions.
Quantum theory and chemistry: Two propositions
Aronowitz, S.
1980-01-01
Two propositions concerning quantum chemistry are proposed. First, it is proposed that the nonrelativistic Schroedinger equation, where the Hamiltonian operator is associated with an assemblage of nuclei and electrons, can never be arranged to yield specific molecules in the chemists' sense. It is argued that this result is a necessary condition if the Schroedinger has relevancy to chemistry. Second, once a system is in a particular state with regard to interactions among its components (the assemblage of nuclei and electrons), it cannot spontaneously eliminate any of those interactions. This leads to a subtle form of irreversibility.
Orbital entanglement in quantum chemistry
Boguslawski, Katharina
2014-01-01
The basic concepts of orbital entanglement and its application to chemistry are briefly reviewed. The calculation of orbital entanglement measures from correlated wavefunctions is discussed in terms of reduced $n$-particle density matrices. Possible simplifications in their evaluation are highlighted in case of seniority-zero wavefunctions. Specifically, orbital entanglement allows us to dissect electron correlation effects in its strong and weak contributions, to determine bond orders, to assess the quality and stability of active space calculations, to monitor chemical reactions, and to identify points along the reaction coordinate where electronic wavefunctions change drastically. Thus, orbital entanglement represents a useful and intuitive tool to interpret complex electronic wavefunctions and to facilitate a qualitative understanding of electronic structure and how it changes in chemical processes.
Quantum Dots: An Experiment for Physical or Materials Chemistry
Winkler, L. D.; Arceo, J. F.; Hughes, W. C.; DeGraff, B. A.; Augustine, B. H.
2005-01-01
An experiment is conducted for obtaining quantum dots for physical or materials chemistry. This experiment serves to both reinforce the basic concept of quantum confinement and providing a useful bridge between the molecular and solid-state world.
Inverse Quantum Chemistry: Concepts and Strategies for Rational Compound Design
Weymuth, Thomas
2014-01-01
The rational design of molecules and materials is becoming more and more important. With the advent of powerful computer systems and sophisticated algorithms, quantum chemistry plays an important role in rational design. While traditional quantum chemical approaches predict the properties of a predefined molecular structure, the goal of inverse quantum chemistry is to find a structure featuring one or more desired properties. Herein, we review inverse quantum chemical approaches proposed so far and discuss their advantages as well as their weaknesses.
Lu, Dawei; Xu, Nanyang; Xu, Boruo; Li, Zhaokai; Chen, Hongwei; Peng, Xinhua; Xu, Ruixue; Du, Jiangfeng
2012-10-13
Quantum computers have been proved to be able to mimic quantum systems efficiently in polynomial time. Quantum chemistry problems, such as static molecular energy calculations and dynamical chemical reaction simulations, become very intractable on classical computers with scaling up of the system. Therefore, quantum simulation is a feasible and effective approach to tackle quantum chemistry problems. Proof-of-principle experiments have been implemented on the calculation of the hydrogen molecular energies and one-dimensional chemical isomerization reaction dynamics using nuclear magnetic resonance systems. We conclude that quantum simulation will surpass classical computers for quantum chemistry in the near future.
First-principles quantum chemistry in the life sciences.
van Mourik, Tanja
2004-12-15
The area of computational quantum chemistry, which applies the principles of quantum mechanics to molecular and condensed systems, has developed drastically over the last decades, due to both increased computer power and the efficient implementation of quantum chemical methods in readily available computer programs. Because of this, accurate computational techniques can now be applied to much larger systems than before, bringing the area of biochemistry within the scope of electronic-structure quantum chemical methods. The rapid pace of progress of quantum chemistry makes it a very exciting research field; calculations that are too computationally expensive today may be feasible in a few months' time! This article reviews the current application of 'first-principles' quantum chemistry in biochemical and life sciences research, and discusses its future potential. The current capability of first-principles quantum chemistry is illustrated in a brief examination of computational studies on neurotransmitters, helical peptides, and DNA complexes.
Alternative algebraic approaches in quantum chemistry
Mezey, Paul G.
2015-01-01
Various algebraic approaches of quantum chemistry all follow a common principle: the fundamental properties and interrelations providing the most essential features of a quantum chemical representation of a molecule or a chemical process, such as a reaction, can always be described by algebraic methods. Whereas such algebraic methods often provide precise, even numerical answers, nevertheless their main role is to give a framework that can be elaborated and converted into computational methods by involving alternative mathematical techniques, subject to the constraints and directions provided by algebra. In general, algebra describes sets of interrelations, often phrased in terms of algebraic operations, without much concern with the actual entities exhibiting these interrelations. However, in many instances, the very realizations of two, seemingly unrelated algebraic structures by actual quantum chemical entities or properties play additional roles, and unexpected connections between different algebraic structures are often giving new insight. Here we shall be concerned with two alternative algebraic structures: the fundamental group of reaction mechanisms, based on the energy-dependent topology of potential energy surfaces, and the interrelations among point symmetry groups for various distorted nuclear arrangements of molecules. These two, distinct algebraic structures provide interesting interrelations, which can be exploited in actual studies of molecular conformational and reaction processes. Two relevant theorems will be discussed.
Disciplines, models, and computers: the path to computational quantum chemistry.
Lenhard, Johannes
2014-12-01
Many disciplines and scientific fields have undergone a computational turn in the past several decades. This paper analyzes this sort of turn by investigating the case of computational quantum chemistry. The main claim is that the transformation from quantum to computational quantum chemistry involved changes in three dimensions. First, on the side of instrumentation, small computers and a networked infrastructure took over the lead from centralized mainframe architecture. Second, a new conception of computational modeling became feasible and assumed a crucial role. And third, the field of computa- tional quantum chemistry became organized in a market-like fashion and this market is much bigger than the number of quantum theory experts. These claims will be substantiated by an investigation of the so-called density functional theory (DFT), the arguably pivotal theory in the turn to computational quantum chemistry around 1990.
From Physical Chemistry to Quantum Chemistry: How Chemists Dealt with Mathematics
Kostas Gavroglu; Ana Simões
2012-01-01
Discussing the relationship of mathematics to chemistry is closely related to the emergence of physical chemistry and of quantum chemistry. We argue that, perhaps, the most significant issue that the 'mathematization of chemistry' has historically raised is not so much methodological, as it is philosophical: the discussion over the ontological status of theoretical entities which were introduced in the process. A systematic study of such an approach to the mathematization of chemistry may, pe...
Steps toward fault-tolerant quantum chemistry.
Energy Technology Data Exchange (ETDEWEB)
Taube, Andrew Garvin
2010-05-01
Developing quantum chemistry programs on the coming generation of exascale computers will be a difficult task. The programs will need to be fault-tolerant and minimize the use of global operations. This work explores the use a task-based model that uses a data-centric approach to allocate work to different processes as it applies to quantum chemistry. After introducing the key problems that appear when trying to parallelize a complicated quantum chemistry method such as coupled-cluster theory, we discuss the implications of that model as it pertains to the computational kernel of a coupled-cluster program - matrix multiplication. Also, we discuss the extensions that would required to build a full coupled-cluster program using the task-based model. Current programming models for high-performance computing are fault-intolerant and use global operations. Those properties are unsustainable as computers scale to millions of CPUs; instead one must recognize that these systems will be hierarchical in structure, prone to constant faults, and global operations will be infeasible. The FAST-OS HARE project is introducing a scale-free computing model to address these issues. This model is hierarchical and fault-tolerant by design, allows for the clean overlap of computation and communication, reducing the network load, does not require checkpointing, and avoids the complexity of many HPC runtimes. Development of an algorithm within this model requires a change in focus from imperative programming to a data-centric approach. Quantum chemistry (QC) algorithms, in particular electronic structure methods, are an ideal test bed for this computing model. These methods describe the distribution of electrons in a molecule, which determine the properties of the molecule. The computational cost of these methods is high, scaling quartically or higher in the size of the molecule, which is why QC applications are major users of HPC resources. The complexity of these algorithms means that
Quantum chemistry-assisted synthesis route development
Energy Technology Data Exchange (ETDEWEB)
Hori, Kenji; Sumimoto, Michinori [Graduate School of Science and Engineering, Yamaguchi University, Tokiwadai, Ube, Yamaguchi 755-8611 (Japan); Murafuji, Toshihiro [Graduate School of Medicine, Yamaguchi University, Yamaguchi, Yamaguchi 753-8512 (Japan)
2015-12-31
We have been investigating “quantum chemistry-assisted synthesis route development” using in silico screenings and applied the method to several targets. Another example was conducted to develop synthesis routes for a urea derivative, namely 1-(4-(trifluoromethyl)-2-oxo-2H-chromen-7-yl)urea. While five synthesis routes were examined, only three routes passed the second in silico screening. Among them, the reaction of 7-amino-4-(trifluoromethyl)-2H-chromen-2-one and O-methyl carbamate with BF{sub 3} as an additive was ranked as the first choice for synthetic work. We were able to experimentally obtain the target compound even though its yield was as low as 21 %. The theoretical result was thus consistent with that observed. The summary of transition state data base (TSDB) is also provided. TSDB is the key to reducing time of in silico screenings.
Stevens, Jonathan
2017-07-01
Continuing advances in computational chemistry has permitted quantum mechanical calculation to assist in research in green chemistry and to contribute to the greening of chemical practice. Presented here are recent examples illustrating the contribution of computational quantum chemistry to green chemistry, including the possibility of using computation as a green alternative to experiments, but also illustrating contributions to greener catalysis and the search for greener solvents. Examples of applications of computation to ambitious projects for green synthetic chemistry using carbon dioxide are also presented.
From transistor to trapped-ion computers for quantum chemistry.
Yung, M-H; Casanova, J; Mezzacapo, A; McClean, J; Lamata, L; Aspuru-Guzik, A; Solano, E
2014-01-07
Over the last few decades, quantum chemistry has progressed through the development of computational methods based on modern digital computers. However, these methods can hardly fulfill the exponentially-growing resource requirements when applied to large quantum systems. As pointed out by Feynman, this restriction is intrinsic to all computational models based on classical physics. Recently, the rapid advancement of trapped-ion technologies has opened new possibilities for quantum control and quantum simulations. Here, we present an efficient toolkit that exploits both the internal and motional degrees of freedom of trapped ions for solving problems in quantum chemistry, including molecular electronic structure, molecular dynamics, and vibronic coupling. We focus on applications that go beyond the capacity of classical computers, but may be realizable on state-of-the-art trapped-ion systems. These results allow us to envision a new paradigm of quantum chemistry that shifts from the current transistor to a near-future trapped-ion-based technology.
Solutions to selected exercise problems in quantum chemistry and spectroscopy
DEFF Research Database (Denmark)
Spanget-Larsen, Jens
2016-01-01
Suggested solutions to a number of problems from the collection "Exercise Problems in Quantum Chemistry and Spectroscopy", previously published on ResearchGate (DOI: 10.13140/RG.2.1.4024.8162).......Suggested solutions to a number of problems from the collection "Exercise Problems in Quantum Chemistry and Spectroscopy", previously published on ResearchGate (DOI: 10.13140/RG.2.1.4024.8162)....
Solutions to selected exercise problems in quantum chemistry and spectroscopy
DEFF Research Database (Denmark)
Spanget-Larsen, Jens
2016-01-01
Suggested solutions to a number of problems from the collection "Exercise Problems in Quantum Chemistry and Spectroscopy", previously published on ResearchGate (DOI: 10.13140/RG.2.1.4024.8162).......Suggested solutions to a number of problems from the collection "Exercise Problems in Quantum Chemistry and Spectroscopy", previously published on ResearchGate (DOI: 10.13140/RG.2.1.4024.8162)....
Quantum chemistry and charge transport in biomolecules with superconducting circuits
García-Álvarez, L.; Las Heras, U.; Mezzacapo, A.; Sanz, M.; Solano, E.; Lamata, L.
2016-06-01
We propose an efficient protocol for digital quantum simulation of quantum chemistry problems and enhanced digital-analog quantum simulation of transport phenomena in biomolecules with superconducting circuits. Along these lines, we optimally digitize fermionic models of molecular structure with single-qubit and two-qubit gates, by means of Trotter-Suzuki decomposition and Jordan-Wigner transformation. Furthermore, we address the modelling of system-environment interactions of biomolecules involving bosonic degrees of freedom with a digital-analog approach. Finally, we consider gate-truncated quantum algorithms to allow the study of environmental effects.
Quantum chemistry and charge transport in biomolecules with superconducting circuits
García-Álvarez, L.; Las Heras, U.; Mezzacapo, A.; Sanz, M.; Solano, E.; Lamata, L.
2016-01-01
We propose an efficient protocol for digital quantum simulation of quantum chemistry problems and enhanced digital-analog quantum simulation of transport phenomena in biomolecules with superconducting circuits. Along these lines, we optimally digitize fermionic models of molecular structure with single-qubit and two-qubit gates, by means of Trotter-Suzuki decomposition and Jordan-Wigner transformation. Furthermore, we address the modelling of system-environment interactions of biomolecules involving bosonic degrees of freedom with a digital-analog approach. Finally, we consider gate-truncated quantum algorithms to allow the study of environmental effects. PMID:27324814
Quantum chemistry and charge transport in biomolecules with superconducting circuits.
García-Álvarez, L; Las Heras, U; Mezzacapo, A; Sanz, M; Solano, E; Lamata, L
2016-06-21
We propose an efficient protocol for digital quantum simulation of quantum chemistry problems and enhanced digital-analog quantum simulation of transport phenomena in biomolecules with superconducting circuits. Along these lines, we optimally digitize fermionic models of molecular structure with single-qubit and two-qubit gates, by means of Trotter-Suzuki decomposition and Jordan-Wigner transformation. Furthermore, we address the modelling of system-environment interactions of biomolecules involving bosonic degrees of freedom with a digital-analog approach. Finally, we consider gate-truncated quantum algorithms to allow the study of environmental effects.
The density matrix renormalization group for ab initio quantum chemistry
Wouters, Sebastian
2014-01-01
During the past 15 years, the density matrix renormalization group (DMRG) has become increasingly important for ab initio quantum chemistry. Its underlying wavefunction ansatz, the matrix product state (MPS), is a low-rank decomposition of the full configuration interaction tensor. The virtual dimension of the MPS, the rank of the decomposition, controls the size of the corner of the many-body Hilbert space that can be reached with the ansatz. This parameter can be systematically increased until numerical convergence is reached. The MPS ansatz naturally captures exponentially decaying correlation functions. Therefore DMRG works extremely well for noncritical one-dimensional systems. The active orbital spaces in quantum chemistry are however often far from one-dimensional, and relatively large virtual dimensions are required to use DMRG for ab initio quantum chemistry (QC-DMRG). The QC-DMRG algorithm, its computational cost, and its properties are discussed. Two important aspects to reduce the computational co...
Computational quantum chemistry and adaptive ligand modeling in mechanistic QSAR.
De Benedetti, Pier G; Fanelli, Francesca
2010-10-01
Drugs are adaptive molecules. They realize this peculiarity by generating different ensembles of prototropic forms and conformers that depend on the environment. Among the impressive amount of available computational drug discovery technologies, quantitative structure-activity relationship approaches that rely on computational quantum chemistry descriptors are the most appropriate to model adaptive drugs. Indeed, computational quantum chemistry descriptors are able to account for the variation of the intramolecular interactions of the training compounds, which reflect their adaptive intermolecular interaction propensities. This enables the development of causative, interpretive and reasonably predictive quantitative structure-activity relationship models, and, hence, sound chemical information finalized to drug design and discovery.
Quantum Mechanics in Chemistry (by Jack Simons and Jeff Nichols)
McCallum, C. Michael
1998-12-01
Topics in Physical Chemistry Series. Oxford University Press: New York, 1997. xxiii + 612 pp. Illustrations. ISBN 0-19-508200-1. $75.00. One of the problems faced by graduate-level quantum mechanics courses in chemistry is that there is often little time for studying chemical problems. Students must learn so much matrix algebra and notation that a first-semester course seems more like a math or physics course than chemistry. Another problem is the focus of most graduate texts. Excellent texts, such as those by Sakurai, and older treatments, such as Messiah and Cohen-Tannoudji, offer a comprehensive amount of mathematical rigor to go along with chemistry problems, but it seems the intended audience is hard-core theoretical or physical chemistry students. Requirements that are more general, such as reaction-path dynamics, structure and term symbols, and symmetry in quantum mechanical problems, are often left behind. Schatz and Ratner's Book Quantum Mechanics in Chemistry (Prentice Hall) is one book that fills this gap (at least for second-semester students); Simons and Nichols' new book is another, but it is a book that requires revision before it can be seriously considered.
Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry
Rappoport, Dmitrij; Galvin, Cooper J.; Zubarev, Dmitry; Aspuru-Guzik, Alan
2014-01-01
While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reacti...
Quantum kernel applications in medicinal chemistry.
Huang, Lulu; Massa, Lou
2012-07-01
Progress in the quantum mechanics of biological molecules is being driven by computational advances. The notion of quantum kernels can be introduced to simplify the formalism of quantum mechanics, making it especially suitable for parallel computation of very large biological molecules. The essential idea is to mathematically break large biological molecules into smaller kernels that are calculationally tractable, and then to represent the full molecule by a summation over the kernels. The accuracy of the kernel energy method (KEM) is shown by systematic application to a great variety of molecular types found in biology. These include peptides, proteins, DNA and RNA. Examples are given that explore the KEM across a variety of chemical models, and to the outer limits of energy accuracy and molecular size. KEM represents an advance in quantum biology applicable to problems in medicine and drug design.
State of the art in quantum chemistry today
Stepanov, Nikolai F.
2004-01-01
Modern quantum chemistry is the quantum theory of structure an dynamics of molecular systems. The development of quantum chemistry for almost 8 decades gave birth to many concepts of modern chemistry and created many calculation technique which are widely used to obtain preliminary as well as high-precision information on molecular properties. In the end of XXth century it becomes the real fundamental base of chemistry and the active tool for the qualitative interpretation of structural features and physical and chemical properties including dynamics of chemical transformations. It turns out to be a very power means to obtaining quantitative results for molecular clusters as well as isolated molecules in free states and in external fields. The computational programs created in the last decades of the XXth century and permanently refined provide the reliable quantitative information on molecular equilibrium configurations, harmonic vibrational frequencies and anharmonic force constants, frequencies and intensities of the first electronic transitions, energies of the formations and potential barriers, the parameters important for interpretation of ESR and NMR spectra, electric and magnetic moments, and many other characteristics of molecular systems. The last two decades turned many quantum chemists to comparatively large molecules especially those with the distinctly pronounced biological activity. Nevertheless, small molecules the calculation results for which can pretend on the highest precision still serve as a strong attractor for the people who deal with methodological as well as applied problems.
Quantum Mechanics and Conceptual Change in High School Chemistry Textbooks.
Shiland, Thomas W.
1997-01-01
Examines the presentation of quantum mechanics in eight secondary chemistry texts for elements associated with a conceptual change model: (1) dissatisfaction; (2) intelligibility; (3) plausibility; and (4) fruitfulness. Reports that these elements were not present in sufficient quantities to promote conceptual change. Presents recommendations for…
Quantum information and computation for chemistry
Kais, Sabre; Rice, Stuart A
2014-01-01
Examines the intersection of quantum information and chemical physics The Advances in Chemical Physics series is dedicated to reviewing new and emerging topics as well as the latest developments in traditional areas of study in the field of chemical physics. Each volume features detailed comprehensive analyses coupled with individual points of view that integrate the many disciplines of science that are needed for a full understanding of chemical physics. This volume of the series explores the latest research findings, applications, and new research paths from the quantum information science
Quantum chemistry, band structures and polymers
André, Jean-Marie
2012-06-01
A short review of the long way from the first calculations on polyenes after the second world war to the recent electronic devices like Organic Light Emitting Diodes or Photovoltaic Cells is given. It shows how quantum chemical methods on one side and synthesis or experiments have (or should have) interacted as incentives to new methods and technologies.
Moll, Nikolaj; Fuhrer, Andreas; Staar, Peter; Tavernelli, Ivano
2016-07-01
Quantum chemistry simulations on a quantum computer suffer from the overhead needed for encoding the Fermionic problem in a system of qubits. By exploiting the block diagonality of a Fermionic Hamiltonian, we show that the number of required qubits can be reduced while the number of terms in the Hamiltonian will increase. All operations for this reduction can be performed in operator space. The scheme is conceived as a pre-computational step that would be performed prior to the actual quantum simulation. We apply this scheme to reduce the number of qubits necessary to simulate both the Hamiltonian of the two-site Fermi-Hubbard model and the hydrogen molecule. Both quantum systems can then be simulated with a two-qubit quantum computer. Despite the increase in the number of Hamiltonian terms, the scheme still remains a useful tool to reduce the dimensionality of specific quantum systems for quantum simulators with a limited number of resources.
Control through operators for quantum chemistry
Laurent, Philippe; Salomon, Julien; Turinici, Gabriel
2012-01-01
We consider the problem of operator identification in quantum control. The free Hamiltonian and the dipole moment are searched such that a given target state is reached at a given time. A local existence result is obtained. As a by-product, our works reveals necessary conditions on the laser field to make the identification feasible. In the last part of this work, some algorithms are proposed to compute effectively these operators.
Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.
Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán
2014-03-11
While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.
The Dalton quantum chemistry program system
DEFF Research Database (Denmark)
Aidas, Kestutis; Angeli, C.; Bak, K.L.
2014-01-01
Dalton is a powerful general-purpose program system for the study of molecular electronic structure at the Hartree–Fock, Kohn–Sham, multiconfigurational self-consistent-field, Møller–Plesset, configuration-interaction, and coupled-cluster levels of theory. Apart from the total energy, a wide vari......-medium and quantum-mechanics/molecular-mechanics models. Large molecules may be studied using linear-scaling and massively parallel algorithms. Dalton is distributed at no cost from http://www.daltonprogram.org for a number of UNIX platforms....
Quantum Chemistry of Solids LCAO Treatment of Crystals and Nanostructures
Evarestov, Robert A
2012-01-01
Quantum Chemistry of Solids delivers a comprehensive account of the main features and possibilities of LCAO methods for the first principles calculations of electronic structure of periodic systems. The first part describes the basic theory underlying the LCAO methods applied to periodic systems and the use of Hartree-Fock(HF), Density Function theory(DFT) and hybrid Hamiltonians. The translation and site symmetry consideration is included to establish connection between k-space solid –state physics and real-space quantum chemistry. The inclusion of electron correlation effects for periodic systems is considered on the basis of localized crystalline orbitals. The possibilities of LCAO methods for chemical bonding analysis in periodic systems are discussed. The second part deals with the applications of LCAO methods for calculations of bulk crystal properties, including magnetic ordering and crystal structure optimization. In the second edition two new chapters are added in the application part II of t...
Quasi-classical alternatives in quantum chemistry
Gineityte, V
2014-01-01
The article contains an overview of authors achievements in development of alternative quantum-chemical approaches oriented towards revival of the classical tradition of qualitative chemical thinking instead of obtaining numerical results. The above-mentioned tradition is concluded to be based mainly on principles (rules) of additivity, transferability and locality of molecular properties. Accordingly, model Hamiltonian matrices are used in the approaches under development (called quasi-classical alternatives), wherein algebraic parameters play the role of matrix elements and these are assumed to be transferable for similar atoms and/or atomic orbitals in addition. Further, passing to delocalized descriptions of electronic structures (as usual) is expected to be the main origin of difficulties seeking to formulate quasi-classical alternatives. In the framework of the canonical method of molecular orbitals (MOs), delocalization is shown to be partially avoidable by invoking a recently-suggested approach to sec...
Quantum Chemistry via Walks in Determinant Space
Energy Technology Data Exchange (ETDEWEB)
Umrigar, Cyrus J. [Cornell Univ., Ithaca, NY (United States)
2016-01-05
There are many chemical questions of practical interest to the DOE that could be answered if there were an electronic structure method that provided consistently accurate results for all systems at an affordable computational cost. The coupled cluster method with single, double and perturbative triple excitations (CCSD(T)) is the most frequently used high-order method, but it has known deficiencies, e.g., in the description of stretched bonds. The full configuration interaction (FCI) method is the most robust method for treating electronic correlations, but it is little used because its computational cost scales exponentially in the size of the system. The largest calculation that has been done to date employed 10 billion determinants. In this regard, there was a major advance in 2010. The Alavi group at Cambridge University developed a stochastic approach to FCI --- combining it with ideas from quantum Monte Carlo (QMC) --- called FCIQMC, that allows one to go to a far larger number of determinants in certain circumstances. The computational cost is exponential in the system and basis size but with a much reduced exponent compared to conventional FCI. In this project Umrigar's group made several major improvements to the FCIQMC method that increased its efficiency by many orders of magnitude. In addition this project resulted in a cross-fertilization of ideas between the FCIQMC method, the older phaseless auxilliary-field quantum Monte Carlo (AFQMC) method developed by Zhang and Krakauer (two of the PI's of this project), and symmetry-restored wavefunctions developed by Scuseria (also a PI of this project).
Ge, Yingbin
2016-01-01
Hands-on exercises are designed for undergraduate physical chemistry students to derive two-dimensional quantum chemistry from scratch for the H atom and H[subscript 2] molecule, both in the ground state and excited states. By reducing the mathematical complexity of the traditional quantum chemistry teaching, these exercises can be completed…
NWChem: Quantum Chemistry Simulations at Scale
Energy Technology Data Exchange (ETDEWEB)
Apra, Edoardo; Kowalski, Karol; Hammond, Jeff R.; Klemm, Michael
2015-01-17
Methods based on quantum mechanics equations have been developed since the 1930's with the purpose of accurately studying the electronic structure of molecules. However, it is only during the last two decades that intense development of new computational algorithms has opened the possibility of performing accurate simulations of challenging molecular processes with high-order many-body methods. A wealth of evidence indicates that the proper inclusion of instantaneous interactions between electrons (or the so-called electron correlation effects) is indispensable for the accurate characterization of chemical reactivity, molecular properties, and interactions of light with matter. The availability of reliable methods for benchmarking of medium-size molecular systems provides also a unique chance to propagate high-level accuracy across spatial scales through the multiscale methodologies. Some of these methods have potential to utilize computational resources in an effi*cient way since they are characterized by high numerical complexity and appropriate level of data granularity, which can be effi*ciently distributed over multi-processor architectures. The broad spectrum of coupled cluster (CC) methods falls into this class of methodologies. Several recent CC implementations clearly demonstrated the scalability of CC formalisms on architectures composed of hundreds thousand computational cores. In this context NWChem provides a collection of Tensor Contraction Engine (TCE) generated parallel implementations of various coupled cluster methods capable of taking advantage of many thousand of cores on leadership class parallel architectures.
Bond additivity corrections for quantum chemistry methods
Energy Technology Data Exchange (ETDEWEB)
C. F. Melius; M. D. Allendorf
1999-04-01
In the 1980's, the authors developed a bond-additivity correction procedure for quantum chemical calculations called BAC-MP4, which has proven reliable in calculating the thermochemical properties of molecular species, including radicals as well as stable closed-shell species. New Bond Additivity Correction (BAC) methods have been developed for the G2 method, BAC-G2, as well as for a hybrid DFT/MP2 method, BAC-Hybrid. These BAC methods use a new form of BAC corrections, involving atomic, molecular, and bond-wise additive terms. These terms enable one to treat positive and negative ions as well as neutrals. The BAC-G2 method reduces errors in the G2 method due to nearest-neighbor bonds. The parameters within the BAC-G2 method only depend on atom types. Thus the BAC-G2 method can be used to determine the parameters needed by BAC methods involving lower levels of theory, such as BAC-Hybrid and BAC-MP4. The BAC-Hybrid method should scale well for large molecules. The BAC-Hybrid method uses the differences between the DFT and MP2 as an indicator of the method's accuracy, while the BAC-G2 method uses its internal methods (G1 and G2MP2) to provide an indicator of its accuracy. Indications of the average error as well as worst cases are provided for each of the BAC methods.
Bosson, Maël; Grudinin, Sergei; Redon, Stephane
2013-03-05
We present a novel Block-Adaptive Quantum Mechanics (BAQM) approach to interactive quantum chemistry. Although quantum chemistry models are known to be computationally demanding, we achieve interactive rates by focusing computational resources on the most active parts of the system. BAQM is based on a divide-and-conquer technique and constrains some nucleus positions and some electronic degrees of freedom on the fly to simplify the simulation. As a result, each time step may be performed significantly faster, which in turn may accelerate attraction to the neighboring local minima. By applying our approach to the nonself-consistent Atom Superposition and Electron Delocalization Molecular Orbital theory, we demonstrate interactive rates and efficient virtual prototyping for systems containing more than a thousand of atoms on a standard desktop computer.
Development of massively parallel quantum chemistry program SMASH
Energy Technology Data Exchange (ETDEWEB)
Ishimura, Kazuya [Department of Theoretical and Computational Molecular Science, Institute for Molecular Science 38 Nishigo-Naka, Myodaiji, Okazaki, Aichi 444-8585 (Japan)
2015-12-31
A massively parallel program for quantum chemistry calculations SMASH was released under the Apache License 2.0 in September 2014. The SMASH program is written in the Fortran90/95 language with MPI and OpenMP standards for parallelization. Frequently used routines, such as one- and two-electron integral calculations, are modularized to make program developments simple. The speed-up of the B3LYP energy calculation for (C{sub 150}H{sub 30}){sub 2} with the cc-pVDZ basis set (4500 basis functions) was 50,499 on 98,304 cores of the K computer.
Relativistic quantum chemistry the fundamental theory of molecular science
Reiher, Markus
2014-01-01
Einstein proposed his theory of special relativity in 1905. For a long time it was believed that this theory has no significant impact on chemistry. This view changed in the 1970s when it was realized that (nonrelativistic) Schrödinger quantum mechanics yields results on molecular properties that depart significantly from experimental results. Especially when heavy elements are involved, these quantitative deviations can be so large that qualitative chemical reasoning and understanding is affected. For this to grasp the appropriate many-electron theory has rapidly evolved. Nowadays relativist
Monte Carlo methods in AB initio quantum chemistry quantum Monte Carlo for molecules
Lester, William A; Reynolds, PJ
1994-01-01
This book presents the basic theory and application of the Monte Carlo method to the electronic structure of atoms and molecules. It assumes no previous knowledge of the subject, only a knowledge of molecular quantum mechanics at the first-year graduate level. A working knowledge of traditional ab initio quantum chemistry is helpful, but not essential.Some distinguishing features of this book are: Clear exposition of the basic theory at a level to facilitate independent study. Discussion of the various versions of the theory: diffusion Monte Carlo, Green's function Monte Carlo, and release n
Applications of Quantum Chemistry to the Study of Carbon Nanotubes
Jaffe, Richard L.
2005-01-01
For several years, scientists at NASA Ames have been studying the properties of carbon nanotubes using various experimental and computational methods. In this talk, I will compare different strategies for using quantum chemistry calculations to describe the electronic structure, deformation and chemical functionalization of single wall carbon nanotubes (SWNT) and the physisorption of small molecules on nanotube surfaces. The SWNT can be treated as an infinite (periodic) or finite length carbon cylinder or as a polycyclic aromatic hydrocarbon (PAH) molecule with an imposed curvature maintained by external constraints (as if it were cut out of the SWNT surface). Calculations are carried out using DFT and MP2 methods and a variety of atomic orbital basis sets from minimal (STO-3G) to valence triple zeta. The optimal approach is based on the particular SWNT property of interest. Examples to be discussed include: nanotube fluorination and other functionalization reactions; coating of nanotubes by water vapor and low-molecular weight organic molecules; and the nature of the interface between SWNT and liquids such as water and amines. In many cases, the quantum chemistry calculations are used to parameterize or validate force fields for molecular dynamics simulations. The results of these calculations have helped explain experimental data and contributed to the design of novel materials and sensors based on carbon nanotubes. Some of this research is described in the following papers:
Mezey, Paul G
2014-09-16
Conspectus Just as complete molecules have no boundaries and have "fuzzy" electron density clouds approaching zero density exponentially at large distances from the nearest nucleus, a physically justified choice for electron density fragments exhibits similar behavior. Whereas fuzzy electron densities, just as any fuzzy object, such as a thicker cloud on a foggy day, do not lend themselves to easy visualization, one may partially overcome this by using isocontours. Whereas a faithful representation of the complete fuzzy density would need infinitely many such isocontours, nevertheless, by choosing a selected few, one can still obtain a limited pictorial representation. Clearly, such images are of limited value, and one better relies on more complete mathematical representations, using, for example, density matrices of fuzzy fragment densities. A fuzzy density fragmentation can be obtained in an exactly additive way, using the output from any of the common quantum chemical computational techniques, such as Hartree-Fock, MP2, and various density functional approaches. Such "fuzzy" electron density fragments properly represented have proven to be useful in a rather wide range of applications, for example, (a) using them as additive building blocks leading to efficient linear scaling macromolecular quantum chemistry computational techniques, (b) the study of quantum chemical functional groups, (c) using approximate fuzzy fragment information as allowed by the holographic electron density theorem, (d) the study of correlations between local shape and activity, including through-bond and through-space components of interactions between parts of molecules and relations between local molecular shape and substituent effects, (e) using them as tools of density matrix extrapolation in conformational changes, (f) physically valid averaging and statistical distribution of several local electron densities of common stoichiometry, useful in electron density databank mining, for
Whiffen, D H
2013-01-01
Expression of Results in Quantum Chemistry recommends the appropriate insertion of physical constants in the output information of a theoretical paper in order to make the numerical end results of theoretical work easily transformed to SI units by the reader. The acceptance of this recommendation would circumvent the need for a set of atomic units each with its own symbol and name. It is the traditional use of the phrase """"atomic units"""" in this area which has obscured the real problem. The four SI dimensions of length, mass, time, and current require four physical constants to be permitte
Few-Qubit Magnetic Resonance Quantum Information Processors: Simulating Chemistry and Physics
Criger, Ben; Baugh, Jonathan
2012-01-01
We review recent progress made in quantum information processing (QIP) which can be applied in the simulation of quantum systems and chemical phenomena. The review is focused on quantum algorithms which are useful for quantum simulation of chemistry and advances in nuclear magnetic resonance (NMR) and electron spin resonance (ESR) QIP. Discussions also include a number of recent experiments demonstrating the current capabilities of the NMR QIP for quantum simulation and prospects for spin-based implementations of QIP.
Quantum-State-Resolved Ion-Molecule Chemistry
Chen, Gary; Yang, Tiangang; Campbell, Wesley; Hudson, Eric
2016-05-01
We propose a method to achieve quantum-state-resolved ion-molecule chemistry by utilizing cryogenic buffer gas cooling techniques and a combination of ion imaging and mass spectrometry of targets in an RF Paul trap. Cold molecular species produced by a cryogenic buffer gas beam (CBGB) are introduced to target ion species in an linear quadrupole trap (LQT) where ion imaging techniques and time of flight mass spectrometry (ToF) are then used to observe the target ions and the charged reaction products [1,2]. By taking advantage of the large ion-neutral interaction cross sections and characteristically long ion trap lifetimes, we can utilize the precision control over quantum states allowed by an ion trap to resolve state-to-state quantum chemical reactions without high-density molecular sample production, well within proposed capabilities. The combination of these two very general cold species production techniques allows for production and observation of a broad range of ion-neutral reactions. We initially plan to study chemical reactions between sympathetically cooled carbon ions (via laser cooled beryllium ions) with buffer gas cooled water. This work is supported by the US Air Force Office of Scientific Research.
Tantillo, Dean J
2013-08-01
This Highlight describes applications of quantum chemical calculations to problems in natural products chemistry, including the elucidation of natural product structures (distinguishing between constitutional isomers, distinguishing between diastereomers, and assigning absolute configuration) and determination of reasonable mechanisms for their formation.
A Quantum Chemistry Study on Structural Properties of Petroleum Resin
Institute of Scientific and Technical Information of China (English)
Wang Daxi; Pan Yueqiu; Zhang Hongye
2007-01-01
The geometries of resins with single-layer (SG), double-layer (DG) and triple-layer (TG) were calculated with the quantum chemistry method. The geometries and net charges of atoms were obtained. The calculated average distances between layers were 0.5348 nm and 0.5051 nm and the action energies were -9.6355 kJ/mol and -32.2803 kJ/mol for resins DG and TG, respectively. Higher electronegative polar atoms can easily form hydrogen bonds with hydrogen atoms of other resin molecules, resulting in resin aggregates. The minimum cross-sectional diameters of resin molecules are too large to enter the pores of zeolite, so they are likely to crack on the surface of zeolite.
Going beyond "no-pair relativistic quantum chemistry".
Liu, Wenjian; Lindgren, Ingvar
2013-07-07
The current field of relativistic quantum chemistry (RQC) has been built upon the no-pair and no-retardation approximations. While retardation effects must be treated in a time-dependent manner through quantum electrodynamics (QED) and are hence outside RQC, the no-pair approximation (NPA) has to be removed from RQC for it has some fundamental defects. Both configuration space and Fock space formulations have been proposed in the literature to do this. However, the former is simply wrong, whereas the latter is still incomplete. To resolve the old problems pertinent to the NPA itself and new problems beyond the NPA, we propose here an effective many-body (EMB) QED approach that is in full accordance with standard methodologies of electronic structure. As a first application, the full second order energy E2 of a closed-shell many-electron system subject to the instantaneous Coulomb-Breit interaction is derived, both algebraically and diagrammatically. It is shown that the same E2 can be obtained by means of 3 Goldstone-like diagrams through the standard many-body perturbation theory or 28 Feynman diagrams through the S-matrix technique. The NPA arises naturally by retaining only the terms involving the positive energy states. The potential dependence of the NPA can be removed by adding in the QED one-body counter terms involving the negative energy states, thereby leading to a "potential-independent no-pair approximation" (PI-NPA). The NPA, PI-NPA, EMB-QED, and full QED then span a continuous spectrum of relativistic molecular quantum mechanics.
Babbush, Ryan; Kivlichan, Ian D; Wei, Annie Y; Love, Peter J; Aspuru-Guzik, Alán
2015-01-01
We introduce novel algorithms for the quantum simulation of molecular systems which are asymptotically more efficient than those based on the Trotter-Suzuki decomposition. We present the first application of a recently developed technique for simulating Hamiltonian evolution using a truncated Taylor series to obtain logarithmic scaling with the inverse of the desired precision, an exponential improvement over all prior methods. The two algorithms developed in this work rely on a second quantized encoding of the wavefunction in which the state of an $N$ spin-orbital system is encoded in ${\\cal O}(N)$ qubits. Our first algorithm has time complexity $\\widetilde{\\cal O}(N^8 t)$. Our second algorithm involves on-the-fly computation of molecular integrals, in a way that is exponentially more precise than classical sampling methods, by using the truncated Taylor series simulation technique. Our second algorithm has the lowest asymptotic time complexity of any second quantized approach to quantum chemistry simulation...
Solved and unsolved problems in relativistic quantum chemistry
Energy Technology Data Exchange (ETDEWEB)
Kutzelnigg, Werner, E-mail: werner.kutzelnigg@rub.de [Lehrstuhl fuer Theoretische Chemie, Ruhr-Universitaet Bochum, D-44780 Bochum (Germany)
2012-02-20
Graphical abstract: The graphical abstract represents the Dirac-Coulomb Hamiltonian in Fock space in a diagrammatic notation. A line (vertical or slanted) with an upgoing arrow represents an eletron, with a downgoing arrow a positron. A cross in the first line means the potential created by a nucleus, a broken line represents the Coulomb interaction between electrons and positrons. Highlights: Black-Right-Pointing-Pointer Relativistic many-electron theory needs a Fock space and a field-dependent vacuum. Black-Right-Pointing-Pointer A good starting point is QED in Coulomb gauge without transversal photons. Black-Right-Pointing-Pointer The Dirac underworld picture is obsolete. Black-Right-Pointing-Pointer A kinetically balanced even-tempered Gaussian basis is complete. Black-Right-Pointing-Pointer 'Quantum chemistry in Fock space is preferable over QED. - Abstract: A hierarchy of approximations in relativistic many-electron theory is discussed that starts with the Dirac equation and its expansion in a kinetically balanced basis, via a formulation of non-interacting electrons in Fock space (which is the only consistent way to deal with negative-energy states). The most straightforward approximate Hamiltonian for interacting electrons is derived from quantum electrodynamics (QED) in Coulomb gauge with the neglect of transversal photons. This allows an exact (non-perturbative) decoupling of the electromagnetic field from the fermionic field. The electric interaction of the fermions is non-retarded and non-quantized. The quantization of the fermionic field leads to a polarizable vacuum. The simplest (but somewhat problematic) approximation is a no-pair projected theory with external-field projectors. The Dirac-Coulomb operator in configuration space (first quantization) is not acceptable, even if the Brown-Ravenhall disease is much less virulent than often claimed. Effects of transversal photons, such as the Breit interaction and renormalized self-interaction can be
Quantum Chemistry Meets Rotational Spectroscopy for Astrochemistry: Increasing Molecular Complexity
Puzzarini, Cristina
2016-06-01
For many years, scientists suspected that the interstellar medium was too hostile for organic species and that only a few simple molecules could be formed under such extreme conditions. However, the detection of approximately 180 molecules in interstellar or circumstellar environments in recent decades has changed this view dramatically. A rich chemistry has emerged, and relatively complex molecules such as C60 and C70 are formed. Recently, researchers have also detected complex organic and potentially prebiotic molecules, such as amino acids, in meteorites and in other space environments. Those discoveries have further stimulated the debate on the origin of the building blocks of life in the universe. Rotational spectroscopy plays a crucial role in the investigation of planetary atmosphere and the interstellar medium. Increasingly these astrochemical investigations are assisted by quantum-mechanical calculations of structures as well as spectroscopic and thermodynamic properties to guide and support observations, line assignments, and data analysis in these new and chemically complicated situations. However, it has proved challenging to extend accurate quantum-chemical computational approaches to larger systems because of the unfavorable scaling with the number of degrees of freedom (both electronic and nuclear). In this contribution, it is demonstrated that it is now possible to compute physicochemical properties of building blocks of biomolecules with an accuracy rivaling that of the most sophisticated experimental techniques. We analyze the spectroscopic properties of representative building blocks of DNA bases (uracil and thiouracil), of proteins (glycine and glycine dipeptide analogue), and also of PAH (phenalenyl radical and cation). V. Barone, M. Biczysko, C. Puzzarini 2015, Acc. Chem. Res., 48, 1413
Whole-Parts Strategies in Quantum Chemistry: Some Philosophical and Mereological Lessons
Directory of Open Access Journals (Sweden)
Jean-Pierre Llored
2014-12-01
Full Text Available Philosophers mainly refer to quantum chemistry in order to address questions about the reducibility or autonomy of chemistry relative to quantum physics, and to argue for or against ontological emergence. To make their point, they scrutinize quantum approximations and formalisms as if they were independent of the questions at stake. This paper proposes a return to history and to the laboratory so as to emphasize how quantum chemists never cease to negotiate the relationships between a molecule, its parts, and its environment. This investigation will enable us to draw methodological conclusions about the role of history within philosophical studies, and to examine how quantum chemistry can clarify important philosophical and mereological issues related to the emergence/reduction debate, or to the way instruments and contexts are involved in the material making and the formal description of wholes and parts.
A quantum chemistry study of natural gas hydrates.
Atilhan, Mert; Pala, Nezih; Aparicio, Santiago
2014-04-01
The structure and properties of natural gas hydrates containing hydrocarbons, CO₂, and N₂ molecules were studied by using computational quantum chemistry methods via the density functional theory approach. All host cages involved in I, II, and H types structures where filled with hydrocarbons up to pentanes, CO₂ and N₂ molecules, depending on their size, and the structures of these host-guest systems optimized. Structural properties, vibrational spectra, and density of states were analyzed together with results from atoms-in-a-molecule and natural bond orbitals methods. The inclusion of dispersion terms in the used functional plays a vital role for obtaining reliable information, and thus, B97D functional was shown to be useful for these systems. Results showed remarkable interaction energies, not strongly affected by the type of host cage, with molecules tending to be placed at the center of the cavities when host cages and guest molecules cavities are of similar size, but with molecules approaching hexagonal faces for larger cages. Vibrational properties show remarkable features in certain regions, with shiftings rising from host-guest interactions, and useful patterns in the terahertz region rising from water surface vibrations strongly coupled with guest molecules. Likewise, calculations on crystal systems for the I and H types were carried out using a pseudopotential approach combined with Grimme's method to take account of dispersion.
The many roles of quantum chemical predictions in synthetic organic chemistry.
Nguyen, Quynh Nhu N; Tantillo, Dean J
2014-03-01
This account discusses representative case studies for various applications of quantum chemical calculations in synthetic organic chemistry. These include confirmation of target structures, methodology development, and catalyst design. These examples demonstrate how predictions from quantum chemical calculations can be utilized to streamline synthetic efforts.
Garritz, Andoni
2013-07-01
This study has the key premise of teaching history and philosophy of physical sciences to illustrate how controversies and rivalries among scientists play a key role in the progress of science and why scientific development is not only founded on the accumulation of experimental data. The author is a defender of teachers who consider philosophical, historical and socio-scientific issues. In particular, the disputes can be used in science teaching to promote students awareness of the "historicity" of science and to facilitate the understanding of scientific progress beyond that of inductive generalizations. The establishment of a theory is accompanied with philosophical interpretations all the way. The author will try to show that it gives excellent results in teaching and learning to bring to the foreground the complexity that surrounds the development of ideas in science, illustrating how controversies, presuppositions, contradictions and inconsistencies find a place in the work of scientists and philosophers alike. In this sense, the case of quantum mechanics and quantum chemistry is very solid because it is historically full of controversies among their heads: Einstein, Bohr, De Broglie, Heisenberg, Schrödinger, Born, Lewis, Langmuir, Bader, Hoffmann and Pauling, at least.
Principles of conjugating quantum dots to proteins via carbodiimide chemistry.
Song, Fayi; Chan, Warren C W
2011-12-09
The covalent coupling of nanomaterials to bio-recognition molecules is a critical intermediate step in using nanomaterials for biology and medicine. Here we investigate the carbodiimide-mediated conjugation of fluorescent quantum dots to different proteins (e.g., immunoglobulin G, bovine serum albumin, and horseradish peroxidase). To enable these studies, we developed a simple method to isolate quantum dot bioconjugates from unconjugated quantum dots. The results show that the reactant concentrations and protein type will impact the overall number of proteins conjugated onto the surfaces of the quantum dots, homogeneity of the protein-quantum dot conjugate population, quantum efficiency, binding avidity, and enzymatic kinetics. We propose general principles that should be followed for the successful coupling of proteins to quantum dots.
Ventegodt, Søren; Hermansen, Tyge Dahl; Flensborg-Madsen, Trine; Nielsen, Maj Lyck; Merrick, Joav
2006-11-14
Deep quantum chemistry is a theory of deeply structured quantum fields carrying the biological information of the cell, making it able to remember, intend, represent the inner and outer world for comparison, understand what it "sees", and make choices on its structure, form, behavior and division. We suggest that deep quantum chemistry gives the cell consciousness and all the qualities and abilities related to consciousness. We use geometric symbolism, which is a pre-mathematical and philosophical approach to problems that cannot yet be handled mathematically. Using Occam's razor we have started with the simplest model that works; we presume this to be a many-dimensional, spiral fractal. We suggest that all the electrons of the large biological molecules' orbitals make one huge "cell-orbital", which is structured according to the spiral fractal nature of quantum fields. Consciousness of single cells, multi cellular structures as e.g. organs, multi-cellular organisms and multi-individual colonies (like ants) and human societies can thus be explained by deep quantum chemistry. When biochemical activity is strictly controlled by the quantum-mechanical super-orbital of the cell, this orbital can deliver energetic quanta as biological information, distributed through many fractal levels of the cell to guide form and behavior of an individual single or a multi-cellular organism. The top level of information is the consciousness of the cell or organism, which controls all the biochemical processes. By this speculative work inspired by Penrose and Hameroff we hope to inspire other researchers to formulate more strict and mathematically correct hypothesis on the complex and coherence nature of matter, life and consciousness.
Problems and solutions in quantum chemistry and physics
Johnson, Charles S
1988-01-01
Unusually varied problems, with detailed solutions, cover quantum mechanics, wave mechanics, angular momentum, molecular spectroscopy, scattering theory, more. 280 problems, plus 139 supplementary exercises.
Flick, Johannes; Ruggenthaler, Michael; Appel, Heiko; Rubio, Angel
2017-03-21
In this work, we provide an overview of how well-established concepts in the fields of quantum chemistry and material sciences have to be adapted when the quantum nature of light becomes important in correlated matter-photon problems. We analyze model systems in optical cavities, where the matter-photon interaction is considered from the weak- to the strong-coupling limit and for individual photon modes as well as for the multimode case. We identify fundamental changes in Born-Oppenheimer surfaces, spectroscopic quantities, conical intersections, and efficiency for quantum control. We conclude by applying our recently developed quantum-electrodynamical density-functional theory to spontaneous emission and show how a straightforward approximation accurately describes the correlated electron-photon dynamics. This work paves the way to describe matter-photon interactions from first principles and addresses the emergence of new states of matter in chemistry and material science.
Photoelectron Imaging as a Quantum Chemistry Visualization Tool
Grumbling, Emily R.; Pichugin, Kostyantyn; Mabbs, Richard; Sanov, Andrei
2011-01-01
An overview and simple example of photoelectron imaging is presented, highlighting its efficacy as a pedagogical tool for visualizing quantum phenomena. Specifically, photoelectron imaging of H[superscript -] (the simplest negative ion) is used to demonstrate several quantum mechanical principles. This example could be incorporated into an…
Linear-scaling and parallelizable algorithms for stochastic quantum chemistry
Booth, George H; Alavi, Ali
2013-01-01
For many decades, quantum chemical method development has been dominated by algorithms which involve increasingly complex series of tensor contractions over one-electron orbital spaces. Procedures for their derivation and implementation have evolved to require the minimum amount of logic and rely heavily on computationally efficient library-based matrix algebra and optimized paging schemes. In this regard, the recent development of exact stochastic quantum chemical algorithms to reduce computational scaling and memory overhead requires a contrasting algorithmic philosophy, but one which when implemented efficiently can often achieve higher accuracy/cost ratios with small random errors. Additionally, they can exploit the continuing trend for massive parallelization which hinders the progress of deterministic high-level quantum chemical algorithms. In the Quantum Monte Carlo community, stochastic algorithms are ubiquitous but the discrete Fock space of quantum chemical methods is often unfamiliar, and the metho...
Orenha, Renato P.; Galembeck, Sérgio E.
2014-01-01
This computational experiment presents qualitative molecular orbital (QMO) and computational quantum chemistry exercises of NO, NO[superscript+], and NO[superscript-]. Initially students explore several properties of the target molecules by Lewis diagrams and the QMO theory. Then, they compare qualitative conclusions with EHT and DFT calculations…
The Relationships between PCK Components: The Case of Quantum Chemistry Professors
Padilla, Kira; Van Driel, Jan
2011-01-01
The purpose of this paper is to capture the pedagogical content knowledge (PCK) of university professors about quantum chemistry. More specifically, we aimed to identify and analyze relationships between specific PCK components, using an adapted version of the model of PCK of Magnusson "et al.". A sample of university professors (n = 6)…
Stefani, Christina; Tsaparlis, Georgios
2009-01-01
We investigated students' knowledge constructions of basic quantum chemistry concepts, namely atomic orbitals, the Schrodinger equation, molecular orbitals, hybridization, and chemical bonding. Ausubel's theory of meaningful learning provided the theoretical framework and phenomenography the method of analysis. The semi-structured interview with…
Big Data Meets Quantum Chemistry Approximations: The Δ-Machine Learning Approach.
Ramakrishnan, Raghunathan; Dral, Pavlo O; Rupp, Matthias; von Lilienfeld, O Anatole
2015-05-12
Chemically accurate and comprehensive studies of the virtual space of all possible molecules are severely limited by the computational cost of quantum chemistry. We introduce a composite strategy that adds machine learning corrections to computationally inexpensive approximate legacy quantum methods. After training, highly accurate predictions of enthalpies, free energies, entropies, and electron correlation energies are possible, for significantly larger molecular sets than used for training. For thermochemical properties of up to 16k isomers of C7H10O2 we present numerical evidence that chemical accuracy can be reached. We also predict electron correlation energy in post Hartree-Fock methods, at the computational cost of Hartree-Fock, and we establish a qualitative relationship between molecular entropy and electron correlation. The transferability of our approach is demonstrated, using semiempirical quantum chemistry and machine learning models trained on 1 and 10% of 134k organic molecules, to reproduce enthalpies of all remaining molecules at density functional theory level of accuracy.
Big Data meets Quantum Chemistry Approximations: The $\\Delta$-Machine Learning Approach
Ramakrishnan, Raghunathan; Rupp, Matthias; von Lilienfeld, O Anatole
2015-01-01
Chemically accurate and comprehensive studies of the virtual space of all possible molecules are severely limited by the computational cost of quantum chemistry. We introduce a composite strategy that adds machine learning corrections to computationally inexpensive approximate legacy quantum methods. After training, highly accurate predictions of enthalpies, free energies, entropies, and electron correlation energies are possible, for significantly larger molecular sets than used for training. For thermochemical properties of up to 16k constitutional isomers of C$_7$H$_{10}$O$_2$ we present numerical evidence that chemical accuracy can be reached. We also predict electron correlation energy in post Hartree-Fock methods, at the computational cost of Hartree-Fock, and we establish a qualitative relationship between molecular entropy and electron correlation. The transferability of our approach is demonstrated, using semi-empirical quantum chemistry and machine learning models trained on 1 and 10\\% of 134k organ...
Dynamical mean-field theory for quantum chemistry.
Lin, Nan; Marianetti, C A; Millis, Andrew J; Reichman, David R
2011-03-04
The dynamical mean-field concept of approximating an unsolvable many-body problem in terms of the solution of an auxiliary quantum impurity problem, introduced to study bulk materials with a continuous energy spectrum, is here extended to molecules, i.e., finite systems with a discrete energy spectrum. The application to small clusters of hydrogen atoms yields ground state energies which are competitive with leading quantum chemical approaches at intermediate and large interatomic distances as well as good approximations to the excitation spectrum.
Test of quantum chemistry in vibrationally-hot hydrogen molecules
Niu, M L; Ubachs, W
2015-01-01
Precision measurements are performed on highly excited vibrational quantum states of molecular hydrogen. The $v=12, J=0-3$ rovibrational levels of H$_2$ ($X^1\\Sigma_g^+$), lying only $2000$ cm$^{-1}$ below the first dissociation limit, were populated by photodissociation of H$_2$S and their level energies were accurately determined by two-photon Doppler-free spectroscopy. A comparison between the experimental results on $v=12$ level energies with the best \\textit{ab initio} calculations shows good agreement, where the present experimental accuracy of $3.5 \\times10^{-3}$ cm$^{-1}$ is more precise than theory, hence providing a gateway to further test theoretical advances in this benchmark quantum system.
Photodissociation of a diatomic molecule in the quantum regime reveals ultracold chemistry
McDonald, M; Apfelbeck, F; Lee, C -H; Majewska, I; Moszynski, R; Zelevinsky, T
2015-01-01
Chemical reactions at temperatures near absolute zero require a full quantum description of the reaction pathways and enable enhanced control of the products via quantum state selection. Ultracold molecule experiments have provided initial insight into the quantum nature of basic chemical processes involving diatomic molecules, for example from studies of bimolecular reactions, but complete control over the reactants and products has remained elusive. The "half-collision" process of photodissociation is an indispensable tool in molecular physics and offers significantly more control than the reverse process of photoassociation. Here we reach a fully quantum regime with photodissociation of ultracold $^{88}$Sr$_2$ molecules where the initial bound state of the molecule and the target continuum state of the fragments are strictly controlled. Detection of the photodissociation products via optical absorption imaging reveals the hallmarks of ultracold chemistry: resonant and nonresonant barrier tunneling, importa...
Directory of Open Access Journals (Sweden)
Régis Casimiro Leal
2010-01-01
Full Text Available Quantum chemical calculations were performed in order to obtain molecular properties such as electronic density, dipole moment, atomic charges, and bond lengths, which were compared to qualitative results based on the theories of the organic chemistry. The quantum chemistry computational can be a useful tool to support the main theories of the organic chemistry.
Structure and Quantum Chemistry Study on Hexaacetyl D-Mannose Hydrazine
Institute of Scientific and Technical Information of China (English)
CAO Rui; LIU Xiao-Hong; CHENG Chang-Mei; WANG Ru-Ji; ZHAO Yu-Fen; WANG Lai-Xi
2007-01-01
Hexaacetyl D-mannose hydrazine is one type of important intermediates in saccharide chemistry. In this paper, its single crystal was obtained and furthermore, X-ray diffraction and quantum chemistry calculation were performed. It belongs to orthorhombic system, space group P212121, with a=16.267(3), b=19.263(3), c=7.1948(12)(A), Mr=446.41, Dc=1.315 g/cm3, V=2254.5(6)(A)3 and Z=4. Meanwhile, the experimental results also provide information for designing a kind of molecular switch based on the mannose nitrogenous derivatives.
Ito, Shingo; Irle, Stephan; Okamoto, Yuko
2016-07-01
The replica-exchange umbrella sampling (REUS) method combines replica-exchange and umbrella sampling methods and allows larger conformational sampling than conventional simulation methods. This method has been used in many studies to understand docking mechanisms and the functions of molecules. However, REUS has not been combined with quantum chemical codes. Therefore, we implemented the REUS simulation technique in the DFTB + quantum chemistry code utilizing approximate density functional theory. We performed REUS simulations of an intra-molecular proton transfer reaction of malonaldehyde and a formation of a phthalocyanine from four phthalonitriles and one iron atom to validate the reliability of our implemented REUS-DFTB + combination.
Jaffe, Richard; Langhoff, Stephen R. (Technical Monitor)
1995-01-01
Ab initio quantum chemistry calculations for model molecules can be used to parameterize force fields for molecular dynamics simulations of polymers. Emphasis in our research group is on using quantum chemistry-based force fields for molecular dynamics simulations of organic polymers in the melt and glassy states, but the methodology is applicable to simulations of small molecules, multicomponent systems and solutions. Special attention is paid to deriving reliable descriptions of the non-bonded and electrostatic interactions. Several procedures have been developed for deriving and calibrating these parameters. Our force fields for aromatic polyimide simulations will be described. In this application, the intermolecular interactions are the critical factor in determining many properties of the polymer (including its color).
Quantum Chemistry of Solids The LCAO First Principles Treatment of Crystals
Evarestov, Robert A
2007-01-01
Quantum Chemistry of Solids delivers a comprehensive account of the main features and possibilities of LCAO methods for the first principles calculations of electronic structure of periodic systems. The first part describes the basic theory underlying the LCAO methods applied to periodic systems and the use of wave-function-based (Hartree-Fock), density-based (DFT) and hybrid hamiltonians. The translation and site symmetry consideration is included to establish connection between k-space solid-state physics and real-space quantum chemistry methods in the framework of cyclic model of an infinite crystal. The inclusion of electron correlation effects for periodic systems is considered on the basis of localized crystalline orbitals. The possibilities of LCAO methods for chemical bonding analysis in periodic systems are discussed. The second part deals with the applications of LCAO methods for calculations of bulk crystal properties, including magnetic ordering and crystal structure optimization. The discussion o...
DEFF Research Database (Denmark)
Gordon, Keith C; McGoverin, Cushla M; Strachan, Clare J
2007-01-01
A number of case studies that illustrate how quantum chemistry may be used in studying pharmaceutical systems are reviewed. A brief introduction to quantum methods is provided and the use of these methods in understanding the structure and properties of indometacin and carbamazepine is discussed....... The use of calculated structures and molecular electrostatic potentials in developing quantitative structure-activity relationships is discussed along with the use of computation chemistry to predict spectroscopic properties....
STUDY OF GRAFT SITES IN EPOXY GRAFT COPOLYMERS BY QUANTUM CHEMISTRY CALCULATIONS
Institute of Scientific and Technical Information of China (English)
Song Chen; Xiao-yu Li
2009-01-01
Exploration and characterization of grafting productions by experimental methods are often cumbersome or sometimes impossible. Therefore, quantum chemistry calculations were performed to characterize the graft sites of epoxy resin. According to the Gibbs free energy criterion of the second law of thermodynamic, the reported graft sites were confirmed, and more important, some unreported graft sites were found. In addition, method of increasing the number of graft sites was studied in this article.
Lipkowitz, Kenny B.
1982-01-01
Describes a graduate-level course in physical-organic chemistry in which students learn to solve problems using computer programs available through the Quantum Chemistry Program Exchange. Includes condensed syllabus and time line showing where various computational programs are introduced. (Author/JN)
Feil, Dirk
1992-01-01
Quantum chemistry and the concepts used daily in chemistry are increasingly growing apart. Among the concepts that are able to bridge the gap between theory and experimental practice, electron density distribution has an important place. The study of this distribution has led to new developments in
Turi, László
2016-04-21
We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory(DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavitystructure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.
Surface Chemistry of Semiconducting Quantum Dots: Theoretical Perspectives.
Kilina, Svetlana V; Tamukong, Patrick K; Kilin, Dmitri S
2016-10-18
Colloidal quantum dots (QDs) are near-ideal nanomaterials for energy conversion and lighting technologies. However, their photophysics exhibits supreme sensitivity to surface passivation and defects, of which control is problematic. The role of passivating ligands in photodynamics remains questionable and is a focus of ongoing research. The optically forbidden nature of surface-associated states makes direct measurements on them challenging. Therefore, computational modeling is imperative for insights into surface passivation and its impact on light-driven processes in QDs. This Account discusses challenges and recent progress in understanding surface effects on the photophysics of QDs addressed via quantum-chemical calculations. We overview different methods, including the effective mass approximation (EMA), time-dependent density functional theory (TDDFT), and multiconfiguration approaches, considering their strengths and weaknesses relevant to modeling of QDs with a complicated surface. We focus on CdSe, PbSe, and Si QDs, where calculations successfully explain experimental trends sensitive to surface defects, doping, and ligands. We show that the EMA accurately describes both linear and nonlinear optical properties of large-sized CdSe QDs (>2.5 nm), while TDDFT is required for smaller QDs where surface effects dominate. Both approaches confirm efficient two-photon absorption enabling applications of QDs as nonlinear optical materials. TDDFT also describes the effects of morphology on the optical response of QDs: the photophysics of stoichiometric, magic-sized XnYn (X = Cd, Pb; Y = S, Se) QDs is less sensitive to their passivation compared with nonstoichiometric Xn≠mYm QDs. In the latter, surface-driven optically inactive midgap states can be eliminated by anionic ligands, explaining the better emission of metal-enriched QDs compared with nonmetal-enriched QDs. Ideal passivation of magic-sized QDs by amines and phosphine oxides leaves lower-energy transitions
Quantum Chemistry, and Eclectic Mix: From Silicon Carbide to Size Consistency
Energy Technology Data Exchange (ETDEWEB)
Rintelman, Jamie Marie [Iowa State Univ., Ames, IA (United States)
2004-12-19
Chemistry is a field of great breadth and variety. It is this diversity that makes for both an interesting and challenging field. My interests have spanned three major areas of theoretical chemistry: applications, method development, and method evaluation. The topics presented in this thesis are as follows: (1) a multi-reference study of the geometries and relative energies of four atom silicon carbide clusters in the gas phase; (2) the reaction of acetylene on the Si(100)-(2x1) surface; (3) an improvement to the Effective Fragment Potential (EFP) solvent model to enable the study of reactions in both aqueous and nonaqueous solution; and (4) an evaluation of the size consistency of Multireference Perturbation Theory (MRPT). In the following section, the author briefly discusses two topics central to, and present throughout, this thesis: Multi-reference methods and Quantum Mechanics/Molecular Mechanics (QM/MM) methods.
Uquantchem: A versatile and easy to use Quantum Chemistry Computational Software
Souvatzis, Petros
2013-01-01
In this paper we present the Uppsala Quantum Chemistry package (UQUANTCHEM), a new and versatile computational platform with capabilities ranging from simple Hartree-Fock calculations to state of the art First principles Extended Lagrangian Born Oppenheimer Molecular Dynamics (XL- BOMD) and diffusion quantum Monte Carlo (DMC). The UQUANTCHEM package is distributed under the general public license and can be directly downloaded from the code web-site. Together with a presentation of the different capabilities of the uquantchem code and a more technical discus- sion on how these capabilities have been implemented, a presentation of the user-friendly aspect of the package on the basis of the large number of default settings will also be presented. Furthermore, since the code has been parallelized within the framework of the message passing interface (MPI), the timing of some benchmark calculations are reported to illustrate how the code scales with the number of computational nodes for different levels of chemic...
Green chemistry for large-scale synthesis of semiconductor quantum dots.
Liu, Jin-Hua; Fan, Jun-Bing; Gu, Zheng; Cui, Jing; Xu, Xiao-Bo; Liang, Zhi-Wu; Luo, Sheng-Lian; Zhu, Ming-Qiang
2008-05-20
Large-scale synthesis of semiconductor nanocrystals or quantum dots (QDs) with high concentration and high yield through simultaneously increasing the precursor concentration was introduced. This synthetic route conducted in diesel has produced gram-scale CdSe semiconductor quantum dots (In optimal scale-up synthetic condition, the one-pot yield of QDs is up to 9.6g). The reaction has been conducted in open air and at relatively low temperature at 190-230 degrees C in the absence of expensive organic phosphine ligands, aliphatic amine and octadecene, which is really green chemistry without high energy cost for high temperature reaction and unessential toxic chemicals except for Cd, which is the essential building block for QDs.
Rossi, Elda; Evangelisti, Stefano; Laganà, Antonio; Monari, Antonio; Rampino, Sergio; Verdicchio, Marco; Baldridge, Kim K; Bendazzoli, Gian Luigi; Borini, Stefano; Cimiraglia, Renzo; Angeli, Celestino; Kallay, Peter; Lüthi, Hans P; Ruud, Kenneth; Sanchez-Marin, José; Scemama, Anthony; Szalay, Peter G; Tajti, Attila
2014-03-30
Code interoperability and the search for domain-specific standard data formats represent critical issues in many areas of computational science. The advent of novel computing infrastructures such as computational grids and clouds make these issues even more urgent. The design and implementation of a common data format for quantum chemistry (QC) and quantum dynamics (QD) computer programs is discussed with reference to the research performed in the course of two Collaboration in Science and Technology Actions. The specific data models adopted, Q5Cost and D5Cost, are shown to work for a number of interoperating codes, regardless of the type and amount of information (small or large datasets) to be exchanged. The codes are either interfaced directly, or transfer data by means of wrappers; both types of data exchange are supported by the Q5/D5Cost library. Further, the exchange of data between QC and QD codes is addressed. As a proof of concept, the H + H2 reaction is discussed. The proposed scheme is shown to provide an excellent basis for cooperative code development, even across domain boundaries. Moreover, the scheme presented is found to be useful also as a production tool in the grid distributed computing environment.
Interactive quantum chemistry: a divide-and-conquer ASED-MO method.
Bosson, Mäel; Richard, Caroline; Plet, Antoine; Grudinin, Sergei; Redon, Stephane
2012-03-15
We present interactive quantum chemistry simulation at the atom superposition and electron delocalization molecular orbital (ASED-MO) level of theory. Our method is based on the divide-and-conquer (D&C) approach, which we show is accurate and efficient for this non-self-consistent semiempirical theory. The method has a linear complexity in the number of atoms, scales well with the number of cores, and has a small prefactor. The time cost is completely controllable, as all steps are performed with direct algorithms, i.e., no iterative schemes are used. We discuss the errors induced by the D&C approach, first empirically on a few examples, and then via a theoretical study of two toy models that can be analytically solved for any number of atoms. Thanks to the precision and speed of the D&C approach, we are able to demonstrate interactive quantum chemistry simulations for systems up to a few hundred atoms on a current multicore desktop computer. When drawing and editing molecular systems, interactive simulations provide immediate, intuitive feedback on chemical structures. As the number of cores on personal computers increases, and larger and larger systems can be dealt with, we believe such interactive simulations-even at lower levels of theory-should thus prove most useful to effectively understand, design and prototype molecules, devices and materials.
A Synthesis of Fluid Dynamics and Quantum Chemistry for the Design of Nanoelectronics
MacDougall, Preston J.
1998-01-01
In 1959, during a famous lecture entitled "There's Plenty of Room at the Bottom", Richard Feynman focused on the startling technical possibilities that would exist at the limit of miniaturization, that being atomically precise devices with dimensions in the nanometer range. A nanometer is both a convenient unit of length for medium to large sized molecules, and the root of the name of the new interdisciplinary field of "nanotechnology". Essentially, "nanoelectronics" denotes the goal of shrinking electronic devices, such as diodes and transistors, as well as integrated circuits of such devices that can perform logical operations, down to dimensions in the range of 100 nanometers. The thirty-year hiatus in the development of nanotechnology can figuratively be seen as a period of waiting for the bottom-up and atomically precise construction skills of synthetic chemistry to meet the top-down reductionist aspirations of device physics. The sub-nanometer domain of nineteenth-century classical chemistry has steadily grown, and state-of-the-art supramolecular chemistry can achieve atomic precision in non-repeating molecular assemblies of the size desired for nanotechnology. For nanoelectronics in particular, a basic understanding of the electron transport properties of molecules must also be developed. Quantum chemistry provides powerful computational methods that can accurately predict the properties of small to medium sized molecules on a desktop workstation, and those of large molecules if one has access to a supercomputer. Of the many properties of a molecule that quantum chemistry routinely predicts, the ability to carry a current is one that had not even been considered until recently. "Currently", there is a controversy over just how to define this key property. Reminiscent of the situation in high-Tc superconductivity, much of the difficulty arises from the different models that are used to simplify the complex electronic structure of real materials. A model
Ruzi, Mahmut; Anderson, David T
2015-12-17
Our group has been working to develop parahydrogen (pH2) matrix isolation spectroscopy as a method to study low-temperature condensed-phase reactions of atomic hydrogen with various reaction partners. Guided by the well-defined studies of cold atom chemistry in rare-gas solids, the special properties of quantum hosts such as solid pH2 afford new opportunities to study the analogous chemical reactions under quantum diffusion conditions in hopes of discovering new types of chemical reaction mechanisms. In this study, we present Fourier transform infrared spectroscopic studies of the 193 nm photoinduced chemistry of nitric oxide (NO) isolated in solid pH2 over the 1.8 to 4.3 K temperature range. Upon short-term in situ irradiation the NO readily undergoes photolysis to yield HNO, NOH, NH, NH3, H2O, and H atoms. We map the postphotolysis reactions of mobile H atoms with NO and document first-order growth in HNO and NOH reaction products for up to 5 h after photolysis. We perform three experiments at 4.3 K and one at 1.8 K to permit the temperature dependence of the reaction kinetics to be quantified. We observe Arrhenius-type behavior with a pre-exponential factor of A = 0.036(2) min(-1) and Ea = 2.39(1) cm(-1). This is in sharp contrast to previous H atom reactions we have studied in solid pH2 that display definitively non-Arrhenius behavior. The contrasting temperature dependence measured for the H + NO reaction is likely related to the details of H atom quantum diffusion in solid pH2 and deserves further study.
Babbush, Ryan; Kivlichan, Ian D; Wei, Annie Y; Love, Peter J; Aspuru-Guzik, Alán
2015-01-01
We present a quantum algorithm for the simulation of molecular systems that is asymptotically more efficient than all previous algorithms in the literature. As in the first paper of this series \\cite{BabbushSparse1}, we employ a recently developed technique for simulating Hamiltonian evolution using a truncated Taylor series to obtain logarithmic scaling with the inverse of the desired precision, which is an exponential improvement over methods based on the Trotter-Suzuki decomposition. The algorithm of this paper involves simulation under an oracle for the sparse, first quantized representation of the Hamiltonian known as the configuration interaction (CI) matrix. We construct and query the CI matrix oracle to allow for on-the-fly computation of molecular integrals in a way that is exponentially more efficient than classical numerical methods. Whereas second quantized representations of the wavefunction require $\\widetilde{\\cal O}(N)$ qubits, where $N$ is the number of single-particle spin-orbitals, the CI m...
Merkl, Jan-Philip; Ostermann, Johannes; Schmidtke, Christian; Kloust, Hauke; Eggers, Robin; Feld, Artur; Wolter, Christopher; Kreuziger, Anna-Marlena; Flessau, Sandra; Mattoussi, Hedi; Weller, Horst
2014-03-01
We describe the design and optimization of an amphiphilic diblock copolymer and its use to provide surface functionalization of colloidal semiconductor nanoparticles (quantum dots, QDs). This polymer coating promotes hydrophilicity of the nanocrystals while providing numerous functional groups ideally suited for biofunctionalization of the QDs using copper-catalyzed azide alkyne Husigen 1,3-cyloaddition (i.e., cupper catalyzed "click" reaction). Copper ions are known to quench the fluorescence of QDs in solution. Thus effective shielding of the nanocrystal surface is essential to apply copper-catalyzed reactions to luminescent QDs without drastically quenching their emission. We have applied a strategy based on micellar encapsulation within poly(isoprene-block- ethylene oxide) diblock-copolymers (PI-b-PEO), where three critical factors promote and control the effectiveness of the shielding of copper ion penetration: 1) The excess of PI-b-PEO, 2) the size of PI-b-PEO and 3) insertion of an additional PS-shell grown via seeded emulsion polymerization (EP) reaction. Due to the amphiphilic character of the block-copolymer, this approach provides a shielding layer surrounding the particles, preventing metal ions from reaching the QD surfaces and maintaining high photoluminescence. The effective shielding allowed the use of copper-catalyzed azide-alkyne 1,3-cycloaddition (CuAAC) to hydrophilic and highly fluorescent QDs, opening up great possibilities for the bio functionalization of QDs.
Olivares-Amaya, Roberto
The understanding of molecular effects in nanoscale environments is becoming increasingly relevant for various emerging fields. These include spectroscopy for molecular identification as well as in finding molecules for energy harvesting. Theoretical quantum chemistry has been increasingly useful to address these phenomena to yield an understanding of these effects. In the first part of this dissertation, we study the chemical effect of surface-enhanced Raman scattering (SERS). We use quantum chemistry simulations to study the metal-molecule interactions present in these systems. We find that the excitations that provide a chemical enhancement contain a mixed contribution from the metal and the molecule. Moreover, using atomistic studies we propose an additional source of enhancement, where a transition metal dopant surface could provide an additional enhancement. We also develop methods to study the electrostatic effects of molecules in metallic environments. We study the importance of image-charge effects, as well as field-bias to molecules interacting with perfect conductors. The atomistic modeling and the electrostatic approximation enable us to study the effects of the metal interacting with the molecule in a complementary fashion, which provides a better understanding of the complex effects present in SERS. In the second part of this dissertation, we present the Harvard Clean Energy Project, a high-throughput approach for a large-scale computational screening and design of organic photovoltaic materials. We create molecular libraries to search for candidates structures and use quantum chemistry, machine learning and cheminformatics methods to characterize these systems and find structure-property relations. The scale of this study requires an equally large computational resource. We rely on distributed volunteer computing to obtain these properties. In the third part of this dissertation we present our work related to the acceleration of electronic structure
Ramabhadran, Raghunath O; Raghavachari, Krishnan
2014-12-16
CONSPECTUS: Quantum chemistry and electronic structure theory have proven to be essential tools to the experimental chemist, in terms of both a priori predictions that pave the way for designing new experiments and rationalizing experimental observations a posteriori. Translating the well-established success of electronic structure theory in obtaining the structures and energies of small chemical systems to increasingly larger molecules is an exciting and ongoing central theme of research in quantum chemistry. However, the prohibitive computational scaling of highly accurate ab initio electronic structure methods poses a fundamental challenge to this research endeavor. This scenario necessitates an indirect fragment-based approach wherein a large molecule is divided into small fragments and is subsequently reassembled to compute its energy accurately. In our quest to further reduce the computational expense associated with the fragment-based methods and overall enhance the applicability of electronic structure methods to large molecules, we realized that the broad ideas involved in a different area, theoretical thermochemistry, are transferable to the area of fragment-based methods. This Account focuses on the effective merger of these two disparate frontiers in quantum chemistry and how new concepts inspired by theoretical thermochemistry significantly reduce the total number of electronic structure calculations needed to be performed as part of a fragment-based method without any appreciable loss of accuracy. Throughout, the generalized connectivity based hierarchy (CBH), which we developed to solve a long-standing problem in theoretical thermochemistry, serves as the linchpin in this merger. The accuracy of our method is based on two strong foundations: (a) the apt utilization of systematic and sophisticated error-canceling schemes via CBH that result in an optimal cutting scheme at any given level of fragmentation and (b) the use of a less expensive second
To investigate the coupled effects of solution chemistry and vadose zone processes on the mobility of quantum dot (QD) nanoparticles, laboratory scale transport experiments were performed. The complex coupled effects of ionic strength, size of QD aggregates, surface tension, contact angle, infiltrat...
Li, Ying; Chan, Maria K Y; Sankaranarayanan, Subramanian; Rouxb, Benoît
2016-01-01
In molecular dynamics (MD) simulation, force field determines the capability of an individual model in capturing physical and chemistry properties. The method for generating proper parameters of the force field form is the key component for computational research in chemistry, biochemistry, and condensed-phase physics. Our study showed that the feasibility to predict experimental condensed phase properties (i.e., density and heat of vaporization) of methanol through problem specific force field from only quantum chemistry information. To acquire the satisfying parameter sets of the force field, the genetic algorithm (GA) is the main optimization method. For electrostatic potential energy, we optimized both the electrostatic parameters of methanol using the GA method, which leads to low deviations of between the quantum mechanics (QM) calculations and the GA optimized parameters. We optimized the van der Waals (vdW) parameters both using GA and guided GA methods by calibrating interaction energy of various met...
Two-electron reduction of ethylene carbonate: a quantum chemistry re-examination of mechanisms
Leung, Kevin
2013-01-01
Passivating solid-electrolyte interphase (SEI) films arising from electrolyte decomposition on low-voltage lithium ion battery anode surfaces are critical for battery operations. We review the recent theoretical literature on electrolyte decomposition and emphasize the modeling work on two-electron reduction of ethylene carbonate (EC, a key battery organic solvent). One of the two-electron pathways, which releases CO gas, is re-examined using simple quantum chemistry calculations. Excess electrons are shown to preferentially attack EC in the order (broken EC^-) > (intact EC^-) > EC. This confirms the viability of two electron processes and emphasizes that they need to be considered when interpreting SEI experiments. An estimate of the crossover between one- and two-electron regimes under a homogeneous reaction zone approximation is proposed.
Neural Network Based on Quantum Chemistry for Predicting Melting Point of Organic Compounds
Institute of Scientific and Technical Information of China (English)
Juan A. Lazzús
2009-01-01
The melting points of organic compounds were estimated using a combined method that includes a backpropagation neural network and quantitative structure property relationship (QSPR) parameters in quantum chemistry. Eleven descriptors that reflect the intermolec-ular forces and molecular symmetry were used as input variables. QSPR parameters were calculated using molecular modeling and PM3 semi-empirical molecular orbital theories. A total of 260 compounds were used to train the network, which was developed using MatLab. Then, the melting points of 73 other compounds were predicted and results were compared to experimental data from the literature. The study shows that the chosen artificial neural network and the quantitative structure property relationships method present an excellent alternative for the estimation of the melting point of an organic compound, with average absolute deviation of 5%.
Tasso, Mariana; Giovanelli, Emerson; Zala, Diana; Bouccara, Sophie; Fragola, Alexandra; Hanafi, Mohamed; Lenkei, Zsolt; Pons, Thomas; Lequeux, Nicolas
2015-11-24
Long-term inspection of biological phenomena requires probes of elevated intra- and extracellular stability and target biospecificity. The high fluorescence and photostability of quantum dot (QD) nanoparticles contributed to foster their promise as bioimaging tools that could overcome limitations associated with traditional fluorophores. However, QDs' potential as a bioimaging platform relies upon a precise control over the surface chemistry modifications of these nano-objects. Here, a zwitterion-vinylimidazole block copolymer ligand was synthesized, which regroups all anchoring groups in one compact terminal block, while the rest of the chain is endowed with antifouling and bioconjugation moieties. By further application of an oriented bioconjugation approach with whole IgG antibodies, QD nanobioconjugates were obtained that display outstanding intra- and extracellular stability as well as biorecognition capacity. Imaging the internalization and intracellular dynamics of a transmembrane cell receptor, the CB1 brain cannabinoid receptor, both in HEK293 cells and in neurons, illustrates the breadth of potential applications of these nanoprobes.
Yanai, Takeshi; Kurashige, Yuki; Neuscamman, Eric; Chan, Garnet Kin-Lic
2010-01-01
We describe the joint application of the density matrix renormalization group and canonical transformation theory to multireference quantum chemistry. The density matrix renormalization group provides the ability to describe static correlation in large active spaces, while the canonical transformation theory provides a high-order description of the dynamic correlation effects. We demonstrate the joint theory in two benchmark systems designed to test the dynamic and static correlation capabilities of the methods, namely, (i) total correlation energies in long polyenes and (ii) the isomerization curve of the [Cu2O2]2+ core. The largest complete active spaces and atomic orbital basis sets treated by the joint DMRG-CT theory in these systems correspond to a (24e,24o) active space and 268 atomic orbitals in the polyenes and a (28e,32o) active space and 278 atomic orbitals in [Cu2O2]2+.
Bridging the Gap Between Quantum Chemistry and Classical Simulations for CO_{2} Capture
Energy Technology Data Exchange (ETDEWEB)
Gagliardi, Laura [Univ. of Minnesota, Minneapolis, MN (United States)
2015-09-17
We have developed a systematic procedure to generate transferable force fields to simulate the behavior of CO_{2} and other gases in open-metal-site metal organic frameworks using high-level quantum chemical calculations. Monte Carlo simulations based on an ab initio force field for CO_{2} in the Mg_{2}(dobpdc) material have been employed to describe the interactions of CO_{2} with open metals. Our study has shed some light on the interpretation of thermodynamic data of flue gas in Mg_{2}(dobpdc). This force field accurately describes the chemistry of the open metal sites, and is transferable to other structures.
Many-body quantum chemistry for the electron gas: convergent perturbative theories
Shepherd, James J
2013-01-01
We investigate the accuracy of a number of wavefunction based methods at the heart of quantum chemistry for metallic systems. Using Hartree-Fock as a reference, perturbative (M{\\o}ller-Plesset, MP) and coupled cluster (CC) theories are used to study the uniform electron gas model. Our findings suggest that non-perturbative coupled cluster theories are acceptable for modelling electronic interactions in metals whilst perturbative coupled cluster theories are not. Using screened interactions, we propose a simple modification to the widely-used coupled-cluster singles and doubles plus perturbative triples method (CCSD(T)) that lifts the divergent behaviour and is shown to give very accurate correlation energies for the homogeneous electron gas.
The Quixote project: Collaborative and Open Quantum Chemistry data management in the Internet age
Directory of Open Access Journals (Sweden)
Adams Sam
2011-10-01
Full Text Available Abstract Computational Quantum Chemistry has developed into a powerful, efficient, reliable and increasingly routine tool for exploring the structure and properties of small to medium sized molecules. Many thousands of calculations are performed every day, some offering results which approach experimental accuracy. However, in contrast to other disciplines, such as crystallography, or bioinformatics, where standard formats and well-known, unified databases exist, this QC data is generally destined to remain locally held in files which are not designed to be machine-readable. Only a very small subset of these results will become accessible to the wider community through publication. In this paper we describe how the Quixote Project is developing the infrastructure required to convert output from a number of different molecular quantum chemistry packages to a common semantically rich, machine-readable format and to build respositories of QC results. Such an infrastructure offers benefits at many levels. The standardised representation of the results will facilitate software interoperability, for example making it easier for analysis tools to take data from different QC packages, and will also help with archival and deposition of results. The repository infrastructure, which is lightweight and built using Open software components, can be implemented at individual researcher, project, organisation or community level, offering the exciting possibility that in future many of these QC results can be made publically available, to be searched and interpreted just as crystallography and bioinformatics results are today. Although we believe that quantum chemists will appreciate the contribution the Quixote infrastructure can make to the organisation and and exchange of their results, we anticipate that greater rewards will come from enabling their results to be consumed by a wider community. As the respositories grow they will become a valuable source of
Maia, Julio Daniel Carvalho; Urquiza Carvalho, Gabriel Aires; Mangueira, Carlos Peixoto; Santana, Sidney Ramos; Cabral, Lucidio Anjos Formiga; Rocha, Gerd B
2012-09-11
In this study, we present some modifications in the semiempirical quantum chemistry MOPAC2009 code that accelerate single-point energy calculations (1SCF) of medium-size (up to 2500 atoms) molecular systems using GPU coprocessors and multithreaded shared-memory CPUs. Our modifications consisted of using a combination of highly optimized linear algebra libraries for both CPU (LAPACK and BLAS from Intel MKL) and GPU (MAGMA and CUBLAS) to hasten time-consuming parts of MOPAC such as the pseudodiagonalization, full diagonalization, and density matrix assembling. We have shown that it is possible to obtain large speedups just by using CPU serial linear algebra libraries in the MOPAC code. As a special case, we show a speedup of up to 14 times for a methanol simulation box containing 2400 atoms and 4800 basis functions, with even greater gains in performance when using multithreaded CPUs (2.1 times in relation to the single-threaded CPU code using linear algebra libraries) and GPUs (3.8 times). This degree of acceleration opens new perspectives for modeling larger structures which appear in inorganic chemistry (such as zeolites and MOFs), biochemistry (such as polysaccharides, small proteins, and DNA fragments), and materials science (such as nanotubes and fullerenes). In addition, we believe that this parallel (GPU-GPU) MOPAC code will make it feasible to use semiempirical methods in lengthy molecular simulations using both hybrid QM/MM and QM/QM potentials.
Fast Quantum Molecular Dynamics Simulations of Shock-induced Chemistry in Organic Liquids
Cawkwell, Marc
2014-03-01
The responses of liquid formic acid and phenylacetylene to shock compression have been investigated via quantum-based molecular dynamics simulations with the self-consistent tight-binding code LATTE. Microcanonical Born-Oppenheimer trajectories with precise conservation of the total energy were computed without relying on an iterative self-consistent field optimization of the electronic degrees of freedom at each time step via the Fast Quantum Mechanical Molecular Dynamics formalism [A. M. N. Niklasson and M. J. Cawkwell, Phys. Rev. B, 86, 174308 (2012)]. The conservation of the total energy in our trajectories was pivotal for the capture of adiabatic shock heating as well as temperature changes arising from endo- or exothermic chemistry. Our self-consistent tight-binding parameterizations yielded very good predictions for the gas-phase geometries of formic acid and phenylacetylene molecules and the principal Hugoniots of the liquids. In accord with recent flyer-plate impact experiments, our simulations revealed i) that formic acid reacts at relatively low impact pressures but with no change in volume between products and reactants, and ii) a two-step polymerization process for phenylacetylene. Furthermore, the evolution of the HOMO-LUMO gap tracked on-the-fly during our simulations could be correlated with changes transient absorption measured during laser-driven shock compression experiments on these liquids.
Lowdin, Per-Olov; Ohrn, N. Y.; Sabin, John R.; Zerner, Michael C.
1993-03-01
The topics covered at the 33rd annual Sanibel Symposium, organized by the faculty and staff of the Quantum Theory Project of the University of Florida, and held March 13 - 20, 1993, include advanced scientific computing, interaction of photons and matter, quantum molecular dynamics, electronic structure methods, polymeric systems, and quantum chemical methods for extended systems.
Thomas, Kolle E; Alemayehu, Abraham B; Conradie, Jeanet; Beavers, Christine M; Ghosh, Abhik
2012-08-21
Although they share some superficial structural similarities with porphyrins, corroles, trianionic ligands with contracted cores, give rise to fundamentally different transition metal complexes in comparison with the dianionic porphyrins. Many metallocorroles are formally high-valent, although a good fraction of them are also noninnocent, with significant corrole radical character. These electronic-structural characteristics result in a variety of fascinating spectroscopic behavior, including highly characteristic, paramagnetically shifted NMR spectra and textbook cases of charge-transfer spectra. Although our early research on corroles focused on spectroscopy, we soon learned that the geometric structures of metallocorroles provide a fascinating window into their electronic-structural characteristics. Thus, we used X-ray structure determinations and quantum chemical studies, chiefly using DFT, to obtain a comprehensive understanding of metallocorrole geometric and electronic structures. This Account describes our studies of the structural chemistry of metallocorroles. At first blush, the planar or mildly domed structure of metallocorroles might appear somewhat uninteresting particularly when compared to metalloporphyrins. Metalloporphyrins, especially sterically hindered ones, are routinely ruffled or saddled, but the missing meso carbon apparently makes the corrole skeleton much more resistant to nonplanar distortions. Ruffling, where the pyrrole rings are alternately twisted about the M-N bonds, is energetically impossible for metallocorroles. Saddling is also uncommon; thus, a number of sterically hindered, fully substituted metallocorroles exhibit almost perfectly planar macrocycle cores. Against this backdrop, copper corroles stand out as an important exception. As a result of an energetically favorable Cu(d(x2-y2))-corrole(π) orbital interaction, copper corroles, even sterically unhindered ones, are inherently saddled. Sterically hindered substituents
Directory of Open Access Journals (Sweden)
Søren Ventegodt
2006-01-01
Full Text Available Deep quantum chemistry is a theory of deeply structured quantum fields carrying the biological information of the cell, making it able to remember, intend, represent the inner and outer world for comparison, understand what it “sees”, and make choices on its structure, form, behavior and division. We suggest that deep quantum chemistry gives the cell consciousness and all the qualities and abilities related to consciousness. We use geometric symbolism, which is a pre-mathematical and philosophical approach to problems that cannot yet be handled mathematically. Using Occams razor we have started with the simplest model that works; we presume this to be a many-dimensional, spiral fractal. We suggest that all the electrons of the large biological molecules orbitals make one huge “cell-orbital”, which is structured according to the spiral fractal nature of quantum fields. Consciousness of single cells, multi cellular structures as e.g. organs, multi-cellular organisms and multi-individual colonies (like ants and human societies can thus be explained by deep quantum chemistry. When biochemical activity is strictly controlled by the quantum-mechanical super-orbital of the cell, this orbital can deliver energetic quanta as biological information, distributed through many fractal levels of the cell to guide form and behavior of an individual single or a multi-cellular organism. The top level of information is the consciousness of the cell or organism, which controls all the biochemical processes. By this speculative work inspired by Penrose and Hameroff we hope to inspire other researchers to formulate more strict and mathematically correct hypothesis on the complex and coherence nature of matter, life and consciousness.
The Study on Application of Quantum Chemistry Software%量子化学软件的应用研究
Institute of Scientific and Technical Information of China (English)
郭瑞萍; 刘旭光
2009-01-01
量化软件的引入对学生学习、理解、应用起到积极作用,激发了学生的学习动机,便于教师调整教学内容和进度, 优化教学过程.通过变分法在Gaussian软件包中的体现、Gaussian软件计算O2+,O2,和O2-的键长,对比键级的结果以及σ-π反馈键三个具体实例说明量子化学软件在教学中的应用,以及应用中的注意原则.%The introduction of quantum chemistry program into the teaching of Structural Chemistry not only plays a positive role for students to learn, understand and apply the Structural Chemistry course but also stimulates students' motivation.This is helpful for teachers to adjust teaching contents and progresses and optimize teaching procedure.The application and its rules of quantum chemistry program in Structural Chemistry are also illustrated by practical examples.
Barone, Vincenzo; Biczysko, Malgorzata; Puzzarini, Cristina
2015-05-19
For many years, scientists suspected that the interstellar medium was too hostile for organic species and that only a few simple molecules could be formed under such extreme conditions. However, the detection of approximately 180 molecules in interstellar or circumstellar environments in recent decades has changed this view dramatically. A rich chemistry has emerged, and relatively complex molecules such as C60 and C70 are formed. Recently, researchers have also detected complex organic and potentially prebiotic molecules, such as amino acids, in meteorites and in other space environments. Those discoveries have further stimulated the debate on the origin of the building blocks of life in the universe. Many efforts continue to focus on the physical, chemical, and astrophysical processes by which prebiotic molecules can be formed in the interstellar dust and dispersed to Earth or to other planets.Spectroscopic techniques, which are widely used to infer information about molecular structure and dynamics, play a crucial role in the investigation of planetary atmosphere and the interstellar medium. Increasingly these astrochemical investigations are assisted by quantum-mechanical calculations of structures as well as spectroscopic and thermodynamic properties, such as transition frequencies and reaction enthalpies, to guide and support observations, line assignments, and data analysis in these new and chemically complicated situations. However, it has proved challenging to extend accurate quantum-chemical computational approaches to larger systems because of the unfavorable scaling with the number of degrees of freedom (both electronic and nuclear).In this Account, we show that it is now possible to compute physicochemical properties of building blocks of biomolecules with an accuracy rivaling that of the most sophisticated experimental techniques, and we summarize specific contributions from our groups. As a test case, we present the underlying computational machinery
Directory of Open Access Journals (Sweden)
Joseph P. Kenny
2008-01-01
Full Text Available Cutting-edge scientific computing software is complex, increasingly involving the coupling of multiple packages to combine advanced algorithms or simulations at multiple physical scales. Component-based software engineering (CBSE has been advanced as a technique for managing this complexity, and complex component applications have been created in the quantum chemistry domain, as well as several other simulation areas, using the component model advocated by the Common Component Architecture (CCA Forum. While programming models do indeed enable sound software engineering practices, the selection of programming model is just one building block in a comprehensive approach to large-scale collaborative development which must also address interface and data standardization, and language and package interoperability. We provide an overview of the development approach utilized within the Quantum Chemistry Science Application Partnership, identifying design challenges, describing the techniques which we have adopted to address these challenges and highlighting the advantages which the CCA approach offers for collaborative development.
Energy Technology Data Exchange (ETDEWEB)
Miyazaki, Tetsuo; Aratono, Yasuyuki; Ichikawa, Tsuneki; Shiotani, Masaru [eds.
1998-02-01
Present report is the proceedings of the 3rd Meeting on Tunneling Reaction and Low Temperature Chemistry held in Oct. 13 and 14, 1997. The main subject of the meeting is `Tunneling Reaction and Quantum Medium`. In the meeting, the physical and chemical phenomena in the liquid helium such as quantum nucleation, spectroscopy of atoms and molecules, and tunneling abstraction reaction of tritium atom were discussed as the main topics as well as the tunneling reactions in the solid hydrogen and organic compounds. Through the meetings held in 1995, 1996, and 1997, the tunneling phenomena proceeding at various temperatures (room temperature to mK) in the wide fields of chemistry, biology, and physics were discussed intensively and the importance of the tunneling phenomena in the science has been getting clear. The 12 of the presented papers are indexed individually. (J.P.N.)
Energy Technology Data Exchange (ETDEWEB)
Miyazaki, Tetsuo; Aratono, Yasuyuki; Ichikawa, Tsuneki; Shiotani, Masaru [eds.
1998-02-01
Present report is the proceedings of the 3rd Meeting on Tunneling Reaction and Low Temperature Chemistry held in Oct. 13 and 14, 1997. The main subject of the meeting is `Tunneling Reaction and Quantum Medium`. In the meeting, the physical and chemical phenomena in the liquid helium such as quantum nucleation, spectroscopy of atoms and molecules, and tunneling abstraction reaction of tritium atom were discussed as the main topics as well as the tunneling reactions in the solid hydrogen and organic compounds. Through the meetings held in 1995, 1996, and 1997, the tunneling phenomena proceeding at various temperatures (room temperature to mK) in the wide fields of chemistry, biology, and physics were discussed intensively and the importance of the tunneling phenomena in the science has been getting clear. The 12 of the presented papers are indexed individually. (J.P.N.)
Jiang, Junhang; Zheng, Canhui; Zhu, Kongkai; Liu, Jia; Sun, Nannan; Wang, Chongqing; Jiang, Hualiang; Zhu, Ju; Luo, Cheng; Zhou, Youjun
2015-03-12
A potent combretastatin A-4 (CA-4) like tubulin polymerization inhibitor 22b was found with strong antitumor activity previously. However, it easily undergoes cis-trans isomerization under natural light, and the resulting decrease in activity limits its further applications. In this study, we used quantum chemistry calculations to explore the molecular basis of its instability. Aided by the calculations, two rounds of structural optimization of 22b were conducted. Accelerated quantitative light stability testing confirmed that the stability of these designed compounds was significantly improved as predicted. Among them, compounds 1 and 3b displayed more potent inhibitory activity on tumor cell growth than 22b. In addition, the potent in vivo antitumor activity of compound 1 was confirmed. Quantum chemistry calculations were used in the optimization of stilbene-like molecules, providing new insight into stilbenoid optimization and important implications for the future development of novel CA-4-like tubulin polymerization inhibitors.
DEFF Research Database (Denmark)
Meusinger, Carl; Berhanu, Tesfaye A.; Erbland, Joseph
2014-01-01
Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes...... undergoing secondary (recombination) chemistry. Modeled NOx emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ∼ 1%, much lower than reported for aqueous chemistry. A companion paper...... presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study....
Marestoni,Luiz D.; Wong,Ademar; Feliciano, Gustavo T.; Marchi,Mary R. R.; Tarley, César R. T.; Sotomayor,Maria D. P. T.
2016-01-01
It is well known that selectivity of molecularly imprinted polymers (MIPs) depends on adequate choice of functional monomer before the experimental synthesis. Computational simulation seems to be an ideal way to produce selective MIPs. In this work, we have proposed the use of semi-empirical simulation to obtain the best monomer able to strongly interact with ciprofloxacin. Twenty functional monomers were evaluated through semi-empirical quantum chemistry method and three MIPs were synthesize...
Jaffe, Richard; Han, Jie; Yoon, Do; Langhoff, Stephen R. (Technical Monitor)
1997-01-01
The so-called oxygen gauche effect in poly(oxyethylene) (POE) and its model molecules such as 1,2-dimethoxyethane (DME) and diglyme (CH3OC2H4OC2H4OCH3) is manifested in the preference for gauche C-C bond conformations over trans. This has also been observed for poly(ethylene terephthalate) (PET). Our previous quantum chemistry calculations demonstrated that the large C-C gauche population in DME is due, in part, to a low-lying tg +/- g+ conformer that exhibits a substantial 1,5 CH ... O attraction. New calculations will be described that demonstrate the accuracy of the original quantum chemistry calculations. In addition, an extension of this work to model molecules for PET will be presented. It is seen that the C-C gauche preference is much stronger in 1,2 diacetoxyethane than in DME. In addition, there exist low-lying tg +/- g+/- and g+/-g+/-g+/- conformers that exhibit 1,5 CH ... O attractions involving the carbonyl oxygens. It is expected that the -O-C-C-O- torsional properties will be quite different in these two polymers. The quantum chemistry results are used to parameterize rotational isomeric states models (RIS) and force fields for molecular dynamics simulations of these polymers.
Boese, A D; Martin, J M L; Marx, D; Chandra, Amalendu; Martin, Jan M.L.; Marx, Dominik
2003-01-01
The ammonia dimer (NH3)2 has been investigated using high--level ab initio quantum chemistry methods and density functional theory (DFT). The structure and energetics of important isomers is obtained to unprecedented accuracy without resorting to experiment. The global minimum of eclipsed C_s symmetry is characterized by a significantly bent hydrogen bond which deviates from linearity by about 20 degrees. In addition, the so-called cyclic C_{2h} structure is extremely close in energy on an overall flat potential energy surface. It is demonstrated that none of the currently available (GGA, meta--GGA, and hybrid) density functionals satisfactorily describe the structure and relative energies of this nonlinear hydrogen bond. We present a novel density functional, HCTH/407+, designed to describe this sort of hydrogen bond quantitatively on the level of the dimer, contrary to e.g. the widely used BLYP functional. This improved functional is employed in Car-Parrinello ab initio molecular dynamics simulations of liq...
Solving a quantum chemistry equations and high-temperature superconductivity problems
Liverts, E Z
2000-01-01
The conventional technique for solving the equation of quantum chemistry (of solids) is unusually extended to the structures possessing certain symmetries. The extension proposed gives a chance to find unoccupied electronic states located lower than the Fermi level of the ground state of a specific system. Such states can be treated as 'spectral holes'. Application of this technique, in particular, when calculating the electronic structure of the HTSC-compound YBa sub 2 Cu sub 3 O sub 7 sub - subdelta (0<= delta<=1) results in the following. For all versions of the examined charge distributions over a crystal lattice, spectral holes of high spatial localization are found. The 'spatial spectral holes' are mainly located at the p sub y -orbitals of the apex oxygens. These orbitals overlap and form linear chains which are parallel too but do not coincide with the known Cu(1)-O chains which disappear when delta is close tio 1. One can suppose that these linear chains of the overlapping hole states from a su...
Surface chemistry of InP quantum dots: a comprehensive study.
Cros-Gagneux, Arnaud; Delpech, Fabien; Nayral, Céline; Cornejo, Alfonso; Coppel, Yannick; Chaudret, Bruno
2010-12-29
Advanced (1)H, (13)C, and (31)P solution and solid-state NMR studies combined with IR spectroscopy were used to probe, at the molecular scale, the composition and the surface chemistry of indium phosphide (InP) quantum dots (QDs) prepared via a non-coordinating solvent strategy. This nanomaterial can be described as a core-multishell object: an InP core, with a zinc blende bulk structure, is surrounded first by a partially oxidized surface shell, which is itself surrounded by an organic coating. This organic passivating layer is composed, in the first coordination sphere, of tightly bound palmitate ligands which display two different bonding modes. A second coordination sphere includes an unexpected dialkyl ketone and residual long-chain non-coordinating solvents (ODE and its isomers) which interact through weak intermolecular bonds with the alkyl chains of the carboxylate ligands. We show that this ketone is formed during the synthesis process via a decarboxylative coupling route and provides oxidative conditions which are responsible for the oxidation of the InP core surface. This phenomenon has a significant impact on the photoluminescence properties of the as-synthesized QDs and probably accounts for the failure of further growth of the InP core.
Investigation of adsorption of surfactant at the air-water interface with quantum chemistry method
Institute of Scientific and Technical Information of China (English)
CHEN MeiLing; WANG ZhengWu; WANG HaiJun; ZHANG GeXin; TAO FuMing
2007-01-01
Density functional theory (DFT) of quantum chemistry was used to optimize the configuration of the anionic surfactant complexes CH3(CH2)7OSO-3(H2O)n (n=0-6) and calculate their molecular frequencies at the B3LYP/6-311+G* level. The interaction of CH3(CH2)7OSO-3 with 1 to 6 water molecules was investigated at the air-water interface with DFT. The results revealed that the hydration shell was formed in the form of H-bond between the hydrophilic group of CH3(CH2)7OSO-3 and 6 waters. The strength of H-bonds belongs to medium. Binding free energy revealed that the hydration shell was stable. The increase of the number of water molecules will cause increases of the total charge of hydrophilic group and S10-O9-C8 bond angle, but decreases of the alkyl chain length and the bond lengths of S10-O11,S10-O12 as well as S10-O13, respectively.
Li, Huihui; Zhu, Houjuan; Sun, Mingtai; Yan, Yehan; Zhang, Kui; Huang, Dejian; Wang, Suhua
2015-08-11
Herein, we report a novel approach to the rapid visual detection of gaseous sulfur dioxide (SO2) by manipulating the surface chemistry of 3-aminopropyltriethoxysilane (APTS)-modified quantum dots (QDs) using fluorescent coumarin-3-carboxylic acid (CCA) for specific reaction with SO2. The CCA molecules are attached to the surface amino groups of the QDs through electrostatic attraction, thus the fluorescence of CCA is greatly suppressed because of the formation of an ion-pair complex between the ATPS-modified QDs and CCA. Such an interaction is vulnerable to SO2 because SO2 can readily react with surface amino groups to form strong charge-transfer complexes and subsequently release the strongly fluorescent CCA molecules. The mechanism has been carefully verified through a series of control experiments. Upon exposure to different amounts of SO2, the fluorescent color of the nanoparticle-based sensor displays continuously changes from red to blue. Most importantly, the approach owns high selectivity for SO2 and a tolerance of interference, which enables the sensor to detect SO2 in a practical application. Using this fluorescence-based sensing method, we have achieved a visual detection limit of 6 ppb for gaseous SO2.
Glycoconjugated amphiphilic polymers via click-chemistry for the encapsulation of quantum dots.
Schmidtke, Christian; Kreuziger, Anna-Marlena; Alpers, Dirk; Jacobsen, Anna; Leshch, Yevgeniy; Eggers, Robin; Kloust, Hauke; Tran, Huong; Ostermann, Johannes; Schotten, Theo; Thiem, Joachim; Thimm, Julian; Weller, Horst
2013-10-08
Herein, we present a strategy for the glycoconjugation of nanoparticles (NPs), with a special focus on fluorescent quantum dots (QDs), recently described by us as "preassembly" approach. Therein, prior to the encapsulation of diverse nanoparticles by an amphiphilic poly(isoprene)-b-poly(ethylene glycol) diblock copolymer (PI-b-PEG), the terminal PEG appendage was modified by covalently attaching a carbohydrate moiety using Huisgen-type click-chemistry. Successful functionalization was proven by NMR spectroscopy. The terminally glycoconjugated polymers were subsequently used for the encapsulation of QDs in a phase transfer process, which fully preserved fluorescence properties. Binding of these nanoconstructs to the lectin Concanavalin A (Con A) was studied via surface plasmon resonance (SPR). Depending on the carbohydrate moiety, namely, D-manno-heptulose, D-glucose, D-galactose, 2-deoxy-2-{[methylamino)carbonyl]amino}-D-glucopyranose ("des(nitroso)-streptozotocin"), or D-maltose, the glycoconjugated QDs showed enhanced affinity constants due to multivalent binding effects. None of the constructs showed toxicity from 0.001 to 1 μM (particle concentration) using standard WST and LDH assays on A549 cells.
Programmability of the HPCS Languages: A Case Study with a Quantum Chemistry Kernel
Energy Technology Data Exchange (ETDEWEB)
Shet, Aniruddha G [ORNL; Elwasif, Wael R [ORNL; Harrison, Robert J [ORNL; Bernholdt, David E [ORNL
2008-01-01
As high-end computer systems present users with rapidly increasing numbers of processors, possibly also incorporating attached co-processors, programmers are increasingly challenged to express the necessary levels of concurrency with the dominant parallel programming model, Fortran+MPI+OpenMP (or minor variations). In this paper, we examine the languages developed under the DARPA High-Productivity Computing Systems (HPCS) program (Chapel, Fortress, and X10) as representatives of a different parallel programming model which might be more effective on coming high-performance systems. The application used in this study is the Hartree-Fock method from quantum chemistry, which combines access to distributed data with a task-parallel algorithm and is characterized by significant irregularity in the computational tasks. We present several different implementation strategies for load balancing of the task parallel computation, as well as distributed array operations, in each of the three languages. We conclude that the HPCS languages provide a wide variety of mechanisms for expressing parallelism, which can be combined at multiple levels, making them quite expressive for this problem.
Energy Technology Data Exchange (ETDEWEB)
Shet, Aniruddha G [ORNL; Elwasif, Wael R [ORNL; Harrison, Robert J [ORNL; Bernholdt, David E [ORNL
2008-04-01
As high-end computer systems present users with rapidly increasing numbers of processors, possibly also incorporating attached co-processors, programmers are increasingly challenged to express the necessary levels of concurrency with the dominant parallel programming model, Fortran+MPI+OpenMP (or minor variations). In this paper, we examine the languages developed under the DARPA High-Productivity Computing Systems (HPCS) program (Chapel, Fortress, and X10) as representatives of a different parallel programming model which might be more effective on coming high-performance systems. The application used in this study is the Hartree-Fock method from quantum chemistry, which combines access to distributed data with a task-parallel algorithm and is characterized by significant irregularity in the computational tasks. We present several different implementation strategies for load balancing of the task parallel computation, as well as distributed array operations, in each of the three languages. We conclude that the HPCS languages provide a wide variety of mechanisms for expressing parallelism, which can be combined at multiple levels, making them quite expressive for this problem.
Gao, Zhengyang; Lv, Shaokun; Yang, Weijie; Yang, Pengfei; Ji, Shuo; Meng, Xinxin
2015-06-01
Ab initio calculations were performed to study the quantum chemistry reactions mechanisms among Hg(0), elemental halogen and O3. The geometry of reactions, transition states (TS), intermediates (M) and products were optimized using the MP2 method at the SDD basis function level for Hg, and using 6-311++G (3df, 3pd) for other species. Molecular energies were calculated at QCISD (T) level with zero point energy. Activation energies were calculated along with pre-exponential factors . The reaction rate constants within 298-1800 K were calculated according to transition state theory (TST). The influences of O3 on the reaction of Hg(0) with halogen are discussed. Hg(0) can be oxidized to Hg(1+) by halogen and O3, and halogen and O3 can be arranged in decreasing order as: Br2 > BrO > O3 > Br > Cl, BrCl > HBr > HCl, Br2 > Cl2 according to reaction rate constants. When O3 is presented, Br2, HBr, BrCl, Cl2 and HCl react with O3 and are initially converted to BrO and ClO. O3 is unfavorable for oxidation of Hg(0) by Br2. The mixture of HBr and O3 has better oxidizing Hg(0) performance than HBr and O3. Cl is less effective than Br for oxidation of Hg(0).
An efficient solver for large structured eigenvalue problems in relativistic quantum chemistry
Shiozaki, Toru
2015-01-01
We report an efficient program for computing the eigenvalues and symmetry-adapted eigenvectors of very large quaternionic (or Hermitian skew-Hamiltonian) matrices, using which structure-preserving diagonalization of matrices of dimension N > 10000 is now routine on a single computer node. Such matrices appear frequently in relativistic quantum chemistry owing to the time-reversal symmetry. The implementation is based on a blocked version of the Paige-Van Loan algorithm [D. Kressner, BIT 43, 775 (2003)], which allows us to use the Level 3 BLAS subroutines for most of the computations. Taking advantage of the symmetry, the program is faster by up to a factor of two than state-of-the-art implementations of complex Hermitian diagonalization; diagonalizing a 12800 x 12800 matrix took 42.8 (9.5) and 85.6 (12.6) minutes with 1 CPU core (16 CPU cores) using our symmetry-adapted solver and Intel MKL's ZHEEV that is not structure-preserving, respectively. The source code is publicly available under the FreeBSD license.
Hartono, Albert; Lu, Qingda; Henretty, Thomas; Krishnamoorthy, Sriram; Zhang, Huaijian; Baumgartner, Gerald; Bernholdt, David E; Nooijen, Marcel; Pitzer, Russell; Ramanujam, J; Sadayappan, P
2009-11-12
Complex tensor contraction expressions arise in accurate electronic structure models in quantum chemistry, such as the coupled cluster method. This paper addresses two complementary aspects of performance optimization of such tensor contraction expressions. Transformations using algebraic properties of commutativity and associativity can be used to significantly decrease the number of arithmetic operations required for evaluation of these expressions. The identification of common subexpressions among a set of tensor contraction expressions can result in a reduction of the total number of operations required to evaluate the tensor contractions. The first part of the paper describes an effective algorithm for operation minimization with common subexpression identification and demonstrates its effectiveness on tensor contraction expressions for coupled cluster equations. The second part of the paper highlights the importance of data layout transformation in the optimization of tensor contraction computations on modern processors. A number of considerations, such as minimization of cache misses and utilization of multimedia vector instructions, are discussed. A library for efficient index permutation of multidimensional tensors is described, and experimental performance data is provided that demonstrates its effectiveness.
Energy Technology Data Exchange (ETDEWEB)
Hartono, Albert; Lu, Qingda; henretty, thomas; Krishnamoorthy, Sriram; zhang, huaijian; Baumgartner, Gerald; Bernholdt, David E.; Nooijen, Marcel; Pitzer, Russell M.; Ramanujam, J.; Sadayappan, Ponnuswamy
2009-11-12
Complex tensor contraction expressions arise in accurate electronic structure models in quantum chemistry, such as the coupled cluster method. This paper addresses two complementary aspects of performance optimization of such tensor contraction expressions. Transformations using algebraic properties of commutativity and associativity can be used to significantly decrease the number of arithmetic operations required for evaluation of these expressions. The identification of common subexpressions among a set of tensor contraction expressions can result in a reduction of the total number of operations required to evaluate the tensor contractions. The first part of the paper describes an effective algorithm for operation minimization with common subexpression identification and demonstrates its effectiveness on tensor contraction expressions for coupled cluster equations. The second part of the paper highlights the importance of data layout transformation in the optimization of tensor contraction computations on modern processors. A number of considerations such as minimization of cache misses and utilization of multimedia vector instructions are discussed. A library for efficient index permutation of multi-dimensional tensors is described and experimental performance data is provided that demonstrates its effectiveness.
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.
Marshall, Ashley R.
Semiconductor quantum dots (QDs) are interesting materials that, after less than 40 years of research, are used in commercial products. QDs are now found in displays, such as Samsung televisions and the Kindle Fire, and have applications in lighting, bio-imaging, quantum computing, and photovoltaics. They offer a large range of desirable properties: a controllable band gap, solution processability, controlled energy levels, and are currently the best materials for multiple exciton generation. The tunable optoelectronic properties of QDs can be controlled using size, shape, composition, and surface treatments--as shown here. Due to the quasi-spherical shape of QDs the surface to volume ratio is high, i.e. many of the constituent atoms are found on the QD surface. This makes QDs highly sensitive to surface chemistry modifications. This thesis encompasses the effects of surface treatments for QDs of two semiconducting materials: lead chalcogenides and CsPbI3. Our group developed a new synthetic technique for lead chalcogenide QDs via the cation exchange of cadmium chalcogenides. An in-depth chemical analysis is paired with optical and electrical studies and we find that metal halide residue contributes to the oxidative stability and decreased trap state density in cation-exchanged PbS QDs. We exploit these properties to make air-stable QD photovoltaic devices from both PbS and PbSe QD materials. Beyond the effects of residual atoms left from the synthetic technique, I investigated how to controllably add atoms onto the surface of QDs. I found that by introducing metal halides as a post-treatment in an electronically coupled array I am able to control the performance parameters in QD photovoltaic devices. These treatments fully infiltrate the assembled film, even under short exposure times and allow me to add controlled quantities of surface atoms to study their effects on film properties and photovoltaic device performance. Finally, I sought to apply the knowledge of
Galland, Nicolas; Kone, Soleymane; Le Questel, Jean-Yves
2012-10-01
A quantitative analysis of the interaction sites of the anti-Alzheimer drug galanthamine with molecular probes (water and benzene molecules) representative of its surroundings in the binding site of acetylcholinesterase (AChE) has been realized through pairwise potentials calculations and quantum chemistry. This strategy allows a full and accurate exploration of the galanthamine potential energy surface of interaction. Significantly different results are obtained according to the distances of approaches between the various molecular fragments and the conformation of the galanthamine N-methyl substituent. The geometry of the most relevant complexes has then been fully optimized through MPWB1K/6-31 + G(d,p) calculations, final energies being recomputed at the LMP2/aug-cc-pVTZ(-f) level of theory. Unexpectedly, galanthamine is found to interact mainly from its hydrogen-bond donor groups. Among those, CH groups in the vicinity of the ammonium group are prominent. The trends obtained provide rationales to the predilection of the equatorial orientation of the galanthamine N-methyl substituent for binding to AChE. The analysis of the interaction energies pointed out the independence between the various interaction sites and the rigid character of galanthamine. The comparison between the cluster calculations and the crystallographic observations in galanthamine-AChE co-crystals allows the validation of the theoretical methodology. In particular, the positions of several water molecules appearing as strongly conserved in galanthamine-AChE co-crystals are predicted by the calculations. Moreover, the experimental position and orientation of lateral chains of functionally important aminoacid residues are in close agreement with the ones predicted theoretically. Our study provides relevant information for a rational drug design of galanthamine based AChE inhibitors.
Galland, Nicolas; Kone, Soleymane; Le Questel, Jean-Yves
2012-10-01
A quantitative analysis of the interaction sites of the anti-Alzheimer drug galanthamine with molecular probes (water and benzene molecules) representative of its surroundings in the binding site of acetylcholinesterase (AChE) has been realized through pairwise potentials calculations and quantum chemistry. This strategy allows a full and accurate exploration of the galanthamine potential energy surface of interaction. Significantly different results are obtained according to the distances of approaches between the various molecular fragments and the conformation of the galanthamine N-methyl substituent. The geometry of the most relevant complexes has then been fully optimized through MPWB1K/6-31 + G(d,p) calculations, final energies being recomputed at the LMP2/aug-cc-pVTZ(-f) level of theory. Unexpectedly, galanthamine is found to interact mainly from its hydrogen-bond donor groups. Among those, CH groups in the vicinity of the ammonium group are prominent. The trends obtained provide rationales to the predilection of the equatorial orientation of the galanthamine N-methyl substituent for binding to AChE. The analysis of the interaction energies pointed out the independence between the various interaction sites and the rigid character of galanthamine. The comparison between the cluster calculations and the crystallographic observations in galanthamine-AChE co-crystals allows the validation of the theoretical methodology. In particular, the positions of several water molecules appearing as strongly conserved in galanthamine-AChE co-crystals are predicted by the calculations. Moreover, the experimental position and orientation of lateral chains of functionally important aminoacid residues are in close agreement with the ones predicted theoretically. Our study provides relevant information for a rational drug design of galanthamine based AChE inhibitors.
Are fragment-based quantum chemistry methods applicable to medium-sized water clusters?
Yuan, Dandan; Shen, Xiaoling; Li, Wei; Li, Shuhua
2016-06-28
Fragment-based quantum chemistry methods are either based on the many-body expansion or the inclusion-exclusion principle. To compare the applicability of these two categories of methods, we have systematically evaluated the performance of the generalized energy based fragmentation (GEBF) method (J. Phys. Chem. A, 2007, 111, 2193) and the electrostatically embedded many-body (EE-MB) method (J. Chem. Theory Comput., 2007, 3, 46) for medium-sized water clusters (H2O)n (n = 10, 20, 30). Our calculations demonstrate that the GEBF method provides uniformly accurate ground-state energies for 10 low-energy isomers of three water clusters under study at a series of theory levels, while the EE-MB method (with one water molecule as a fragment and without using the cutoff distance) shows a poor convergence for (H2O)20 and (H2O)30 when the basis set contains diffuse functions. Our analysis shows that the neglect of the basis set superposition error for each subsystem has little effect on the accuracy of the GEBF method, but leads to much less accurate results for the EE-MB method. The accuracy of the EE-MB method can be dramatically improved by using an appropriate cutoff distance and using two water molecules as a fragment. For (H2O)30, the average deviation of the EE-MB method truncated up to the three-body level calculated using this strategy (relative to the conventional energies) is about 0.003 hartree at the M06-2X/6-311++G** level, while the deviation of the GEBF method with a similar computational cost is less than 0.001 hartree. The GEBF method is demonstrated to be applicable for electronic structure calculations of water clusters at any basis set.
Grimme, Stefan; Bauer, Christopher Alexander
2015-01-01
The gas-phase decomposition pathways of electron ionization (EI)-induced radical cations of the nucleobases uracil, thymine, cytosine, and guanine are investigated by means of mixed quantum-classical molecular dynamics. No preconceived fragmentation channels are used in the calculations. The results compare well to a plethora of experimental and theoretical data for these important biomolecules. With our combined stochastic and dynamic approach, one can access in an unbiased way the energetically available decomposition mechanisms. Additionally, we are able to separate the EI mass spectra of different tautomers of cytosine and guanine. Our method (previously termed quantum chemistry electron ionization mass spectra) reproduces free nucleobase experimental mass spectra well and provides detailed mechanistic in-sight into high-energy unimolecular decomposition processes.
Shi, Yu
2015-01-01
2015 is the International Year of Light and Light-based Technologies (IYL), while the physics and chemistry Nobel Prizes 2014 are both about light. The work leading to the two prizes share the same basic theoretical foundation: when an electron jumps from a higher energy level to a lower energy level, the energy difference is transformed into a photon. This basic way of light generation is a key part of the Old Quantum Theory. Interestingly, the date of announcing the 2014 Nobel Prize for physics coincided with the birthdays of Niels Bohr and, especially, of Planck's blackbody radiation formula. In connection with the two 2014 Nobel Prizes, we recall the development of the Old Quantum Theory by Planck, Einstein and Bohr.
Energy Technology Data Exchange (ETDEWEB)
Meusinger, Carl; Johnson, Matthew S. [Department of Chemistry, University of Copenhagen, Copenhagen (Denmark); Berhanu, Tesfaye A.; Erbland, Joseph; Savarino, Joel, E-mail: jsavarino@lgge.obs.ujf-grenoble.fr [Univ. Grenoble Alpes, LGGE, F-38000 Grenoble (France); CNRS, LGGE, F-38000 Grenoble (France)
2014-06-28
Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes are understood. It has been shown that photolysis of nitrate in the snowpack plays a major role in nitrate loss and that the photolysis products have a significant influence on the local troposphere as well as on other species in the snow. Reported quantum yields for the main reaction spans orders of magnitude – apparently a result of whether nitrate is located at the air-ice interface or in the ice matrix – constituting the largest uncertainty in models of snowpack NO{sub x} emissions. Here, a laboratory study is presented that uses snow from Dome C and minimizes effects of desorption and recombination by flushing the snow during irradiation with UV light. A selection of UV filters allowed examination of the effects of the 200 and 305 nm absorption bands of nitrate. Nitrate concentration and photon flux were measured in the snow. The quantum yield for loss of nitrate was observed to decrease from 0.44 to 0.003 within what corresponds to days of UV exposure in Antarctica. The superposition of photolysis in two photochemical domains of nitrate in snow is proposed: one of photolabile nitrate, and one of buried nitrate. The difference lies in the ability of reaction products to escape the snow crystal, versus undergoing secondary (recombination) chemistry. Modeled NO{sub x} emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ∼1%, much lower than reported for aqueous chemistry. A companion paper presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study.
Meusinger, Carl; Berhanu, Tesfaye A; Erbland, Joseph; Savarino, Joel; Johnson, Matthew S
2014-06-28
Post-depositional processes alter nitrate concentration and nitrate isotopic composition in the top layers of snow at sites with low snow accumulation rates, such as Dome C, Antarctica. Available nitrate ice core records can provide input for studying past atmospheres and climate if such processes are understood. It has been shown that photolysis of nitrate in the snowpack plays a major role in nitrate loss and that the photolysis products have a significant influence on the local troposphere as well as on other species in the snow. Reported quantum yields for the main reaction spans orders of magnitude - apparently a result of whether nitrate is located at the air-ice interface or in the ice matrix - constituting the largest uncertainty in models of snowpack NOx emissions. Here, a laboratory study is presented that uses snow from Dome C and minimizes effects of desorption and recombination by flushing the snow during irradiation with UV light. A selection of UV filters allowed examination of the effects of the 200 and 305 nm absorption bands of nitrate. Nitrate concentration and photon flux were measured in the snow. The quantum yield for loss of nitrate was observed to decrease from 0.44 to 0.003 within what corresponds to days of UV exposure in Antarctica. The superposition of photolysis in two photochemical domains of nitrate in snow is proposed: one of photolabile nitrate, and one of buried nitrate. The difference lies in the ability of reaction products to escape the snow crystal, versus undergoing secondary (recombination) chemistry. Modeled NOx emissions may increase significantly above measured values due to the observed quantum yield in this study. The apparent quantum yield in the 200 nm band was found to be ∼1%, much lower than reported for aqueous chemistry. A companion paper presents an analysis of the change in isotopic composition of snowpack nitrate based on the same samples as in this study.
Nakatani, Naoki; Chan, Garnet Kin-Lic
2013-04-07
We investigate tree tensor network states for quantum chemistry. Tree tensor network states represent one of the simplest generalizations of matrix product states and the density matrix renormalization group. While matrix product states encode a one-dimensional entanglement structure, tree tensor network states encode a tree entanglement structure, allowing for a more flexible description of general molecules. We describe an optimal tree tensor network state algorithm for quantum chemistry. We introduce the concept of half-renormalization which greatly improves the efficiency of the calculations. Using our efficient formulation we demonstrate the strengths and weaknesses of tree tensor network states versus matrix product states. We carry out benchmark calculations both on tree systems (hydrogen trees and π-conjugated dendrimers) as well as non-tree molecules (hydrogen chains, nitrogen dimer, and chromium dimer). In general, tree tensor network states require much fewer renormalized states to achieve the same accuracy as matrix product states. In non-tree molecules, whether this translates into a computational savings is system dependent, due to the higher prefactor and computational scaling associated with tree algorithms. In tree like molecules, tree network states are easily superior to matrix product states. As an illustration, our largest dendrimer calculation with tree tensor network states correlates 110 electrons in 110 active orbitals.
Directory of Open Access Journals (Sweden)
Evangelos Mavroudakis
2015-09-01
Full Text Available Throughout the last 25 years, computational chemistry based on quantum mechanics has been applied to the investigation of reaction kinetics in free radical polymerization (FRP with growing interest. Nowadays, quantum chemistry (QC can be considered a powerful and cost-effective tool for the kinetic characterization of many individual reactions in FRP, especially those that cannot yet be fully analyzed through experiments. The recent focus on copolymers and systems where secondary reactions play a major role has emphasized this feature due to the increased complexity of these kinetic schemes. QC calculations are well-suited to support and guide the experimental investigation of FRP kinetics as well as to deepen the understanding of polymerization mechanisms. This paper is intended to provide an overview of the most relevant QC results obtained so far from the investigation of FRP. A comparison between computational results and experimental data is given, whenever possible, to emphasize the performances of the two approaches in the prediction of kinetic data. This work provides a comprehensive database of reaction rate parameters of FRP to assist in the development of advanced models of polymerization and experimental studies on the topic.
Greca Dufranc, Ileana María; Freire Junior, Olival
2014-01-01
Finding the best ways to introduce quantum physics to undergraduate students in all scientific areas, in particular for chemistry students, is a pressing, but hardly a simple task. In this paper, we discuss the relevance of taking into account lessons from the history of the discipline and the ongoing controversy over its interpretations and foundations in the search for new ways of improving the teaching of quantum physics. We also review and discuss the recent research in science education ...
Sugisaki, Kenji; Yamamoto, Satoru; Nakazawa, Shigeaki; Toyota, Kazuo; Sato, Kazunobu; Shiomi, Daisuke; Takui, Takeji
2016-08-18
Quantum computers are capable to efficiently perform full configuration interaction (FCI) calculations of atoms and molecules by using the quantum phase estimation (QPE) algorithm. Because the success probability of the QPE depends on the overlap between approximate and exact wave functions, efficient methods to prepare accurate initial guess wave functions enough to have sufficiently large overlap with the exact ones are highly desired. Here, we propose a quantum algorithm to construct the wave function consisting of one configuration state function, which is suitable for the initial guess wave function in QPE-based FCI calculations of open-shell molecules, based on the addition theorem of angular momentum. The proposed quantum algorithm enables us to prepare the wave function consisting of an exponential number of Slater determinants only by a polynomial number of quantum operations.
InAs Colloidal Quantum Dots Synthesis via Aminopnictogen Precursor Chemistry.
Grigel, Valeriia; Dupont, Dorian; De Nolf, Kim; Hens, Zeger; Tessier, Mickael D
2016-10-05
Despite their various potential applications, InAs colloidal quantum dots have attracted considerably less attention than more classical II-VI materials because of their complex syntheses that require hazardous precursors. Recently, amino-phosphine has been introduced as a cheap, easy-to-use and efficient phosphorus precursor to synthesize InP quantum dots. Here, we use aminopnictogen precursors to implement a similar approach for synthesizing InAs quantum dots. We develop a two-step method based on the combination of aminoarsine as the arsenic precursor and aminophosphine as the reducing agent. This results in state-of-the-art InAs quantum dots with respect to the size dispersion and band-gap range. Moreover, we present shell coating procedures that lead to the formation of InAs/ZnS(e) core/shell quantum dots that emit in the infrared region. This innovative synthesis approach can greatly facilitate the research on InAs quantum dots and may lead to synthesis protocols for a wide range of III-V quantum dots.
A Surface Chemistry Approach to Enhancing Colloidal Quantum Dot Solids for Photovoltaics
Carey, Graham Hamilton
Colloidal quantum dot (CQD) photovoltaic devices have improved rapidly over the past decade of research. By taking advantage of the quantum confinement effect, solar cells constructed using films of infrared-bandgap nanoparticles are able to capture previously untapped ranges of the solar energy spectrum. Additionally, films are fabricated using simple, cheap, reproducible solution processing techniques, enabling the creation of low-cost, flexible photovoltaic devices. A key factor limiting the creation of high efficiency CQD solar cells is the short charge carrier diffusion length in films. Driven by a combination of limited carrier mobility, poor nanoparticle surface passivation, and the presence of unexamined electrically active impurities throughout the film, the poor diffusion length limits the active layer thickness in CQD solar cells, leading to lower-than-desired light absorption, and curtailing the photocurrent generated by such devices. This thesis seeks to address poor diffusion length by addressing each of the limiting factors in turn. Electrical transport in quantum dot solids is examined in the context of improved quantum dot packing; methods are developed to improve packing by using actively densifying components, or by dramatically lowering the volume change required between quantum dots in solution and in solid state. Quantum dot surface passivation is improved by introducing a crucial secondary, small halide ligand source, and by surveying the impact of the processing environment on the final quality of the quantum dot surface. A heretofore unidentified impurity present in quantum dot solids is identified, characterized, and chemically eliminated. Finally, lessons learned through these experiments are combined into a single, novel materials system, leading to quantum dot devices with a significantly improved diffusion length (enhanced from 70 to 230 nm). This enabled thick, high current density (30 mA cm -2, compared to typical values in the 20
Carrier mobility in double-helix DNA and RNA: A quantum chemistry study with Marcus-Hush theory
Wu, Tao; Sun, Lei; Shi, Qi; Deng, Kaiming; Deng, Weiqiao; Lu, Ruifeng
2016-12-01
Charge mobilities of six DNAs and RNAs have been computed using quantum chemistry calculation combined with the Marcus-Hush theory. Based on this simulation model, we obtained quite reasonable results when compared with the experiment, and the obtained charge mobility strongly depends on the molecular reorganization and electronic coupling. Besides, we find that hole mobilities are larger than electron mobilities no matter in DNAs or in RNAs, and the hole mobility of 2L8I can reach 1.09 × 10-1 cm2 V-1 s-1 which can be applied in the molecular wire. The findings also show that our theoretical model can be regarded as a promising candidate for screening DNA- and RNA-based molecular electronic devices.
Jaffe, Richard; Han, Jie; Matsuda, Tsunetoshi; Yoon, Do; Langhoff, Stephen R. (Technical Monitor)
1997-01-01
Confirmations of 2,4-dihydroxypentane (DHP), a model molecule for poly(vinyl alcohol), have been studied by quantum chemistry (QC) calculations and molecular dynamics (MD) simulations. QC calculations at the 6-311G MP2 level show the meso tt conformer to be lowest in energy followed by the racemic tg, due to intramolecular hydrogen bond between the hydroxy groups. The Dreiding force field has been modified to reproduce the QC conformer energies for DHP. MD simulations using this force field have been carried out for DHP molecules in the gas phase, melt, and CHCl3 and water solutions. Extensive intramolecular hydrogen bonding is observed for the gas phase and CHCl3 solution, but not for the melt or aqueous solution, Such a condensed phase effect due to intermolecular interactions results in a drastic change in chain conformations, in agreement with experiments.
Carrier mobility in double-helix DNA and RNA: A quantum chemistry study with Marcus-Hush theory.
Wu, Tao; Sun, Lei; Shi, Qi; Deng, Kaiming; Deng, Weiqiao; Lu, Ruifeng
2016-12-21
Charge mobilities of six DNAs and RNAs have been computed using quantum chemistry calculation combined with the Marcus-Hush theory. Based on this simulation model, we obtained quite reasonable results when compared with the experiment, and the obtained charge mobility strongly depends on the molecular reorganization and electronic coupling. Besides, we find that hole mobilities are larger than electron mobilities no matter in DNAs or in RNAs, and the hole mobility of 2L8I can reach 1.09 × 10(-1) cm(2) V(-1) s(-1) which can be applied in the molecular wire. The findings also show that our theoretical model can be regarded as a promising candidate for screening DNA- and RNA-based molecular electronic devices.
Ion chemistry in the early universe: revisiting the role of HeH+ with new quantum calculations
Bovino, Stefano; Gianturco, Francesco A; Galli, Daniele
2011-01-01
The role of HeH+ has been newly assessed with the aid of newly calculated rates which use entirely ab initio methods, thereby allowing us to compute more accurately the relevant abundances within the global chemical network of the early universe. A comparison with the similar role of the ionic molecule LiH+ is also presented. Quantum calculations have been carried out for the gas-phase reaction of HeH+ with H atoms with our new in-house code, based on the negative imaginary potential method. Integral cross sections and reactive rate coefficients obtained under the general conditions of early universe chemistry are presented and discussed. With the new reaction rate, the abundance of HeH+ in the early universe is more than one order of magnitude larger than in previous studies. Our more accurate findings further buttress the possibility to detect cosmological signatures of HeH+.
Institute of Scientific and Technical Information of China (English)
YAN XiuFen; JIANG Nan; MA Jing
2009-01-01
A series of theoretical approaches,including conventional FF03 and FF03-based polarization model,as well as the generalized energy-based fragmentation (GEBF) quantum chemistry method,have been applied to investigate the interactions between acetate ion (CH_3COO~-) and the α-subunit of human adult hemoglobin (designated as Hb-α) at four binding sites (Lys16,Lys90,Arg92,and Lys127),respectively.The FF03-based polarizable force fields show that the interaction energies between the CH_3COO~-group and Hb-α follow the trend of Arg92＞Lys127＞Lys90＞Lys16.The complexation of CH_3COO~-with Hb-α is governed by the long-range electrostatic interactions and steric effect.
Institute of Scientific and Technical Information of China (English)
无
2009-01-01
A series of theoretical approaches,including conventional FF03 and FF03-based polarization model,as well as the generalized energy-based fragmentation(GEBF) quantum chemistry method,have been applied to investigate the interactions between acetate ion(CH3COO-) and the α-subunit of human adult hemoglobin(designated as Hb-α) at four binding sites(Lys16,Lys90,Arg92,and Lys127),respectively.The FF03-based polarizable force fields show that the interaction energies between the CH3COO-group and Hb-α follow the trend of Arg92>Lys127>Lys90>Lys16.The complexation of CH3COO-with Hb-α is governed by the long-range electrostatic interactions and steric effect.
Khaikin, L. S.; Grikina, O. E.; Karasev, N. M.; Kovtun, D. M.; Kochikov, I. V.
2014-04-01
The equilibrium structure of the urotropine molecule is characterized by means of gas electron diffraction (GED) with the involvement of quantum chemistry and vibrational spectroscopy. A structural analysis of the GED data is performed based on the parameters of the intramolecular potential function using of the program complex SYMM/DISP/ELDIFF/LARGE. The quadratic and cubic force constants of the urotropine molecule were obtained earlier on the basis of calculations at the MP2(full)/cc-pVTZ level and assuming molecular symmetry T d . The values of the equilibrium geometric parameters r e of the urotropine molecule are found. The experimental structural parameters are in good agreement with those calculated at the MP2(full)/cc-pVTZ level.
Allen, Emily Christine
Mental models for scientific learning are often defined as, "cognitive tools situated between experiments and theories" (Duschl & Grandy, 2012). In learning, these cognitive tools are used to not only take in new information, but to help problem solve in new contexts. Nancy Nersessian (2008) describes a mental model as being "[loosely] characterized as a representation of a system with interactive parts with representations of those interactions. Models can be qualitative, quantitative, and/or simulative (mental, physical, computational)" (p. 63). If conceptual parts used by the students in science education are inaccurate, then the resulting model will not be useful. Students in college general chemistry courses are presented with multiple abstract topics and often struggle to fit these parts into complete models. This is especially true for topics that are founded on quantum concepts, such as atomic structure and molecular bonding taught in college general chemistry. The objectives of this study were focused on how students use visual tools introduced during instruction to reason with atomic and molecular structure, what misconceptions may be associated with these visual tools, and how visual modeling skills may be taught to support students' use of visual tools for reasoning. The research questions for this study follow from Gilbert's (2008) theory that experts use multiple representations when reasoning and modeling a system, and Kozma and Russell's (2005) theory of representational competence levels. This study finds that as students developed greater command of their understanding of abstract quantum concepts, they spontaneously provided additional representations to describe their more sophisticated models of atomic and molecular structure during interviews. This suggests that when visual modeling with multiple representations is taught, along with the limitations of the representations, it can assist students in the development of models for reasoning about
A Writing and Ethics Component for a Quantum Mechanics, Physical Chemistry Course
Reilly, John T.; Strickland, Michael
2010-01-01
A writing-across-the-curriculum and ethics component is presented for a second-semester, physical chemistry course. The activity involves introducing ethical issues pertinent to scientists. Students are asked to read additional material, participate in discussions, and write essays and a paper on an ethical issue. The writing and discussion…
Humbert, Christophe; Dahi, Abdellatif; Dalstein, Laetitia; Busson, Bertrand; Lismont, Marjorie; Colson, Pierre; Dreesen, Laurent
2015-05-01
We develop an innovative manufacturing process, based on radio-frequency magnetron sputtering (RFMS), to prepare neat CdSe quantum dots (QDs) on glass and silicon substrates and further chemically functionalize them. In order to validate the fabrication protocol, their optical properties are compared with those of QDs obtained from commercial solutions and deposited by wet chemistry on the substrates. Firstly, AFM measurements attest that nano-objects with a mean diameter around 13 nm are located on the substrate after RFMS treatment. Secondly, the UV-Vis absorption study of this deposited layer shows a specific optical absorption band, located at 550 nm, which is related to a discrete energy level of QDs. Thirdly, by using two-color sum-frequency generation (2C-SFG) nonlinear optical spectroscopy, we show experimentally the functionalization efficiency of the RFMS CdSe QDs layer with thiol derived molecules, which is not possible on the QDs layer prepared by wet chemistry due to the surfactant molecules from the native solution. Finally, 2C-SFG spectroscopy, performed at different visible wavelengths, highlights modifications of the vibration mode shape whatever the QDs deposition method, which is correlated to the discrete energy level of the QDs.
Mishra, H.; Colussi, A. J.; Enami, S.; Nielsen, R. J.; Hoffmann, M. R.; Goddard, W. A.
2012-12-01
It has become increasingly apparent that atmospheric chemistry involves more than gas-phase reactions. Key processes, such as the decay of NO2 in urban plumes and the associated daytime formation of HONO, and the rapid chemistries observed in and over forest canopies at nighttime defy explanation by conventional atmospheric chemistry mechanisms. We have recently reported experimental results on several gas-liquid reactions of atmospheric interest, such as the facile protonation of gaseous isoprene on mildly acidic (pH bioenergetics coupling, 'on-water' catalysis, self-assembly and molecular recognition, little is known about the molecular mechanisms of such reactions. Herein we apply quantum mechanics to investigate how biogenic or anthropogenic olefins may get protonated and undergo oligomerization at the air-water interface by performing model calculations on small water clusters carrying an excess proton as surrogates for the surface of mildly acidic water as sensed by gaseous isoprene (ISO). We find that ISO binds weakly to the surface of water and accepts a proton from H+(H2O)3, leading to ISOH+ via a proton transfer hindered by a ΔG1‡ = 5.6 kcal mol-1 kinetic barrier. Subsequently, another ISO attaches loosely to this ensemble, before being attacked by the ISOH+. This process, which represents the first step of the cationic polymerization of ISO, is hindered by a similar ΔG2‡ = 5.7 kcal mol-1 barrier. Our theoretical results are consistent with experimental (~ 10-4) uptake coefficients for ISO measured on acidic water.
IMPLEMENTATION OF REACTION FIELD METHODS IN QUANTUM-CHEMISTRY COMPUTER CODES
DEVRIES, AH; VANDUIJNEN, PT; JUFFER, AH; RULLMANN, JAC; DIJKMAN, JP; MERENGA, H; THOLE, BT
1995-01-01
The embedding of a quantum mechanically described subsystem by classical representations of its surroundings is reviewed. The choices for a distributed monopole representation and a distributed (group) polarizability representation, as well as the continuum approach to model bulk effects, are discus
The Variation Theorem Applied to H-2+: A Simple Quantum Chemistry Computer Project
Robiette, Alan G.
1975-01-01
Describes a student project which requires limited knowledge of Fortran and only minimal computing resources. The results illustrate such important principles of quantum mechanics as the variation theorem and the virial theorem. Presents sample calculations and the subprogram for energy calculations. (GS)
Dynamics of the Chemistry of Electronically Excited Atoms in Defined Quantum States.
1978-05-01
laser development . In essence, this research concerns itself with the elucidation of the role of electronic energy in affecting the chemistry or photochemistry of excited halogen atoms and molecules. While much is known about the dynamics of chemical and physical processes which are carried out on the lowest potential energy hypersurface correlating with reactants and products in their electronic ground state, relatively little is known about the dynamics of such phenomena as energy transfer and chemical reactivity on higher-lying potential
One-Step Synthesis of Boron Nitride Quantum Dots: Simple Chemistry Meets Delicate Nanotechnology.
Liu, Bingping; Yan, Shihai; Song, Zhongqian; Liu, Mengli; Ji, Xuqiang; Yang, Wenrong; Liu, Jingquan
2016-12-23
Herein, a conceptually new and straightforward aqueous route is described for the synthesis of hydroxyl- and amino-functionalized boron nitride quantum dots (BNQDs) with quantum yields (QY) as high as 18.3 % by using a facile bottom-up approach, in which a mixture of boric acid and ammonia solution was hydrothermally treated in one pot at 200 °C for 12 h. The functionalized BNQDs, with excellent photoluminescence properties, could be easily dispersed in an aqueous medium and applied as fluorescent probes for the detection of ferrous (Fe(2+) ) and ferric (Fe(3+) ) ions with excellent selectivity and low detection limits. The mechanisms for the hydrothermal reaction and fluorescence quenching were also simulated by using density functional theory (DFT), which confirmed the feasibility and advantages of this strategy. It provides a scalable and eco-friendly method for preparation of BNQDs with good dispersability and could also be generalized to the synthesis of other 2D quantum dots and nanoplates.
Yb-based heavy fermion compounds and field tuned quantum chemistry
Energy Technology Data Exchange (ETDEWEB)
Mun, Eundeok [Iowa State Univ., Ames, IA (United States)
2010-01-01
The motivation of this dissertation was to advance the study of Yb-based heavy fermion (HF) compounds especially ones related to quantum phase transitions. One of the topics of this work was the investigation of the interaction between the Kondo and crystalline electric field (CEF) energy scales in Yb-based HF systems by means of thermoelectric power (TEP) measurements. In these systems, the Kondo interaction and CEF excitations generally give rise to large anomalies such as maxima in ρ(T) and as minima in S(T). The TEP data were use to determine the evolution of Kondo and CEF energy scales upon varying transition metals for YbT_{2}Zn_{20} (T = Fe, Ru, Os, Ir, Rh, and Co) compounds and applying magnetic fields for YbAgGe and YbPtBi. For YbT_{2}Zn_{20} and YbPtBi, the Kondo and CEF energy scales could not be well separated in S(T), presumably because of small CEF level splittings. A similar effect was observed for the magnetic contribution to the resistivity. For YbAgGe, S(T) has been successfully applied to determine the Kondo and CEF energy scales due to the clear separation between the ground state and thermally excited CEF states. The Kondo temperature, T_{K}, inferred from the local maximum in S(T), remains finite as magnetic field increases up to 140 kOe. In this dissertation we have examined the heavy quasi-particle behavior, found near the field tuned AFM quantum critical point (QCP), with YbAgGe and YbPtBi. Although the observed nFL behaviors in the vicinity of the QCP are different between YbAgGe and YbPtBi, the constructed H-T phase diagram including the two crossovers are similar. For both YbAgGe and YbPtBi, the details of the quantum criticality turn out to be complicated. We expect that YbPtBi will provide an additional example of field tuned quantum criticality, but clearly there are further experimental investigations left and more ideas needed to understand the basic physics of field-induced quantum
Institute of Scientific and Technical Information of China (English)
陆荣健; 杨华铮; 尚贞锋; 汪惟为; 潘荫明; 赵学庄
1996-01-01
In view of quantum pharmacology, the structure-activity relationships of different kinds of fused heterocydic sulfonamides with the same mode of action were first investigated using molecular mechanics, quantum chemistry and discriminatory analysis. It has been found that the process of the interaction of the fused heterocydic sulfonamide with ALS enzyme involves the electropositive region of the sulfonyl bridge chain and the electronegative region of the heterocydic moiety. The herbicidal activity is related to the potency of electric charge translocation of the related regions.
Sharma, Sandeep; Booth, George H; Umrigar, C J; Chan, Garnet Kin-Lic
2014-01-01
We combine explicit correlation via the canonical transcorrelation approach with the density matrix renormalization group and initiator full configuration interaction quantum Monte Carlo methods to compute a near-exact beryllium dimer curve, {\\it without} the use of composite methods. In particular, our direct density matrix renormalization group calculations produce a well-depth of $D_e$=931.2 cm$^{-1}$ which agrees very well with recent experimentally derived estimates $D_e$=929.7$\\pm 2$~cm$^{-1}$ [Science, 324, 1548 (2009)] and $D_e$=934.6~cm$^{-1}$ [Science, 326, 1382 (2009)
QED-SCF, MCSCF and Coupled-cluster Methods in Quantum Chemistry
Ohsaku, Tadafumi; Yamaguchi, Kizashi
2001-01-01
We investigate the method to combine the techniques of quantum chemisty with QED. In our theory, we treat the N-electron system and the Dirac sea on an equal footing; we regard both of them as the dynamical degrees of freedom of a many-body system. After the introduction of our QED-SCF method, the QED-SCF solutions are classified into several classes on the basis of group-theoretical operations such as time reversal, parity and O(3) rotational symmetry. The natural orbitals of general QED-SCF...
Lounnas, Valère; Wedler, Henry B; Newman, Timothy; Schaftenaar, Gijs; Harrison, Jason G; Nepomuceno, Gabriella; Pemberton, Ryan; Tantillo, Dean J; Vriend, Gert
2014-11-01
In molecular sciences, articles tend to revolve around 2D representations of 3D molecules, and sighted scientists often resort to 3D virtual reality software to study these molecules in detail. Blind and visually impaired (BVI) molecular scientists have access to a series of audio devices that can help them read the text in articles and work with computers. Reading articles published in this journal, though, is nearly impossible for them because they need to generate mental 3D images of molecules, but the article-reading software cannot do that for them. We have previously designed AsteriX, a web server that fully automatically decomposes articles, detects 2D plots of low molecular weight molecules, removes meta data and annotations from these plots, and converts them into 3D atomic coordinates. AsteriX-BVI goes one step further and converts the 3D representation into a 3D printable, haptic-enhanced format that includes Braille annotations. These Braille-annotated physical 3D models allow BVI scientists to generate a complete mental model of the molecule. AsteriX-BVI uses Molden to convert the meta data of quantum chemistry experiments into BVI friendly formats so that the entire line of scientific information that sighted people take for granted-from published articles, via printed results of computational chemistry experiments, to 3D models-is now available to BVI scientists too. The possibilities offered by AsteriX-BVI are illustrated by a project on the isomerization of a sterol, executed by the blind co-author of this article (HBW).
Robblee, Karen M.
Current science education reform efforts promote inquiry-based learning, a goal that requires appropriate tools and instructional approaches. This study investigated the influence of the beliefs and knowledge of four experienced secondary chemistry teachers in their use of new instructional software that generates models of atoms and molecules based on quantum mechanics. The software, which was developed through a National Science Foundation funded project, Quantum Science Across Disciplines (QSAD), was designed to promote inquiry learning. Qualitative research methods were used for this multiple case study. Data from surveys, interviews, and extended classroom observations revealed a close correlation between a teacher's model of the learner and his or her model of teaching. Combined models of learner and teacher had the greatest influence on their decisions about implementing QSAD software. Teachers who espoused a constructivist model of learning and related models of teaching used the software to promote student investigations and inductive approaches to learning. Other factors that appeared to support the use of inquiry methods included sufficient time for students to investigate phenomena, the extent of the teacher's pedagogical content knowledge, and the amount of training using QSAD software. The Views-On-Science-Technology-Society (VOSTS) instrument was used to compare the informants' beliefs about the epistemology of science to their classroom practices. Data related to the role of teachers' beliefs about scientific knowledge were inconclusive, and VOSTS results were inconsistent with the informants' stated beliefs. All four cases revealed that the teachers acted as agents of the school culture. In schools that promoted development of critical thinking, questioning, and self-direction in students, teachers were more likely to use a variety of instructional methods and emphasize construction of knowledge. These findings suggest that educational reform
Krull, Ulrich J.; W. Russ Algar
2011-01-01
The use of quantum dots (QDs) as donors in fluorescence resonance energy transfer (FRET) offer several advantages for the development of multiplexed solid-phase QD-FRET nucleic acid hybridization assays. Designs for multiplexing have been demonstrated, but important challenges remain in the optimization of these systems. In this work, we identify several strategies based on the design of interfacial chemistry for improving sensitivity, obtaining lower limits of detection (LOD) and enabling th...
Liu, Fang; Kulik, Heather J; Martínez, Todd J
2015-01-01
The conductor-like polarization model (C-PCM) with switching/Gaussian smooth discretization is a widely used implicit solvation model in chemical simulations. However, its application in quantum mechanical calculations of large-scale biomolecular systems can be limited by computational expense of both the gas phase electronic structure and the solvation interaction. We have previously used graphical processing units (GPUs) to accelerate the first of these steps. Here, we extend the use of GPUs to accelerate electronic structure calculations including C-PCM solvation. Implementation on the GPU leads to significant acceleration of the generation of the required integrals for C-PCM. We further propose two strategies to improve the solution of the required linear equations: a dynamic convergence threshold and a randomized block-Jacobi preconditioner. These strategies are not specific to GPUs and are expected to be beneficial for both CPU and GPU implementations. We benchmark the performance of the new implementat...
Nicolaides, Cleanthes A
2015-01-01
Recent developments toward the production and laboratory use of pulses of high intensity, and/or of very high frequency, and/or of ultrashort duration, make possible experiments which can produce time-resolved data on ultrafast transformations involving motions of electrons. The formulation, quantitative understanding and prediction of related new phenomena entail the possibility of computing and applying solutions of the many-electron time-dependent Schroedinger equation, for arbitrary electronic structures, including the dominant effects of Rydberg series, of multiply excited states and of the multi-channel continuous spectrum. To this purpose, we have proposed and applied to many prototypical cases the state-specific expansion approach (SSEA). (Mercouris, Komninos and Nicolaides, Adv. Quantum Chem. 60, 333 (2010)). The paper explains briefly the SSEA, and outlines four of its applications to recently formulated problems concerning time-resolved electronic processes, where electron correlations are crucial....
Quantum chemistry study of molecular structure and vibrational spectrum of naproxen.
Liu, Lekun; Gao, Hongwei
2012-02-01
The purpose of this research was to compare the performance of different DFT methods at different basis sets in predicting geometry and vibrational spectrum of naproxen. The molecular structure and infrared spectrum of naproxen was studied. Quantum chemical calculations using density functional theory (DFT) with functions LSDA, B3LYP, B3PW91, BPV86, mPW1PW91 and PBEPBE at various basis set levels (LANL2DZ, SDD, 3-21G, 6-31G, 6-311G and STO-3G) were performed. The computed result indicates that LSDA/6-311G level is distinctly superior to all the remaining DFT methods in predicting molecular structure of naproxen. The vibrational spectral analysis indicates the LSDA/3-21G level and LSDA/6-311G level are both better than the other methods at all the remaining basis sets.
High-throughput quantum chemistry and virtual screening for OLED material components
Halls, Mathew D.; Giesen, David J.; Hughes, Thomas F.; Goldberg, Alexander; Cao, Yixiang
2013-09-01
Computational structure enumeration, analysis using an automated simulation workflow and filtering of large chemical structure libraries to identify lead systems, has become a central paradigm in drug discovery research. Transferring this paradigm to challenges in materials science is now possible due to advances in the speed of computational resources and the efficiency and stability of chemical simulation packages. State-of-the-art software tools that have been developed for drug discovery can be applied to efficiently explore the chemical design space to identify solutions for problems such as organic light-emitting diode material components. In this work, virtual screening for OLED materials based on intrinsic quantum mechanical properties is illustrated. Also, a new approach to more reliably identify candidate systems is introduced that is based on the chemical reaction energetics of defect pathways for OLED materials.
Spectral methods in chemistry and physics applications to kinetic theory and quantum mechanics
Shizgal, Bernard
2015-01-01
This book is a pedagogical presentation of the application of spectral and pseudospectral methods to kinetic theory and quantum mechanics. There are additional applications to astrophysics, engineering, biology and many other fields. The main objective of this book is to provide the basic concepts to enable the use of spectral and pseudospectral methods to solve problems in diverse fields of interest and to a wide audience. While spectral methods are generally based on Fourier Series or Chebychev polynomials, non-classical polynomials and associated quadratures are used for many of the applications presented in the book. Fourier series methods are summarized with a discussion of the resolution of the Gibbs phenomenon. Classical and non-classical quadratures are used for the evaluation of integrals in reaction dynamics including nuclear fusion, radial integrals in density functional theory, in elastic scattering theory and other applications. The subject matter includes the calculation of transport coefficient...
Directory of Open Access Journals (Sweden)
Neng-Zhong Xie
Full Text Available Three strong interactions between amino acid side chains (salt bridge, cation-π, and amide bridge are studied that are stronger than (or comparable to the common hydrogen bond interactions, and play important roles in protein-protein interactions.Quantum chemical methods MP2 and CCSD(T are used in calculations of interaction energies and structural optimizations.The energies of three types of amino acid side chain interactions in gaseous phase and in aqueous solutions are calculated using high level quantum chemical methods and basis sets. Typical examples of amino acid salt bridge, cation-π, and amide bridge interactions are analyzed, including the inhibitor design targeting neuraminidase (NA enzyme of influenza A virus, and the ligand binding interactions in the HCV p7 ion channel. The inhibition mechanism of the M2 proton channel in the influenza A virus is analyzed based on strong amino acid interactions.(1 The salt bridge interactions between acidic amino acids (Glu- and Asp- and alkaline amino acids (Arg+, Lys+ and His+ are the strongest residue-residue interactions. However, this type of interaction may be weakened by solvation effects and broken by lower pH conditions. (2 The cation- interactions between protonated amino acids (Arg+, Lys+ and His+ and aromatic amino acids (Phe, Tyr, Trp and His are 2.5 to 5-fold stronger than common hydrogen bond interactions and are less affected by the solvation environment. (3 The amide bridge interactions between the two amide-containing amino acids (Asn and Gln are three times stronger than hydrogen bond interactions, which are less influenced by the pH of the solution. (4 Ten of the twenty natural amino acids are involved in salt bridge, or cation-, or amide bridge interactions that often play important roles in protein-protein, protein-peptide, protein-ligand, and protein-DNA interactions.
Cysewski, Piotr; Jeliński, Tomasz
2013-10-01
The electronic spectrum of four different anthraquinones (1,2-dihydroxyanthraquinone, 1-aminoanthraquinone, 2-aminoanthraquinone and 1-amino-2-methylanthraquinone) in methanol solution was measured and used as reference data for theoretical color prediction. The visible part of the spectrum was modeled according to TD-DFT framework with a broad range of DFT functionals. The convoluted theoretical spectra were validated against experimental data by a direct color comparison in terms of CIE XYZ and CIE Lab tristimulus model color. It was found, that the 6-31G** basis set provides the most accurate color prediction and there is no need to extend the basis set since it does not improve the prediction of color. Although different functionals were found to give the most accurate color prediction for different anthraquinones, it is possible to apply the same DFT approach for the whole set of analyzed dyes. Especially three functionals seem to be valuable, namely mPW1LYP, B1LYP and PBE0 due to very similar spectra predictions. The major source of discrepancies between theoretical and experimental spectra comes from L values, representing the lightness, and the a parameter, depicting the position on green→magenta axis. Fortunately, the agreement between computed and observed blue→yellow axis (parameter b) is very precise in the case of studied anthraquinone dyes in methanol solution. Despite discussed shortcomings, color prediction from first principle quantum chemistry computations can lead to quite satisfactory results, expressed in terms of color space parameters.
Jung, Julie; Guennic, Boris Le; Fedin, Matvey V; Ovcharenko, Victor I; Calzado, Carmen J
2015-07-20
The gradual magnetostructural transition in breathing crystals based on copper(II) and pyrazolyl-substituted nitronyl nitroxides has been analyzed by means of DDCI quantum chemistry calculations. The magnetic coupling constants (J) within the spin triads of Cu(hfac)2L(Bu)·0.5C8H18 have been evaluated for the X-ray structures reported at different temperatures. The coupling is strongly antiferromagnetic at low temperature and becomes ferromagnetic when the temperature increases. The intercluster magnetic coupling (J') is antiferromagnetic and shows a marked dependence on temperature. The magnetostructural transition can be reproduced using the calculated J values for each structure in the simulation of the magnetic susceptibility. However, the μ(T) curve can be improved nicely by considering the coexistence of two phases in the transition region, whose ratio varies with temperature corresponding to both the weakly and strongly coupled spin states. These results complement a recent VT-FTIR study on the parent Cu(hfac)2L(Pr) compound with a gradual magnetostructural transition.
Institute of Scientific and Technical Information of China (English)
REN Yong-Gang; CHEN Zhi-Rong; LI Hao-Hong; ZHAO Bin; HUANG Chang-Cang; LI Jun-Qian
2005-01-01
The title compound [Cu(dafone)2(DMF)2](2ClO4 1 (dafone = 4,5-diazafluoren- 9-one, dmf = N,N(A)-dimethyl formamide) was synthesized by the reaction of Cu(ClO4 )2 and dafone in DMF solution at room temperature with pH = 3.0.The single-crystal X-ray analysis has revealed that 1 crystallizes in monoclinic, space group P21/n with a = 8.4853(8), b = 13.1520 (14), c = 14.3866(12) (A), β = 102.629(3)o, V = 1566.7(3) (A)3, C28H26Cl2CuN6O12, Mr = 773.00, Z = 2, Dc = 1.639 g/cm3 , F(000) = 790, μ = 0.942 mm-1, the final R = 0.0438 and wR = 0.1214 for 3165 obser- ved reflections with I > 2σ(I).X-ray analysis shows that compound 1 has unsymmetric chelation of dafone with one Cu-N bond being much longer than the other.Coordination geometry of Cu is a highly distorted octahedron and the whole structure is stabilized by π-π stacking and static attractive forces from [ClO4]- anions.Based on the crystal data, quantum chemistry calculation at the DFT/ B3LPY level was used to reveal the electronic structure of 1.
New algorithms for iterative matrix-free eigensolvers in quantum chemistry.
Zuev, Dmitry; Vecharynski, Eugene; Yang, Chao; Orms, Natalie; Krylov, Anna I
2015-02-15
New algorithms for iterative diagonalization procedures that solve for a small set of eigen-states of a large matrix are described. The performance of the algorithms is illustrated by calculations of low and high-lying ionized and electronically excited states using equation-of-motion coupled-cluster methods with single and double substitutions (EOM-IP-CCSD and EOM-EE-CCSD). We present two algorithms suitable for calculating excited states that are close to a specified energy shift (interior eigenvalues). One solver is based on the Davidson algorithm, a diagonalization procedure commonly used in quantum-chemical calculations. The second is a recently developed solver, called the "Generalized Preconditioned Locally Harmonic Residual (GPLHR) method." We also present a modification of the Davidson procedure that allows one to solve for a specific transition. The details of the algorithms, their computational scaling, and memory requirements are described. The new algorithms are implemented within the EOM-CC suite of methods in the Q-Chem electronic structure program.
Inactivation of ovine cyclooxygenase-1 by bromoaspirin and aspirin: a quantum chemistry description.
Barroso-Neto, Ito L; Marques, João Paulo C; da Costa, Roner F; Caetano, Ewerton W S; Cavada, Benildo S; Gottfried, Carmem; Freire, Valder N
2012-03-15
The resulting noncovalent bonding of the salicylic acid to ovine COX-1 after bromoaspirin and aspirin acetylation by Ser530 is investigated within the scope of density functional theory considering a 6.5 Å radius binding pocket. We have not only took full advantage of published X-ray structural data for the ovine COX-1 cocrystallized with bromoaspirin, but we also have improved that data through computation, finding good estimates for the hydrogen atom positions at the residues of the binding pocket, and repositioning the Ser530Ac[Br;H] lateral chain and salicylic acid by total energy minimization procedures employing LDA and GGA+D exchange-correlation functionals. Using bromoaspirin as a template, we have simulated the positioning of aspirin in the binding pocket, estimating its interaction energy with each of its neighbor COX-1 residues. We demonstrate that the binding energies of bromoaspirin and aspirin to COX-1 are very close when second-order quantum refinements of the structural data are performed, which points to an explanation on why the IC(50) values for the 126 μM COX-1 activity of both bromoaspirin and aspirin are practically the same. Attracting and repelling residues were identified, being shown that Arg120 is the most effective residue attracting the salicylic acid, followed by Ala527, Leu531, Leu359, and Ser353. On the other hand, Glu524 was found the most effective repulsive residue (strength interaction comparable to Arg120). © 2012 American Chemical Society
Ferres, Lynn; Mouhib, Halima; Stahl, Wolfgang; Schwell, Martin; Nguyen, Ha Vinh Lam
2017-07-01
Phenyl formate has been investigated by molecular jet Fourier-transform microwave spectroscopy in the frequency range from 2 to 26.5 GHz. Quantum chemical calculations at the MP2/6-311++G(d,p) level of theory indicate that this molecule does not have a plane of symmetry at equilibrium, and that the phenyl ring performs a large amplitude tunneling motion from one side of the Cs configuration to the other. The tilt angle of the ring out of the Hsbnd (Cdbnd O)O plane is ±70° and the calculated tunneling barrier is only 28 cm-1. The two lowest torsional states vt = 0 and 1 are assigned in the experimental spectrum and fitted using the program SPFIT/SPCAT. The Coriolis splitting ΔE between these states is 46.2231(25) GHz, very close to the value of 48.24 GHz calculated using a simple two-top torsional Hamiltonian of the formate group and the phenyl ring.
A spin-adapted Density Matrix Renormalization Group algorithm for quantum chemistry
Sharma, Sandeep
2014-01-01
We extend the spin-adapted density matrix renormalization group (DMRG) algorithm of McCulloch and Gulacsi [Europhys. Lett.57, 852 (2002)] to quantum chemical Hamiltonians. This involves two key modifications to the non-spin-adapted DMRG algorithm: the use of a quasi-density matrix to ensure that the renormalised DMRG states are eigenvalues of $S^2$ , and the use of the Wigner-Eckart theorem to greatly reduce the overall storage and computational cost. We argue that the advantages of the spin-adapted DMRG algorithm are greatest for low spin states. Consequently, we also implement the singlet-embedding strategy of Nishino et al [Phys. Rev. E61, 3199 (2000)] which allows us to target high spin states as a component of a mixed system which is overall held in a singlet state. We evaluate our algorithm on benchmark calculations on the Fe$_2$S$_2$ and Cr$_2$ transition metal systems. By calculating the full spin ladder of Fe$_2$S$_2$ , we show that the spin-adapted DMRG algorithm can target very closely spaced spin ...
Towards ab initio self-energy embedding theory in quantum chemistry
Lan, Tran Nguyen; Zgid, Dominika
2015-01-01
The self-energy embedding theory (SEET), in which the active space self-energy is embedded in the self-energy obtained from a perturbative method treating the non-local correlation effects, was recently developed in our group. In SEET the double counting problem does not appear and the accuracy can be improved either by increasing the perturbation order or by enlarging the active space. This method was first calibrated for the 2D Hubbard lattice showing promising results. In this paper, we report an extension of SEET to quantum chemical ab initio Hamiltonians for applications to molecular systems. The self-consistent second-order Green's function (GF2) method is used to describe the non-local correlations, while the full configuration interaction (FCI) method is carried out to capture strong correlation within the active space. Using few proof-of-concept examples, we show that SEET yields results of comparable quality to $n-$electron valence state second-order perturbation theory (NEVPT2) with the same active...
Communication: Towards ab initio self-energy embedding theory in quantum chemistry
Energy Technology Data Exchange (ETDEWEB)
Lan, Tran Nguyen, E-mail: latran@umich.edu [Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109 (United States); Department of Physics, University of Michigan, Ann Arbor, Michigan 48109 (United States); Kananenka, Alexei A.; Zgid, Dominika [Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109 (United States)
2015-12-28
The self-energy embedding theory (SEET), in which the active space self-energy is embedded in the self-energy obtained from a perturbative method treating the non-local correlation effects, was recently developed in our group. In SEET, the double counting problem does not appear and the accuracy can be improved either by increasing the perturbation order or by enlarging the active space. This method was first calibrated for the 2D Hubbard lattice showing promising results. In this paper, we report an extension of SEET to quantum chemical ab initio Hamiltonians for applications to molecular systems. The self-consistent second-order Green’s function method is used to describe the non-local correlations, while the full configuration interaction method is carried out to capture strong correlation within the active space. Using few proof-of-concept examples, we show that SEET yields results of comparable quality to n-electron valence state second-order perturbation theory with the same active space, and furthermore, the full active space can be split into smaller active spaces without further implementation. Moreover, SEET avoids intruder states and does not require any high-order reduced density matrices. These advantages show that SEET is a promising method to describe physical and chemical properties of challenging molecules requiring large active spaces.
Quantum dot surface chemistry and functionalization for cell targeting and imaging.
Bilan, Regina; Fleury, Fabrice; Nabiev, Igor; Sukhanova, Alyona
2015-04-15
Quantum dots (QDs) are highly fluorescent nanoscale crystals with size-dependent emission spectra. Due to their excellent photophysical properties, QDs are a promising alternative to organic fluorescent dyes and fluorescent proteins for cell targeting, imaging, and drug delivery. For biomedical applications, QDs should be chemically modified to be stable in aqueous solutions and tagged with the recognition molecules or drugs. Here, we review surface modification approaches to, and strategies for, conjugation of bioactive molecules with QDs. There are a variety of methods of QD surface modification and QD incorporation into larger delivery systems that yield fluorescent nanocarriers from 10 nm to several micrometers. Conjugates of QDs with peptides, proteins, antibodies, oligonucleotides, and small molecules have been used for fluorescent targeting, tracking, and imaging both in vitro and in vivo. Due to an extremely high stability to photobleaching, QDs were used for long-term visualization. QD applications pave the way for new generations of ultrasensitive detection, diagnostic systems, as well as drug delivery approaches, combining accurate targeting, delivery, and imaging in a single assay.
Communication: Towards ab initio self-energy embedding theory in quantum chemistry.
Lan, Tran Nguyen; Kananenka, Alexei A; Zgid, Dominika
2015-12-28
The self-energy embedding theory (SEET), in which the active space self-energy is embedded in the self-energy obtained from a perturbative method treating the non-local correlation effects, was recently developed in our group. In SEET, the double counting problem does not appear and the accuracy can be improved either by increasing the perturbation order or by enlarging the active space. This method was first calibrated for the 2D Hubbard lattice showing promising results. In this paper, we report an extension of SEET to quantum chemical ab initio Hamiltonians for applications to molecular systems. The self-consistent second-order Green's function method is used to describe the non-local correlations, while the full configuration interaction method is carried out to capture strong correlation within the active space. Using few proof-of-concept examples, we show that SEET yields results of comparable quality to n-electron valence state second-order perturbation theory with the same active space, and furthermore, the full active space can be split into smaller active spaces without further implementation. Moreover, SEET avoids intruder states and does not require any high-order reduced density matrices. These advantages show that SEET is a promising method to describe physical and chemical properties of challenging molecules requiring large active spaces.
A quantum chemistry study for ionic liquids applied to gas capture and separation.
Damas, Giane B; Dias, Amina B A; Costa, Luciano T
2014-07-31
In recent years, the global climate change is in evidence and it is almost a consensus that it is caused by the greenhouse gases emissions. An alternative to reduce these emissions is carbon capture and storage (CCS), which employs solvents based on amine compounds. In this scene, ionic liquids (IL) have been investigated to a greater extent for this application. In this work, we make an evaluation of interactions between gases (CO2, SO2, and H2S) and anion/cation from IL, as well as cation-anion interactions. For this, quantum calculations under vacuum were performed at the B3LYP/6-311+G** level of theory and using the M06-2X functional, where dispersion effects are considered. Among the well-studied systems based on imidazolium cations and fluorinated anions, we also studied the tetraalkylammonium, tetraalkylphosphonium, ether-functionalized imidazolium based systems, and tetrahexylammonium bis(trifluoromethanesulfonyl)imide, [THA][Tf2N], as a potential prototype. The ion pairs evaluated include [Tf2N](-)-based IL, with alkyl chain varying from [C1mim](+) to [C8mim](+) and [C1mim](+)-based IL. We found that the anion becomes more available to interact with gas with the weakening of the cation-anion interaction. [THA][Tf2N] has a binding energy of -274.89 kJ/mol at the B3LYP/6-311+G** level of theory, which is considered energetically interesting to gas capture applications.
RM1 Semiempirical Quantum Chemistry: Parameters for Trivalent Lanthanum, Cerium and Praseodymium.
Directory of Open Access Journals (Sweden)
José Diogo L Dutra
Full Text Available The RM1 model for the lanthanides is parameterized for complexes of the trications of lanthanum, cerium, and praseodymium. The semiempirical quantum chemical model core stands for the [Xe]4fn electronic configuration, with n =0,1,2 for La(III, Ce(III, and Pr(III, respectively. In addition, the valence shell is described by three electrons in a set of 5d, 6s, and 6p orbitals. Results indicate that the present model is more accurate than the previous sparkle models, although these are still very good methods provided the ligands only possess oxygen or nitrogen atoms directly coordinated to the lanthanide ion. For all other different types of coordination, the present RM1 model for the lanthanides is much superior and must definitely be used. Overall, the accuracy of the model is of the order of 0.07Å for La(III and Pr(III, and 0.08Å for Ce(III for lanthanide-ligand atom distances which lie mostly around the 2.3Å to 2.6Å interval, implying an error around 3% only.
Aggregation and growth of ZnO quantum dots prepared from sol-gel chemistry
Energy Technology Data Exchange (ETDEWEB)
Santilli, C.V.; Pulcinelli, S.H.; Caetano, B.L. [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Araraquara, SP (Brazil); Briois, V.B [Synchrotron SOLEIL, Saint-Aubin (France)
2016-07-01
Full text: Herein we discuss in depth the mechanisms of growth control of ZnO quantum dots (Q-dot) prepared from the zinc oxy-acetate ethanolic solution by the addition of LiOH. Through in situ monitoring of Q-dot radii and of aggregation index calculated from UV-Vis absorption spectra and small-angle X-ray scattering (SAXS) the aggregation and growth of ZnO nanocrystal was well described from two kinetic models: during the first step (t< 50 min) the structural evolution is controlled by the coalescence caused by the oriented attachment between the nanocrystal aggregates while at the advanced time (t> 50 min) the Q-dot coarsening follows the Ostwald ripening (OR) mechanism. From the higher oriented attachment efficiency observed here as compared with early reported synthesis using NaOH and KOH, we propose an universal mechanism to control coalescence and coarsening of ZnO nanocrystal provided from the shield caused by the adsorption of the alkali cation. From X-ray diffraction and transmission electron microscopy results we demonstrate that this mechanism is also useful to prepare Q-dot powders with controlled size. (author)
Kwac, Kijeong; Lee, Chewook; Jung, Yousung; Han, Jaebeom; Kwak, Kyungwon; Zheng, Junrong; Fayer, M D; Cho, Minhaeng
2006-12-28
Molecular dynamics (MD) simulations and quantum mechanical electronic structure calculations are used to investigate the nature and dynamics of the phenol-benzene complex in the mixed solvent, benzene/CCl4. Under thermal equilibrium conditions, the complexes are continuously dissociating and forming. The MD simulations are used to calculate the experimental observables related to the phenol hydroxyl stretching mode, i.e., the two dimensional infrared vibrational echo spectrum as a function of time, which directly displays the formation and dissociation of the complex through the growth of off-diagonal peaks, and the linear absorption spectrum, which displays two hydroxyl stretch peaks, one for the complex and one for the free phenol. The results of the simulations are compared to previously reported experimental data and are found to be in quite reasonable agreement. The electronic structure calculations show that the complex is T shaped. The classical potential used for the phenol-benzene interaction in the MD simulations is in good accord with the highest level of the electronic structure calculations. A variety of other features is extracted from the simulations including the relationship between the structure and the projection of the electric field on the hydroxyl group. The fluctuating electric field is used to determine the hydroxyl stretch frequency-frequency correlation function (FFCF). The simulations are also used to examine the number distribution of benzene and CCl4 molecules in the first solvent shell around the phenol. It is found that the distribution is not that of the solvent mole fraction of benzene. There are substantial probabilities of finding a phenol in either a pure benzene environment or a pure CCl4 environment. A conjecture is made that relates the FFCF to the local number of benzene molecules in phenol's first solvent shell.
Chan, Bun; Kawashima, Yukio; Katouda, Michio; Nakajima, Takahito; Hirao, Kimihiko
2016-02-03
We have carried out large-scale computational quantum chemistry calculations on the K computer to obtain heats of formation for C60 and some higher fullerenes with the DSD-PBE-PBE/cc-pVQZ double-hybrid density functional theory method. Our best estimated values are 2520.0 ± 20.7 (C60), 2683.4 ± 17.7 (C70), 2862.0 ± 18.5 (C76), 2878.8 ± 13.3 (C78), 2946.4 ± 14.5 (C84), 3067.3 ± 15.4 (C90), 3156.6 ± 16.2 (C96), 3967.7 ± 33.4 (C180), 4364 (C240) and 5415 (C320) kJ mol(-1). In our assessment, we also find that the B3-PW91-D3BJ and BMK-D3(BJ) functionals perform reasonably well. Using the convergence behavior for the calculated per-atom heats of formation, we obtained the formula ΔfH per carbon = 722n(-0.72) + 5.2 kJ mol(-1) (n = the number of carbon atoms), which enables an estimation of ΔfH for higher fullerenes more generally. A slow convergence to the graphene limit is observed, which we attribute to the relatively small proportion of fullerene carbons that are in "low-strain" regions. We further propose that it would take tens, if not hundreds, of thousands of carbons for a fullerene to roughly approach the limit. Such a distinction may be a contributing factor to the discrete properties between the two types of nanomaterials. During the course of our study, we also observe a fairly reliable means for the theoretical calculation of heats of formation for medium-sized fullerenes. This involves the use of isodesmic-type reactions with fullerenes of similar sizes to provide a good balance of the chemistry and to minimize the use of accompanying species.
Information carriers and (reading them through) information theory in quantum chemistry.
Geerlings, Paul; Borgoo, Alex
2011-01-21
This Perspective discusses the reduction of the electronic wave function via the second-order reduced density matrix to the electron density ρ(r), which is the key ingredient in density functional theory (DFT) as a basic carrier of information. Simplifying further, the 1-normalized density function turns out to contain essentially the same information as ρ(r) and is even of preferred use as an information carrier when discussing the periodic properties along Mendeleev's table where essentially the valence electrons are at stake. The Kullback-Leibler information deficiency turns out to be the most interesting choice to obtain information on the differences in ρ(r) or σ(r) between two systems. To put it otherwise: when looking for the construction of a functional F(AB) = F[ζ(A)(r),ζ(B)(r)] for extracting differences in information from an information carrier ζ(r) (i.e. ρ(r), σ(r)) for two systems A and B the Kullback-Leibler information measure ΔS is a particularly adequate choice. Examples are given, varying from atoms, to molecules and molecular interactions. Quantum similarity of atoms indicates that the shape function based KL information deficiency is the most appropriate tool to retrieve periodicity in the Periodic Table. The dissimilarity of enantiomers for which different information measures are presented at global and local (i.e. molecular and atomic) level leads to an extension of Mezey's holographic density theorem and shows numerical evidence that in a chiral molecule the whole molecule is pervaded by chirality. Finally Kullback-Leibler information profiles are discussed for intra- and intermolecular proton transfer reactions and a simple S(N)2 reaction indicating that the theoretical information profile can be used as a companion to the energy based Hammond postulate to discuss the early or late transition state character of a reaction. All in all this Perspective's answer is positive to the question of whether an even simpler carrier of
What can quantum chemistry tell us about Pa(V) hydration and hydrolysis?
Energy Technology Data Exchange (ETDEWEB)
Siboulet, B. [CEA Marcoule, Lab. de Conception des Architectures Moleculaires (DRCP/SCPS), 30 (France); Marsden, C.J. [Universite P. Sabatier, Lab. de Physique Quantique, CNRS-UMR 5626, 31 - Toulouse (France); Vitorge, P. [CEA Saclay, Lab. de Speciation des Radionucleides et Molecules (UMR 8587DPC/SECR), 91 - Gif-sur-Yvette (France)
2008-12-15
Published liquid-liquid extraction studies of Pa(V) were interpreted with aqueous mono-, di- and tri cations. B3LYP DFT is applied here to such cations surrounded by two explicit hydration layers: Linear or tetrahedral geometries are found for the Pa(V) aquo ions. PaO{sub 2}{sup +} is similar to the other AnO{sub 2}{sup +} cations, but has strong apical bonds, resulting from the highly negative O{sub yl} charge, which decreases along the An(V) series. This explains the instability of PaO{sub 2}{sup +} in water, and the differences with the heavier An(V). PaO{sub 2}{sup +} di-protonates to give Pa(OH){sub 2}{sup 3+} and can further di-hydrolyze to give T{sub d}-Pa(OH){sub 4}{sup +}, which might very well be the most stable Pa(V) mono cation. PaOOH{sup 2+} is confirmed to be the Pa(V) aqueous di cation invoked in the literature for pH{<=} 1.4 {+-} 0.7. PaO{sup 3+} is confirmed in sulfate solution, with a bond length close to 180 pm. Pa(OH){sub 2}{sup 3+} cannot be excluded in other conditions. The strong influence of the solvent was not fully taken into account in most previous theoretical studies that focused only on bare or partially solvated PaO{sub 2}{sup +}. Toraishi et al. have studied hydrated Pa(V) and our work confirms this study and its qualitative interpretation. The new tetrahedral Pa(OH){sub 4}{sup +} geometry that is shown here to be important opens the field to further quantum chemical studies of Pa(V) and other f-elements. As a test for the two-shell model approach for Pa(V), fluoride coordination to Pa(V) is studied and compared with published EXAFS data: an excellent fit is obtained with the well-established species PaF{sub 7}{sup 2-}, but most other stoichiometries tested are precluded. (authors)
Al-Khalili, Jim
2003-01-01
In this lively look at quantum science, a physicist takes you on an entertaining and enlightening journey through the basics of subatomic physics. Along the way, he examines the paradox of quantum mechanics--beautifully mathematical in theory but confoundingly unpredictable in the real world. Marvel at the Dual Slit experiment as a tiny atom passes through two separate openings at the same time. Ponder the peculiar communication of quantum particles, which can remain in touch no matter how far apart. Join the genius jewel thief as he carries out a quantum measurement on a diamond without ever touching the object in question. Baffle yourself with the bizzareness of quantum tunneling, the equivalent of traveling partway up a hill, only to disappear then reappear traveling down the opposite side. With its clean, colorful layout and conversational tone, this text will hook you into the conundrum that is quantum mechanics.
Lao, Ka Un; Herbert, John M
2015-01-15
We present an overview of "XSAPT", a family of quantum chemistry methods for noncovalent interactions. These methods combine an efficient, iterative, monomer-based approach to computing many-body polarization interactions with a two-body version of symmetry-adapted perturbation theory (SAPT). The result is an efficient method for computing accurate intermolecular interaction energies in large noncovalent assemblies such as molecular and ionic clusters, molecular crystals, clathrates, or protein-ligand complexes. As in traditional SAPT, the XSAPT energy is decomposable into physically meaningful components. Dispersion interactions are problematic in traditional low-order SAPT, and two new approaches are introduced here in an attempt to improve this situation: (1) third-generation empirical atom-atom dispersion potentials, and (2) an empirically scaled version of second-order SAPT dispersion. Comparison to high-level ab initio benchmarks for dimers, water clusters, halide-water clusters, a methane clathrate hydrate, and a DNA intercalation complex illustrate both the accuracy of XSAPT-based methods as well as their limitations. The computational cost of XSAPT scales as O(N(3))-O(N(5)) with respect to monomer size, N, depending upon the particular version that is employed, but the accuracy is typically superior to alternative ab initio methods with similar scaling. Moreover, the monomer-based nature of XSAPT calculations makes them trivially parallelizable, such that wall times scale linearly with respect to the number of monomer units. XSAPT-based methods thus open the door to both qualitative and quantitative studies of noncovalent interactions in clusters, biomolecules, and condensed-phase systems.
Dudev, Todor; Devereux, Mike; Meuwly, Markus; Lim, Carmay; Piquemal, Jean-Philip; Gresh, Nohad
2015-02-15
The alkali metal cations in the series Li(+)-Cs(+) act as major partners in a diversity of biological processes and in bioinorganic chemistry. In this article, we present the results of their calibration in the context of the SIBFA polarizable molecular mechanics/dynamics procedure. It relies on quantum-chemistry (QC) energy-decomposition analyses of their monoligated complexes with representative O-, N-, S-, and Se- ligands, performed with the aug-cc-pVTZ(-f) basis set at the Hartree-Fock level. Close agreement with QC is obtained for each individual contribution, even though the calibration involves only a limited set of cation-specific parameters. This agreement is preserved in tests on polyligated complexes with four and six O- ligands, water and formamide, indicating the transferability of the procedure. Preliminary extensions to density functional theory calculations are reported.
Energy Technology Data Exchange (ETDEWEB)
Brown, N.J. [Lawrence Berkeley Laboratory, CA (United States)
1993-12-01
This research is concerned with the development and use of sensitivity analysis tools to probe the response of dependent variables to model input variables. Sensitivity analysis is important at all levels of combustion modeling. This group`s research continues to be focused on elucidating the interrelationship between features in the underlying potential energy surface (obtained from ab initio quantum chemistry calculations) and their responses in the quantum dynamics, e.g., reactive transition probabilities, cross sections, and thermal rate coefficients. The goals of this research are: (i) to provide feedback information to quantum chemists in their potential surface refinement efforts, and (ii) to gain a better understanding of how various regions in the potential influence the dynamics. These investigations are carried out with the methodology of quantum functional sensitivity analysis (QFSA).
Chernev, Petko; Zaharieva, Ivelina; Rossini, Emanuele; Galstyan, Artur; Dau, Holger; Knapp, Ernst-Walter
2016-10-12
Structural data of the oxygen-evolving complex (OEC) in photosystem II (PSII) determined by X-ray crystallography, quantum chemistry (QC), and extended X-ray absorption fine structure (EXAFS) analyses are presently inconsistent. Therefore, a detailed study of what information can be gained about the OEC through a comparison of QC and crystallographic structure information combined with the information from range-extended EXAFS spectra was undertaken. An analysis for determining the precision of the atomic coordinates of the OEC by QC is carried out. OEC model structures based on crystallographic data that are obtained by QC from different research groups are compared with one another and with structures obtained by high-resolution crystallography. The theory of EXAFS spectra is summarized, and the application of EXAFS spectra to the experimental determination of the structure of the OEC is detailed. We discriminate three types of parameters entering the formula for the EXAFS spectrum: (1) model-independent, predefined, and fixed; (2) model-dependent that can be computed or adjusted; and (3) model-dependent that must be adjusted. The information content of EXAFS spectra is estimated and is related to the precision of atomic coordinates and resolution power to discriminate different atom-pair distances of the OEC. It is demonstrated how a precise adjustment of atomic coordinates can yield a nearly perfect representation of the experimental OEC EXAFS spectrum, but at the expense of overfitting and losing the knowledge of the initial OEC model structure. Introducing a novel type of penalty function, it is shown that moderate adjustment of atomic coordinates to the EXAFS spectrum limited by constraints avoids overfitting and can be used to validate different OEC model structures. This technique is used to identify the OEC model structures whose computed OEC EXAFS spectra agree best with the measured spectrum. In this way, the most likely S-state and protonation pattern
Alexandre, Maxime T.A.; Domratcheva, Tatiana; Bonetti, Cosimo; van Wilderen, Luuk J.G.W.; van Grondelle, Rienk; Groot, Marie-Louise; Hellingwerf, Klaas J.; Kennis, John T.M.
2009-01-01
Abstract Phototropins, major blue-light receptors in plants, are sensitive to blue light through a pair of flavin mononucleotide (FMN)-binding light oxygen and voltage (LOV) domains, LOV1 and LOV2. LOV2 undergoes a photocycle involving light-driven covalent adduct formation between a conserved cysteine and the FMN C(4a) atom. Here, the primary reactions of Avena sativa phototropin 1 LOV2 (AsLOV2) were studied using ultrafast mid-infrared spectroscopy and quantum chemistry. The singlet excited state (S1) evolves into the triplet state (T1) with a lifetime of 1.5 ns at a yield of ∼50%. The infrared signature of S1 is characterized by absorption bands at 1657 cm−1, 1495–1415 cm−1, and 1375 cm−1. The T1 state shows infrared bands at 1657 cm−1, 1645 cm−1, 1491–1438 cm−1, and 1390 cm−1. For both electronic states, these bands are assigned principally to C=O, C=N, C-C, and C-N stretch modes. The overall downshifting of C=O and C=N bond stretch modes is consistent with an overall bond-order decrease of the conjugated isoalloxazine system upon a π-π∗ transition. The configuration interaction singles (CIS) method was used to calculate the vibrational spectra of the S1 and T1 excited ππ∗ states, as well as respective electronic energies, structural parameters, electronic dipole moments, and intrinsic force constants. The harmonic frequencies of S1 and T1, as calculated by the CIS method, are in satisfactory agreement with the evident band positions and intensities. On the other hand, CIS calculations of a T1 cation that was protonated at the N(5) site did not reproduce the experimental FMN T1 spectrum. We conclude that the FMN T1 state remains nonprotonated on a nanosecond timescale, which rules out an ionic mechanism for covalent adduct formation involving cysteine-N(5) proton transfer on this timescale. Finally, we observed a heterogeneous population of singly and doubly H-bonded FMN C(4)=O conformers in the dark state, with stretch frequencies
Uyusur, Burcu; Darnault, Christophe J. G.; Snee, Preston T.; Kokën, Emre; Jacobson, Astrid R.; Wells, Robert R.
2010-11-01
To investigate the coupled effects of solution chemistry and hydrodynamics on the mobility of quantum dot (QD) nanoparticles in the vadose zone, laboratory scale transport experiments involving single and/or sequential infiltrations of QDs in unsaturated and saturated porous media, and computations of total interaction and capillary potential energies were performed. As ionic strength increased, QD retention in the unsaturated porous media increased; however, this retention was significantly suppressed in the presence of a non-ionic surfactant in the infiltration suspensions as indicated by surfactant enhanced transport of QDs. In the vadose zone, the non-ionic surfactant limited the formation of QD aggregates, enhanced QD mobility and transport, and lowered the solution surface tension, which resulted in a decrease in capillary forces that not only led to a reduction in the removal of QDs, but also impacted the vadose zone flow processes. When chemical transport conditions were favorable (ionic strength of 5 × 10 -4 M and 5 × 10 -3 M, or ionic strengths of 5 × 10 -2 M and 0.5 M with surfactant), the dominating phenomena controlling the mobility and transport of QDs in the vadose zone were meso-scale processes, where infiltration by preferential flow results in the rapid transport of QDs. When chemical transport conditions were unfavorable (ionic strength of 5 × 10 -2 M and 0.5 M) the dominating phenomena controlling the mobility and transport of QDs in the vadose zone were pore-scale processes governed by gas-water interfaces (GWI) that impact the mobility of QDs. The addition of surfactant enhanced the transport of QDs both in favorable and unfavorable chemical transport conditions. The mobility and retention of QDs was controlled by interaction and capillary forces, with the latter being the most influential. GWI were found to be the dominant mechanism and site for QD removal compared with solid-water interfaces (SWI) and pore straining. Additionally
Mathematics for quantum chemistry
Anderson, Jay Martin
2005-01-01
This concise volume offers undergraduates an introduction to mathematical formalism in problems of molecular structure and motion. The main topics cover the calculus of orthogonal functions, algebra of vector spaces, and Lagrangian and Hamiltonian formulation of classical mechanics and applications to molecular motion. Answers to problems. 1966 edition.
Morrison, Adrian F; Herbert, John M
2015-11-05
We introduce a charge-embedding scheme for an excited-state quantum chemistry method aimed at weakly interacting molecular aggregates. The Hamiltonian matrix for the aggregate is constructed in a basis of direct products of configuration-state functions for the monomers, and diagonalization of this matrix affords excitation energies within ∼0.2 eV of the corresponding supersystem calculation. Both the basis states and the coupling matrix elements can be computed in a distributed way, resulting in an algorithm whose time-to-solution is independent of the number of chromophores, and we report calculations on systems with almost 55 000 basis functions using fewer than 450 processors. In a semiconducting organic nanotube, we find evidence of ultrafast, coherent dynamics followed by energy localization driven by static disorder. Truncation of the model system has a qualitative effect on the energy-transfer dynamics, demonstrating the importance of simulating an extended portion of the nanotube, which is not feasible using traditional quantum chemistry.
Bylaska, Eric J; Weare, Jonathan Q; Weare, John H
2013-08-21
distributed computing environment using very slow transmission control protocol/Internet protocol networks. Scripts written in Python that make calls to a precompiled quantum chemistry package (NWChem) are demonstrated to provide an actual speedup of 8.2 for a 2.5 ps AIMD simulation of HCl + 4H2O at the MP2/6-31G* level. Implemented in this way these algorithms can be used for long time high-level AIMD simulations at a modest cost using machines connected by very slow networks such as WiFi, or in different time zones connected by the Internet. The algorithms can also be used with programs that are already parallel. Using these algorithms, we are able to reduce the cost of a MP2/6-311++G(2d,2p) simulation that had reached its maximum possible speedup in the parallelization of the electronic structure calculation from 32 s/time step to 6.9 s/time step.
Bylaska, Eric J.; Weare, Jonathan Q.; Weare, John H.
2013-08-01
environment using very slow transmission control protocol/Internet protocol networks. Scripts written in Python that make calls to a precompiled quantum chemistry package (NWChem) are demonstrated to provide an actual speedup of 8.2 for a 2.5 ps AIMD simulation of HCl + 4H2O at the MP2/6-31G* level. Implemented in this way these algorithms can be used for long time high-level AIMD simulations at a modest cost using machines connected by very slow networks such as WiFi, or in different time zones connected by the Internet. The algorithms can also be used with programs that are already parallel. Using these algorithms, we are able to reduce the cost of a MP2/6-311++G(2d,2p) simulation that had reached its maximum possible speedup in the parallelization of the electronic structure calculation from 32 s/time step to 6.9 s/time step.
Energy Technology Data Exchange (ETDEWEB)
Bylaska, Eric J., E-mail: Eric.Bylaska@pnnl.gov [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352 (United States); Weare, Jonathan Q., E-mail: weare@uchicago.edu [Department of Mathematics, University of Chicago, Chicago, Illinois 60637 (United States); Weare, John H., E-mail: jweare@ucsd.edu [Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093 (United States)
2013-08-21
to 14.3. The parallel in time algorithms can be implemented in a distributed computing environment using very slow transmission control protocol/Internet protocol networks. Scripts written in Python that make calls to a precompiled quantum chemistry package (NWChem) are demonstrated to provide an actual speedup of 8.2 for a 2.5 ps AIMD simulation of HCl + 4H{sub 2}O at the MP2/6-31G* level. Implemented in this way these algorithms can be used for long time high-level AIMD simulations at a modest cost using machines connected by very slow networks such as WiFi, or in different time zones connected by the Internet. The algorithms can also be used with programs that are already parallel. Using these algorithms, we are able to reduce the cost of a MP2/6-311++G(2d,2p) simulation that had reached its maximum possible speedup in the parallelization of the electronic structure calculation from 32 s/time step to 6.9 s/time step.
Cheng, Xiaoyu; Hinde, Elizabeth; Owen, Dylan M; Lowe, Stuart B; Reece, Peter J; Gaus, Katharina; Gooding, J Justin
2015-10-28
Fluorescence lifetime imaging microscopy is successfully demonstrated in both one- and two-photon cases with surface modified, nanocrystalline silicon quantum dots in the context of bioimaging. The technique is further demonstrated in combination with Förster resonance energy transfer studies where the color of the nanoparticles is tuned by using organic dye acceptors directly conjugated onto the nanoparticle surface.
Sahu, Bibhuti Bhusan; Yin, Yongyi; Han, Jeon Geon; Shiratani, Masaharu
2016-06-21
The advanced materials process by non-thermal plasmas with a high plasma density allows the synthesis of small-to-big sized Si quantum dots by combining low-temperature deposition with superior crystalline quality in the background of an amorphous hydrogenated silicon nitride matrix. Here, we make quantum dot thin films in a reactive mixture of ammonia/silane/hydrogen utilizing dual-frequency capacitively coupled plasmas with high atomic hydrogen and nitrogen radical densities. Systematic data analysis using different film and plasma characterization tools reveals that the quantum dots with different sizes exhibit size dependent film properties, which are sensitively dependent on plasma characteristics. These films exhibit intense photoluminescence in the visible range with violet to orange colors and with narrow to broad widths (∼0.3-0.9 eV). The observed luminescence behavior can come from the quantum confinement effect, quasi-direct band-to-band recombination, and variation of atomic hydrogen and nitrogen radicals in the film growth network. The high luminescence yields in the visible range of the spectrum and size-tunable low-temperature synthesis with plasma and radical control make these quantum dot films good candidates for light emitting applications.
Algar, W Russ; Krull, Ulrich J
2011-01-01
The use of quantum dots (QDs) as donors in fluorescence resonance energy transfer (FRET) offer several advantages for the development of multiplexed solid-phase QD-FRET nucleic acid hybridization assays. Designs for multiplexing have been demonstrated, but important challenges remain in the optimization of these systems. In this work, we identify several strategies based on the design of interfacial chemistry for improving sensitivity, obtaining lower limits of detection (LOD) and enabling the regeneration and reuse of solid-phase QD-FRET hybridization assays. FRET-sensitized emission from acceptor dyes associated with hybridization events at immobilized QD donors provides the analytical signal in these assays. The minimization of active sensing area reduces background from QD donor PL and allows the resolution of smaller amounts of acceptor emission, thus lowering the LOD. The association of multiple acceptor dyes with each hybridization event can enhance FRET efficiency, thereby improving sensitivity. Many previous studies have used interfacial protein layers to generate selectivity; however, transient destabilization of these layers is shown to prevent efficient regeneration. To this end, we report a protein-free interfacial chemistry and demonstrate the specific detection of as little as 2 pmol of target, as well as an improved capacity for regeneration.
Shimada, Toru; Hasegawa, Takeshi
2017-10-05
The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pKa'. The determination of pKa' is performed for various ionic strengths, which reveals the thermodynamic acid constant (pKa=7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of -1 and the blue form that of -2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed. Copyright © 2017 Elsevier B.V. All rights reserved.
Khan, Salman A
2017-02-08
2-amino-4-(4-bromophenyl)-8-methoxy-5,6-dihydrobenzo[h]quinoline-3-carbonitrile (ABDC) was synthesized by the reaction of (2E)-2-(4 bromobenzylidene) - 6 -methoxy-3,4-dihydronaphthalen-1(2H)-one (Chalcone) with malononitrile and ammonium acetate under microwave irradiation. Chalcone was synthesised by the reaction 4-bromobenzaldehyd, 6-methoxy-1,2,3,4-tetrahydro-naphthalin-1-one under the same condition. Structure of ABDC was conformed by (1)H and (13)C NMR, FT-IR, EI-MS spectral studies and elemental analysis. The electronic absorption and fluorescence spectra of ABDC have been studied in solvents of different polarities, and the data were used to study the solvatochromic properties such as excitation coefficient, stokes shift, oscillator strength, transition dipole moment and fluorescence quantum yield. The absorption maximum and fluorescence emission maximum was observed red shift when increase solvent polarity n-Hexane to DMSO. ABDC undergoes solubilization in different micelles and may be used as a probe and quencher to determine the critical micelle concentration (CMC) of CTAB and SDS. The anti-bacterial activity of chalcone and its cyclized product ABDC was tested in vitro by the disk diffusion assay against two Gram-positive and two Gram-negative bacteria was determined with the reference of standard drug Tetracycline. Results showed that the ABDC is better anti-bacterial agent as compared to chalcone. The anti-bacterial activity was further supported by the quantum chemistry calculation.
Shimada, Toru; Hasegawa, Takeshi
2017-10-01
The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pKa‧. The determination of pKa‧ is performed for various ionic strengths, which reveals the thermodynamic acid constant (pKa = 7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of - 1 and the blue form that of - 2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed.
Orsini, Gabriele
2015-01-01
The ever-increasing impact of molecular quantum calculations over chemical sciences implies a strong and urgent need for the elaboration of proper teaching strategies in university curricula. In such perspective, this paper proposes an extensive project for a student-driven, cooperative, from-scratch implementation of a general Hartree-Fock…
R. Tonner; P. Schwerdtfeger; A. L. May; J.D. Steill; G. Berden; J. Oomens; S. R. Campagna; R.N. Compton
2012-01-01
In an effort to understand the chemical factors that stabilize dianions, experimental and theoretical studies on the stability of the tartrate dianion were performed. Quantum chemical calculations at the coupled cluster level reveal only a metastable state with a possible decomposition pathway (O2C-
Tonner, R.; Schwerdtfeger, P.; May, A. L.; Steill, J. D.; G. Berden,; Oomens, J.; Campagna, S. R.; Compton, R. N.
2012-01-01
In an effort to understand the chemical factors that stabilize dianions, experimental and theoretical studies on the stability of the tartrate dianion were performed. Quantum chemical calculations at the coupled cluster level reveal only a metastable state with a possible decomposition pathway (O2C-
Tonner, R.; Schwerdtfeger, P.; May, A. L.; Steill, J. D.; G. Berden,; Oomens, J.; Campagna, S. R.; Compton, R. N.
2012-01-01
In an effort to understand the chemical factors that stabilize dianions, experimental and theoretical studies on the stability of the tartrate dianion were performed. Quantum chemical calculations at the coupled cluster level reveal only a metastable state with a possible decomposition pathway
Tonner, R.; Schwerdtfeger, P.; May, A. L.; Steill, J.D.; Berden, G.; Oomens, J.; Campagna, S. R.; Compton, R.N.
2012-01-01
In an effort to understand the chemical factors that stabilize dianions, experimental and theoretical studies on the stability of the tartrate dianion were performed. Quantum chemical calculations at the coupled cluster level reveal only a metastable state with a possible decomposition pathway
Bishop, David M
1993-01-01
Group theoretical principles are an integral part of modern chemistry. Not only do they help account for a wide variety of chemical phenomena, they simplify quantum chemical calculations. Indeed, knowledge of their application to chemical problems is essential for students of chemistry. This complete, self-contained study, written for advanced undergraduate-level and graduate-level chemistry students, clearly and concisely introduces the subject of group theory and demonstrates its application to chemical problems.To assist chemistry students with the mathematics involved, Professor Bishop ha
Boeyens, Jan C A
2016-01-01
This volume, written by a highly cited author, presents the history of quantum theory together with open questions and remaining problems in terms of the plausibility of quantum chemistry and physics. It also provides insights into the theory of matter-wave mechanics. The content is aimed at students and lecturers in chemistry, physics and the philosophy of science.
Energy Technology Data Exchange (ETDEWEB)
Vallet, V. [Munich Univ., Institute for Theoretical Chemistry, Technical (Germany)
2003-01-01
Molecular and nano-molecular systems containing rare earth and actinides elements have extraordinary chemical and physical properties. Computer simulations using quantum chemistry methods can play an important role in many investigative procedures and provide help in understanding the microscopic nature of the interactions governing these macroscopic properties. The recent theoretical efforts have been devoted to the development of accurate and efficient methods that take into account all important interactions influencing the electronic structures, such as electron correlation and relativity. In particular, we illustrate the importance of relativity on chemical and spectroscopic properties. We will then focus on the modelling aspects of solution chemistry. (author)
Lan, Tran Nguyen; Zgid, Dominika
2016-01-01
We present a detailed discussion of self-energy embedding theory (SEET) which is a quantum embedding scheme allowing us to describe a chosen subsystem very accurately while keeping the description of the environment at a lower cost. We apply SEET to molecular examples where commonly our chosen subsystem is made out of a set of strongly correlated orbitals while the weakly correlated orbitals constitute an environment. Such a self-energy separation is very general and to make this procedure applicable to multiple systems a detailed and practical procedure for the evaluation of the system and environment self-energy is necessary. We list all the intricacies for one of the possible procedures while focusing our discussion on many practical implementation aspects such as the choice of best orbital basis, impurity solver, and many steps necessary to reach chemical accuracy. Finally, on a set of carefully chosen molecular examples, we demonstrate that SEET which is a controlled, systematically improvable Green's fu...
Directory of Open Access Journals (Sweden)
Ricardo Vessecchi
2008-01-01
Full Text Available The field of application of mass spectrometry (MS has increased considerably due to the development of ionization techniques. Other factors that have stimulated the use of MS are the tandem mass spectrometry (MS/MS and sequential mass spectrometry (MSn techniques. However, the interpretation of the MS/MS and MSn data may lead to speculative conclusions. Thus, various quantum chemical methods have been applied for obtaining high quality thermochemical data in gas phase. In this review, we show some applications of computational quantum chemistry to understand the formation and fragmentation of gaseous ions of organic compounds in a MS analysis.
Vogt, Leslie; Olivares-Amaya, Roberto; Kermes, Sean; Shao, Yihan; Amador-Bedolla, Carlos; Aspuru-Guzik, Alan
2008-03-13
The modification of a general purpose code for quantum mechanical calculations of molecular properties (Q-Chem) to use a graphical processing unit (GPU) is reported. A 4.3x speedup of the resolution-of-the-identity second-order Møller-Plesset perturbation theory (RI-MP2) execution time is observed in single point energy calculations of linear alkanes. The code modification is accomplished using the compute unified basic linear algebra subprograms (CUBLAS) library for an NVIDIA Quadro FX 5600 graphics card. Furthermore, speedups of other matrix algebra based electronic structure calculations are anticipated as a result of using a similar approach.
Ficek, Zbigniew
2016-01-01
The textbook introduces students to the main ideas of quantum physics and the basic mathematical methods and techniques used in the fields of advanced quantum physics, atomic physics, laser physics, nanotechnology, quantum chemistry, and theoretical mathematics. The textbook explains how microscopic objects (particles) behave in unusual ways, giving rise to what's called quantum effects. It contains a wide range of tutorial problems from simple confidence-builders to fairly challenging exercises that provide adequate understanding of the basic concepts of quantum physics.
Durrant, Marcus C
2007-01-01
The process of gene-based molecular evolution has been simulated in silico by using massively parallel density functional theory quantum calculations, coupled with a genetic algorithm, to test for fitness with respect to a target chemical reaction in populations of genetically encoded molecules. The goal of this study was the identification of transition-metal complexes capable of mediating a known reaction, namely the cleavage of N(2) to give the metal nitride. Each complex within the search space was uniquely specified by a nanogene consisting of an eight-digit number. Propagation of an individual nanogene into successive generations was determined by the fitness of its phenotypic molecule to perform the target reaction and new generations were created by recombination and mutation of surviving nanogenes. In its simplest implementation, the quantum-directed genetic algorithm (QDGA) quickly located a local minimum on the evolutionary fitness hypersurface, but proved incapable of progressing towards the global minimum. A strategy for progressing beyond local minima consistent with the Darwinian paradigm by the use of environmental variations coupled with mass extinctions was therefore developed. This allowed for the identification of nitriding complexes that are very closely related to known examples from the chemical literature. Examples of mutations that appear to be beneficial at the genetic level but prove to be harmful at the phenotypic level are described. As well as revealing fundamental aspects of molecular evolution, QDGA appears to be a powerful tool for the identification of lead compounds capable of carrying out a target chemical reaction.
Loew, G. H.; Berkowitz, D.; Chang, S.
1975-01-01
Using the Iterative Extended Huckel Theory (IEHT) calculations of the electron distribution and orbital energies of a series of thirteen amines, nitriles and amino-nitriles relevant to prebiotic and cosmo-chemistry have been carried out. Ground state properties such as the energy and nature of the highest occupied (HOMO) and lowest empty (LEMO) molecular orbitals, net atomic charges and number of nonbonding electrons have been identified as criteria for correlating the relative nucleophilicity of amine and nitrile nitrogens and the electrophilicity of nitrile and other unsaturated carbon atoms. The results of such correlations can be partially verified by known chemical behavior of these compounds and are used to predict and understand their role in prebiotic organic synthesis.
Loew, G. H.; Berkowitz, D.; Chang, S.
1975-01-01
Using the Iterative Extended Huckel Theory (IEHT) calculations of the electron distribution and orbital energies of a series of thirteen amines, nitriles and amino-nitriles relevant to prebiotic and cosmo-chemistry have been carried out. Ground state properties such as the energy and nature of the highest occupied (HOMO) and lowest empty (LEMO) molecular orbitals, net atomic charges and number of nonbonding electrons have been identified as criteria for correlating the relative nucleophilicity of amine and nitrile nitrogens and the electrophilicity of nitrile and other unsaturated carbon atoms. The results of such correlations can be partially verified by known chemical behavior of these compounds and are used to predict and understand their role in prebiotic organic synthesis.
Lemke, K.; Sadjadi, S.; Seward, T.
2010-12-01
The structures and energetic properties of ionic alkali metal halide clusters play a significant role in our understanding of aqueous geochemical processes such as salt dissolution, precipitation and neutralization reactions. Mass spectrometric and quantum chemical studies of such systems offer new opportunities to study the size-dependent evolution of cluster structures, the occurrence of magic number species as well as their fundamental properties. The work here presents new results for the stability, abundance and structure of pure [Na(NaClm)]+ , [K(KCl)m]+ and mixed [Na(NaCl)p(KCl)q]+ metal halide clusters with mQB3 and G4 methods and comment on the onset of the doubly charged cluster series. FT-ICR mass spectra for [Na(NaCl)n]+ clusters generated from 1mM NaCl in 20%H2O 80% acetonitrile in positive ion mode.
Alrawashdeh, Lubna R; Cronin, Michael P; Woodward, Clifford E; Day, Anthony I; Wallace, Lynne
2016-07-01
The weaker emission typically seen for iridium(III) cyclometalated complexes in aqueous medium can be reversed via encapsulation in cucurbit[10]uril (Q[10]). The Q[10] cavity is shown to effectively maximize quantum yields for the complexes, compared to any other medium. This may provide significant advantages for a number of sensor applications. NMR studies show that the complexes are accommodated similarly within the host molecule, even with cationic substituents attached to the ppy ligands, indicating that the hydrophobic effect is the dominant driving force for binding. Cavity-encapsulated 1:1 host-guest species dominate the emission, but 1:2 species are also indicated, which also give some enhancement of intensity. Results demonstrate that the enhancement is due primarily to much lower rates of nonradiative decay but also suggest that the encapsulation can cause a change in character of the emitting state.
Energy Technology Data Exchange (ETDEWEB)
Giansante, Carlo, E-mail: carlo.giansante@iit.it [Center for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia, Via Barsanti 1, 73010 Arnesano, LE (Italy); NNL-CNR Istituto di Nanoscienze, Via per Arnesano, 73100 Lecce (Italy); Carbone, Luigi [IPCF-CNR UOS di Pisa, Via G. Moruzzi 1, 56124 Pisa (Italy); Giannini, Cinzia; Altamura, Davide [IC-CNR Istituto di Cristallografia, Via Amendola 122/O, 70126 Bari (Italy); Ameer, Zoobia [Dipartimento di Matematica e Fisica ‘E. De Giorgi’, Università del Salento, Via per Arnesano, 73100 Lecce (Italy); Maruccio, Giuseppe [Center for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia, Via Barsanti 1, 73010 Arnesano, LE (Italy); NNL-CNR Istituto di Nanoscienze, Via per Arnesano, 73100 Lecce (Italy); Dipartimento di Matematica e Fisica ‘E. De Giorgi’, Università del Salento, Via per Arnesano, 73100 Lecce (Italy); Loiudice, Anna [Center for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia, Via Barsanti 1, 73010 Arnesano, LE (Italy); Belviso, Maria R. [NNL-CNR Istituto di Nanoscienze, Via per Arnesano, 73100 Lecce (Italy); Cozzoli, P. Davide [NNL-CNR Istituto di Nanoscienze, Via per Arnesano, 73100 Lecce (Italy); Dipartimento di Matematica e Fisica ‘E. De Giorgi’, Università del Salento, Via per Arnesano, 73100 Lecce (Italy); Rizzo, Aurora [Center for Biomolecular Nanotechnologies @UNILE, Istituto Italiano di Tecnologia, Via Barsanti 1, 73010 Arnesano, LE (Italy); NNL-CNR Istituto di Nanoscienze, Via per Arnesano, 73100 Lecce (Italy); and others
2014-06-02
Suitable post-synthesis surface modification of lead-chalcogenide quantum dots (QDs) is crucial to enable their integration in photovoltaic devices. We have developed a solution-phase ligand exchange strategy that exploits arenethiolate anions to replace the pristine oleate ligands on PbS QDs, while preserving the long-term colloidal stability of QDs and allowing their solution-based processability into photoconductive thin-films. Complete QD surface modification is demonstrated by IR spectroscopy analysis, whereas UV–Vis–NIR Absorption Spectroscopy provides quantitative evaluation of stoichiometry and thermodynamic stability of the resulting system. Arenethiolate ligands permit to reduce the inter-particle distance in PbS QD solids, leading to a drastic improvement of the photoinduced charge transport properties. Therefore, smooth dense-packed thin-films of arenethiolate-capped PbS QDs obtained via a single solution-processing step are integrated in heterojunction solar cells: such devices generate remarkable photocurrent densities (14 mA cm{sup −2}) and overall efficiencies (1.85%), which are outstanding for a single PbS QD layer. Solution-phase surface modification of QDs thus represents an effective intermediate step towards low-cost processing for all-inorganic and hybrid organic/inorganic QD-based photovoltaics. - Highlights: • We developed a solution-phase ligand exchange strategy on PbS quantum dots (QDs). • We evaluated stoichiometry and thermodynamic stability of the resulting system. • Arenethiolate ligands preserve the long-term colloidal stability of PbS QDs. • Arenethiolate ligands allow QD solution-casting into photoconductive thin-films. • Photovoltaic devices based on a single PbS QD layer show outstanding performances.
KAMINSKI, GEORGE A.; STERN, HARRY A.; BERNE, B. J.; FRIESNER, RICHARD A.; CAO, YIXIANG X.; MURPHY, ROBERT B.; ZHOU, RUHONG; HALGREN, THOMAS A.
2014-01-01
We present results of developing a methodology suitable for producing molecular mechanics force fields with explicit treatment of electrostatic polarization for proteins and other molecular system of biological interest. The technique allows simulation of realistic-size systems. Employing high-level ab initio data as a target for fitting allows us to avoid the problem of the lack of detailed experimental data. Using the fast and reliable quantum mechanical methods supplies robust fitting data for the resulting parameter sets. As a result, gas-phase many-body effects for dipeptides are captured within the average RMSD of 0.22 kcal/mol from their ab initio values, and conformational energies for the di- and tetrapeptides are reproduced within the average RMSD of 0.43 kcal/mol from their quantum mechanical counterparts. The latter is achieved in part because of application of a novel torsional fitting technique recently developed in our group, which has already been used to greatly improve accuracy of the peptide conformational equilibrium prediction with the OPLS-AA force field.1 Finally, we have employed the newly developed first-generation model in computing gas-phase conformations of real proteins, as well as in molecular dynamics studies of the systems. The results show that, although the overall accuracy is no better than what can be achieved with a fixed-charges model, the methodology produces robust results, permits reasonably low computational cost, and avoids other computational problems typical for polarizable force fields. It can be considered as a solid basis for building a more accurate and complete second-generation model. PMID:12395421
Goldwaser, Elodie; de Courcy, Benoit; Demange, Luc; Garbay, Christiane; Raynaud, Françoise; Hadj-Slimane, Reda; Piquemal, Jean-Philip; Gresh, Nohad
2014-11-01
We investigate the conformational properties of a potent inhibitor of neuropilin-1, a protein involved in cancer processes and macular degeneration. This inhibitor consists of four aromatic/conjugated fragments: a benzimidazole, a methylbenzene, a carboxythiourea, and a benzene-linker dioxane, and these fragments are all linked together by conjugated bonds. The calculations use the SIBFA polarizable molecular mechanics procedure. Prior to docking simulations, it is essential to ensure that variations in the ligand conformational energy upon rotations around its six main-chain torsional bonds are correctly represented (as compared to high-level ab initio quantum chemistry, QC). This is done in two successive calibration stages and one validation stage. In the latter, the minima identified following independent stepwise variations of each of the six main-chain torsion angles are used as starting points for energy minimization of all the torsion angles simultaneously. Single-point QC calculations of the minimized structures are then done to compare their relative energies ΔE conf to the SIBFA ones. We compare three different methods of deriving the multipoles and polarizabilities of the central, most critical moiety of the inhibitor: carboxythiourea (CTU). The representation that gives the best agreement with QC is the one that includes the effects of the mutual polarization energy E pol between the amide and thioamide moieties. This again highlights the critical role of this contribution. The implications and perspectives of these findings are discussed.
Lasitha, P; Prasad, Edamana
2016-07-18
Perylene diimide (PDI) derivatives exhibit a high propensity for aggregation, which causes the aggregation-induced quenching of emission from the system. Host-guest chemistry is one of the best-known methods for preventing aggregation through the encapsulation of guest molecules. Herein we report the use of 18-crown-6 (18-C-6) as a host system to disaggregate suitably substituted PDI derivatives in methanol. 18-C-6 formed complexes with amino-substituted PDIs in methanol, which led to disaggregation and enhanced emission from the systems. Furthermore, the embedding of the PDI⋅18-C-6 complexes in poly(vinyl alcohol) (PVA) films generated remarkably high emission quantum yields (60-70 %) from the PDI derivatives. More importantly, the host-guest systems were tested for their ability to conduct electricity in PVA films. The electrical conductivities of the self-assembled systems in PVA were measured by electrochemical impedance spectroscopy (EIS) and the highest conductivity observed was 2.42×10(-5) S cm(-1) .
Tang, Yuan; Han, Songling; Liu, Hongmei; Chen, Xin; Huang, Li; Li, Xiaohui; Zhang, Jianxiang
2013-11-01
To examine the effect of surface chemistry and surface charge on in vivo biodistribution and toxicity of CdSe/ZnS core-shell quantum dots (QDs), QDs with positive, negative, or PEG coating are used in this study for in vivo evaluation in a mouse model. The results suggest that QDs coated with cationic polydiallyldimethylammonium chloride (PDDA) preferentially deposit in the lung other than in the liver, while the negative and PEGylated QDs render abundant accumulation in the liver. At higher doses positive QDs with PDDA coating show severe acute toxicity due to pulmonary embolism. Independent of their surface coatings, all QDs cause injuries in specific tissues like liver, spleen, lung, and kidney, after acute and long-term exposure, and the degree of injuries is dominated by their surface properties. For the positively charged QDs, the acute phase toxicity is primarily contributed by the coating material PDDA, while coating on QDs may amplify both in vitro and in vivo toxicity of PDDA. PEGylated QDs display the slightest chronic injuries in the long-term toxicity examination in comparison to positive or negative ones.
Tetko, Igor V; Varbanov, Hristo P; Galanski, Markus; Talmaciu, Mona; Platts, James A; Ravera, Mauro; Gabano, Elisabetta
2016-03-01
The octanol/water partition coefficient, logP, is one of the most important physico-chemical parameters for the development of new metal-based anticancer drugs with improved pharmacokinetic properties. This study addresses an issue with the absence of publicly available models to predict logP of Pt(IV) complexes. Following data collection and subsequent development of models based on 187 complexes from literature, we validate new and previously published models on a new set of 11 Pt(II) and 35 Pt(IV) complexes, which were kept blind during the model development step. The error of the consensus model, 0.65 for Pt(IV) and 0.37 for Pt(II) complexes, indicates its good accuracy of predictions. The lower accuracy for Pt(IV) complexes was attributed to experimental difficulties with logP measurements for some poorly-soluble compounds. This model was developed using general-purpose descriptors such as extended functional groups, molecular fragments and E-state indices. Surprisingly, models based on quantum-chemistry calculations provided lower prediction accuracy. We also found that all the developed models strongly overestimate logP values for the three complexes measured in the presence of DMSO. Considering that DMSO is frequently used as a solvent to store chemicals, its effect should not be overlooked when logP measurements by means of the shake flask method are performed. The final models are freely available at http://ochem.eu/article/76903.
Li, Chunyan; Li, Feng; Zhang, Yejun; Zhang, Wenjing; Zhang, Xian-En; Wang, Qiangbin
2015-12-22
Protein nanocages (PNCs) have been recognized as a promising platform for nanomedicine innovation. Real-time in vivo tracking of PNCs can provide critically important information for the development of PNC-based diagnostics and therapeutics. Here we demonstrate a general strategy for monitoring the behaviors of PNCs in vivo by encapsulating a Ag2S quantum dot (QD) with fluorescence in the second near-infrared window (NIR-II, 1000-1700 nm) inside the PNC, using simian virus 40 (SV40) PNC (PNCSV40) as a model. Benefiting from the high spatiotemporal resolution and deep tissue penetration of NIR-II fluorescence imaging, the dynamic distribution of the PNCSV40 in living mice was tracked in real time with high fidelity, and adopting the PEGylation strategy, surface chemistry-dependent in vivo behaviors of PNCSV40 were clearly revealed. This study represents the first evidence of real-time tracking of the intrinsic behaviors of PNCs in vivo without interference in PNC-host interactions by encapsulating nanoprobes inside. The as-described imaging strategy will facilitate the study of interactions between exogenously introduced PNCs and host body and prompt the development of future protein-based drugs, sensors, and high-efficacy targeted delivery systems.
Alauddin, Mohammad; Gloaguen, Eric; Brenner, Valérie; Tardivel, Benjamin; Mons, Michel; Zehnacker-Rentien, Anne; Declerck, Valérie; Aitken, David J
2015-11-09
This work describes the use of conformer-selective laser spectroscopy following supersonic expansion to probe the local folding proclivities of four-membered ring cyclic β-amino acid building blocks. Emphasis is placed on stereochemical effects as well as on the structural changes induced by the replacement of a carbon atom of the cycle by a nitrogen atom. The amide A IR spectra are obtained and interpreted with the help of quantum chemistry structure calculations. Results provide evidence that the building block with a trans-substituted cyclobutane ring has a predilection to form strong C8 hydrogen bonds. Nitrogen-atom substitution in the ring induces the formation of the hydrazino turn, with a related but distinct hydrogen-bonding network: the structure is best viewed as a bifurcated C8/C5 bond with the N heteroatom lone electron pair playing a significant acceptor role, which supports recent observations on the hydrazino turn structure in solution. Surprisingly, this study shows that the cis-substituted cyclobutane ring derivative also gives rise predominantly to a C8 hydrogen bond, although weaker than in the two former cases, a feature that is not often encountered for this building block.
Gresh, Nohad; Sponer, Judit E; Devereux, Mike; Gkionis, Konstantinos; de Courcy, Benoit; Piquemal, Jean-Philip; Sponer, Jiri
2015-07-30
Until now, atomistic simulations of DNA and RNA and their complexes have been executed using well calibrated but conceptually simple pair-additive empirical potentials (force fields). Although such simulations provided many valuable results, it is well established that simple force fields also introduce errors into the description, underlying the need for development of alternative anisotropic, polarizable molecular mechanics (APMM) potentials. One of the most abundant forces in all kinds of nucleic acids topologies is base stacking. Intra- and interstrand stacking is assumed to be the most essential factor affecting local conformational variations of B-DNA. However, stacking also contributes to formation of all kinds of noncanonical nucleic acids structures, such as quadruplexes or folded RNAs. The present study focuses on 14 stacked cytosine (Cyt) dimers and the doubly H-bonded dimer. We evaluate the extent to which an APMM procedure, SIBFA, could account quantitatively for the results of high-level quantum chemistry (QC) on the total interaction energies, and the individual energy contributions and their nonisotropic behaviors. Good agreements are found at both uncorrelated HF and correlated DFT and CCSD(T) levels. Resorting in SIBFA to distributed QC multipoles and to an explicit representation of the lone pairs is essential to respectively account for the anisotropies of the Coulomb and of the exchange-repulsion QC contributions.
Balabin, Roman M; Lomakina, Ekaterina I
2011-06-28
A multilayer feed-forward artificial neural network (MLP-ANN) with a single, hidden layer that contains a finite number of neurons can be regarded as a universal non-linear approximator. Today, the ANN method and linear regression (MLR) model are widely used for quantum chemistry (QC) data analysis (e.g., thermochemistry) to improve their accuracy (e.g., Gaussian G2-G4, B3LYP/B3-LYP, X1, or W1 theoretical methods). In this study, an alternative approach based on support vector machines (SVMs) is used, the least squares support vector machine (LS-SVM) regression. It has been applied to ab initio (first principle) and density functional theory (DFT) quantum chemistry data. So, QC + SVM methodology is an alternative to QC + ANN one. The task of the study was to estimate the Møller-Plesset (MPn) or DFT (B3LYP, BLYP, BMK) energies calculated with large basis sets (e.g., 6-311G(3df,3pd)) using smaller ones (6-311G, 6-311G*, 6-311G**) plus molecular descriptors. A molecular set (BRM-208) containing a total of 208 organic molecules was constructed and used for the LS-SVM training, cross-validation, and testing. MP2, MP3, MP4(DQ), MP4(SDQ), and MP4/MP4(SDTQ) ab initio methods were tested. Hartree-Fock (HF/SCF) results were also reported for comparison. Furthermore, constitutional (CD: total number of atoms and mole fractions of different atoms) and quantum-chemical (QD: HOMO-LUMO gap, dipole moment, average polarizability, and quadrupole moment) molecular descriptors were used for the building of the LS-SVM calibration model. Prediction accuracies (MADs) of 1.62 ± 0.51 and 0.85 ± 0.24 kcal mol(-1) (1 kcal mol(-1) = 4.184 kJ mol(-1)) were reached for SVM-based approximations of ab initio and DFT energies, respectively. The LS-SVM model was more accurate than the MLR model. A comparison with the artificial neural network approach shows that the accuracy of the LS-SVM method is similar to the accuracy of ANN. The extrapolation and interpolation results show that LS-SVM is
Canneaux, Sébastien; Bohr, Frédéric; Henon, Eric
2014-01-05
Kinetic and Statistical Thermodynamical Package (KiSThelP) is a cross-platform free open-source program developed to estimate molecular and reaction properties from electronic structure data. To date, three computational chemistry software formats are supported (Gaussian, GAMESS, and NWChem). Some key features are: gas-phase molecular thermodynamic properties (offering hindered rotor treatment), thermal equilibrium constants, transition state theory rate coefficients (transition state theory (TST), variational transition state theory (VTST)) including one-dimensional (1D) tunnelling effects (Wigner, and Eckart) and Rice-Ramsperger-Kassel-Marcus (RRKM) rate constants, for elementary reactions with well-defined barriers. KiSThelP is intended as a working tool both for the general public and also for more expert users. It provides graphical front-end capabilities designed to facilitate calculations and interpreting results. KiSThelP enables to change input data and simulation parameters directly through the graphical user interface and to visually probe how it affects results. Users can access results in the form of graphs and tables. The graphical tool offers customizing of 2D plots, exporting images and data files. These features make this program also well-suited to support and enhance students learning and can serve as a very attractive courseware, taking the teaching content directly from results in molecular and kinetic modelling. © 2013 Wiley Periodicals, Inc.
McWeeny, Roy
2004-01-01
Originally delivered as a series of lectures, this volume systematically traces the evolution of the ""spin"" concept from its role in quantum mechanics to its assimilation into the field of chemistry. Author Roy McWeeny presents an in-depth illustration of the deductive methods of quantum theory and their application to spins in chemistry, following the path from the earliest concepts to the sophisticated physical methods employed in the investigation of molecular structure and properties. Starting with the origin and development of the spin concept, the text advances to an examination of sp
Yu, Weili
2015-01-01
Efficient photocatalytic hydrogen generation in a suspension system requires a sophisticated nano-device that combines a photon absorber with effective redox catalysts. This study demonstrates an innovative molecular linking strategy for fabricating photocatalytic materials that allow effective charge separation of excited carriers, followed by efficient hydrogen evolution. The method for the sequential replacement of ligands with appropriate molecules developed in this study tethers both quantum dots (QDs), as photosensitizers, and metal nanoparticles, as hydrogen evolution catalysts, to TiO2 surfaces in a controlled manner at the nano-level. Combining hydrophobic and hydrophilic interactions on the surface, CdSe-ZnS core-shell QDs and an Au-Pt alloy were attached to TiO2 without overlapping during the synthesis. The resultant nano-photocatalysts achieved substantially high-performance visible-light-driven photocatalysis for hydrogen evolution. All syntheses were conducted at room temperature and in ambient air, providing a promising route for fabricating visible-light-responsive photocatalysts.
Mayhall, Nicholas J; Head-Gordon, Martin
2015-05-21
We provide a simple procedure for using inexpensive ab initio calculations to compute exchange coupling constants, J(AB), for multiradical molecules containing both an arbitrary number of radical sites and an arbitrary number of unpaired electrons. For a system comprised of 2M unpaired electrons, one needs only to compute states having the Ŝ(z) quantum number M - 1. Conveniently, these are precisely the states that are accessed by the family of single spin-flip methods. Building an effective Hamiltonian with these states allows one to extract all of the J(AB) constants in the molecule. Unlike approaches based on density functional theory, this procedure relies on neither spin-contaminated states nor nonunique spin-projection formulas. A key benefit is that it is possible to obtain completely spin-pure exchange coupling constants with inexpensive ab initio calculations. A couple of examples are provided to illustrate the approach, including a 4-nickel cubane complex and a 6-chromium horseshoe complex with 18 entangled electrons.
Arkan, Foroogh; Izadyar, Mohammad; Nakhaeipour, Ali
2015-12-01
In this work, ten porphyrin derivatives, including free-base zinc-metalised compounds were studied by varying the position of the carboxyl anchoring group and the alkyl substituents length on the remaining three phenyl rings with the aim of the cell efficiency investigation. Theoretical performances of the sensitisers in the dye-sensitised solar cell systems have been discussed by analysis of the optical absorption, the oxidised potential of ground and excited states, light-harvesting efficiency and electron injection efficiency. Due to lower symmetry of free-based porphyrins, they showed broader bands than zinc porphyrins. The second group sensitisers are better than the first one due to the smaller oxidation potential energy, higher open-circuit voltage and light-harvesting efficiency. The influence of long alkyl substituents on the photovoltaic parameters is not perceptible but ortho and meta positions of anchoring group modify the solar cell performance. Finally, some correlations between the quantum reactivity indices and photovoltaic parameters have obtained and discussed.
Vlcek, Lukas; Uhlik, Filip; Moucka, Filip; Nezbeda, Ivo; Chialvo, Ariel A
2015-01-22
We evaluate the ability of selected classical molecular models to describe the thermodynamic and structural aspects of gas-phase hydration of alkali metal halide ions and the formation of small water clusters. To understand the effect of many-body interactions (polarization) and charge penetration effects on the accuracy of a force field, we perform Monte Carlo simulations with three rigid water models using different functional forms to account for these effects: (i) point charge nonpolarizable SPC/E, (ii) Drude point charge polarizable SWM4-DP, and (iii) Drude Gaussian charge polarizable BK3. Model predictions are compared with experimental Gibbs free energies and enthalpies of ion hydration, and with microscopic structural properties obtained from quantum DFT calculations. We find that all three models provide comparable predictions for pure water clusters and cation hydration but differ significantly in their description of anion hydration. None of the investigated classical force fields can consistently and quantitatively reproduce the experimental gas-phase hydration thermodynamics. The outcome of this study highlights the relation between the functional form that describes the effective intermolecular interactions and the accuracy of the resulting ion hydration properties.
Tonner, Ralf; Schwerdtfeger, Peter; May, Amanda L; Steill, Jeffrey D; Berden, Giel; Oomens, Jos; Campagna, Shawn R; Compton, Robert N
2012-05-17
In an effort to understand the chemical factors that stabilize dianions, experimental and theoretical studies on the stability of the tartrate dianion were performed. Quantum chemical calculations at the coupled cluster level reveal only a metastable state with a possible decomposition pathway (O(2)C-CH(OH)-CH(OH)-CO(2))(2-) → (O(2)C-CH(OH)-CH(OH))(•-) + CO(2) + e(-) explaining the observed gas-phase instability of this dianion. Further theoretical data were collected for the bare dianion, this molecule complexed to water, sodium, and a proton, in both the meso and l forms as well as for the uncomplexed radical anion and neutral diradical. The calculations suggest that the l-tartrate dianion is more thermodynamically stable than the dianion of the meso stereoisomer and that either dianion can be further stabilized by association with a separate species that can help to balance the charge of the molecular complex. Mass spectrometry was then used to measure the energy needed to initiate collisionally induced dissociation of the racemic tartrate dianion and for the proton and sodium adducts of both the racemic and meso form of this molecule. Infrared action spectra of the dianion stereoisomers complexed with sodium were also acquired to determine the influence of the metal ion on the vibrations of the dianions and validate the computationally predicted structures. These experimental data support the theoretical conclusions and highlight the instability of the bare tartrate dianion. From the experimental work, it could also be concluded that the pathway leading to dissociation is under kinetic control because the sodium adduct of the racemic stereoisomer dissociated at lower collisional energy, although it was calculated to be more stable, and that decomposition proceeded via C-C bond dissociation as computationally predicted. Taken together, these data provide insight into the gas-phase stability of the tartrate dianion and highlight the role of adducts in
Sato, Harumi; Dybal, Jiří; Murakami, Rumi; Noda, Isao; Ozaki, Yukihiro
2005-06-01
This review paper reports infrared (IR) and Raman spectroscopy and quantum chemistry calculation studies of C-H⋯O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoates. IR and Raman spectra were measured for poly(3-hydroxybutyrate) (PHB) and a new type of bacterial copolyester, poly(3-hydroxybutyrate- co-3-hydroxyhexanoate), P(HB- co-HHx) (HHx=12 mol%) over a temperature range of 20 °C to higher temperatures (PHB, 200 °C; HHx=12 mol%, 140 °C) to explore their structure and thermal behavior. One of bands due to the CH 3 asymmetric stretching modes appears near 3010 cm -1 in the IR and Raman spectra of PHB and P(HB- co-HHx) at 20 °C. These frequencies of IR and Raman CH 3 asymmetric stretching bands are much higher than usual. These anomalous frequencies of the CH 3 asymmetric stretching bands together with the X-ray crystallographic structure of PHB have suggested that there is an inter- or intra-molecular C-H⋯O hydrogen bond between the C dbnd6 O group in one helical structure and the CH 3 group in the other helical structure in PHB and P(HB- co-HHx). The quantum chemical calculation of model compounds of PHB also has suggested the existence of C-H⋯O hydrogen bonds in PHB and P(HB- co-HHx). It is very likely that a chain of C-H⋯O hydrogen bond pairs link two parallel helical structures in the crystalline parts. The temperature-dependent IR and Raman spectral variations have revealed that the crystallinity of P(HB- co-HHx) (HHx=12 mol%) decreases gradually from a fairly low temperature (about 60 °C), while the crystallinity of PHB remains almost unchanged until just below its melting temperature. It has also been found from the IR and Raman studies that for both PHB and P(HB- co-HHx) the weakening of the C-H⋯O hydrogen bonds starts from just above room temperature, but the deformation of helical structures occurs after the weakening of the C-H⋯O hydrogen bonds advances to some extent.
Jaffe, Richard; Han, Jie; Globus, Al; Chancellor, Marisa K. (Technical Monitor)
1997-01-01
Considerable progress has been made in recent years in chemical functionalization of fullerene molecules. In some cases, the predominant reaction products are different from those obtained (using the same reactants) from polycyclic aromatic hydrocarbons (PAHs). One such example is the cycloaddition of o-benzyne to C60. It is well established that benzyne adds across one of the rings in naphthalene, anthracene and other PAHs forming the [2+4] cycloaddition product (benzobicyclo[2.2.2.]-octatriene with naphthalene and triptycene with anthracene). However, Hoke et al demonstrated that the only reaction path for o-benzyne with C60 leads to the [2+2] cycloaddition product in which benzyne adds across one of the interpentagonal bonds (forming a cyclobutene ring in the process). Either reaction product results in a loss of aromaticity and distortion of the PAH or fullerene substrate, and in a loss of strain in the benzyne. It is not clear, however, why different products are preferred in these cases. In the current paper, we consider the stability of benzyne-nanotube adducts and the ability of Brenner's potential energy model to describe the structure and stability of these adducts. The Brenner potential has been widely used for describing diamondoid and graphitic carbon. Recently it has also been used for molecular mechanics and molecular dynamics simulations of fullerenes and nanotubes. However, it has not been tested for the case of functionalized fullerenes (especially with highly strained geometries). We use the Brenner potential for our companion nanogear simulations and believe that it should be calibrated to insure that those simulations are physically reasonable. In the present work, Density Functional theory (DFT) calculations are used to determine the preferred geometric structures and energetics for this calibration. The DFT method is a kind of ab initio quantum chemistry method for determining the electronic structure of molecules. For a given basis set
Rethinking Undergraduate Physical Chemistry Curricula
Miller, Stephen R.
2016-01-01
A summary of fundamental changes made to the undergraduate physical chemistry curriculum in the Chemistry Department at Gustavus Adolphus College (beginning in the 2013-2014 academic year) is presented. The yearlong sequence now consists of an introductory semester covering both quantum mechanics and thermodynamics/kinetics, followed by a second…
Rethinking Undergraduate Physical Chemistry Curricula
Miller, Stephen R.
2016-01-01
A summary of fundamental changes made to the undergraduate physical chemistry curriculum in the Chemistry Department at Gustavus Adolphus College (beginning in the 2013-2014 academic year) is presented. The yearlong sequence now consists of an introductory semester covering both quantum mechanics and thermodynamics/kinetics, followed by a second…
Lee, Yong-Sok; Siméon, Fabrice G; Briard, Emmanuelle; Pike, Victor W
2012-04-18
Eighteen kilodalton translocator protein (TSPO) is an important target for drug discovery and for clinical molecular imaging of brain and peripheral inflammatory processes. PK 11195 [1a; 1-(2-chlorophenyl)-N-methyl-(1-methylpropyl)-3-isoquinoline carboxamide] is the major prototypical high-affinity ligand for TSPO. Elucidation of the solution structure of 1a is of interest for understanding small-molecule ligand interactions with the lipophilic binding site of TSPO. Dynamic (1)H/(13)C NMR spectroscopy of 1a revealed four quite stable but interconverting rotamers, due to amide bond and 2-chlorophenyl group rotation. These rotamers have been neglected in previous descriptions of the structure of 1a and of the binding of 1a to TSPO. Here, we used quantum chemistry at the level of B3LYP/6-311+G(2d,p) to calculate (13)C and (1)H chemical shifts for the rotamers of 1a and for the very weak TSPO ligand, N-desmethyl-PK 11195 (1b). These data, plus experimental NMR data, were then used to characterize the structures of rotamers of 1a and 1b in organic solution. Energy barriers for both the amide bond and 2'-chlorophenyl group rotation of 1a were determined from dynamic (1)H NMR to be similar (ca.17 to 18 kcal/mol), and they compared well with those calculated at the level of B3LYP/6-31G*. Furthermore, the computed barrier for Z to E rotation is considerably lower in 1a(18.7 kcal/mol) than in 1b (25.4 kcal/mol). NMR (NOE) unequivocally demonstrated that the E rotamer of 1a is the more stable in solution by about 0.4 kcal/mol. These detailed structural findings will aid future TSPO ligand design and support the notion that TSPO prefers to bind ligands as amide E-rotamers.
Nakatsuji, Hiroshi
2012-09-18
Just as Newtonian law governs classical physics, the Schrödinger equation (SE) and the relativistic Dirac equation (DE) rule the world of chemistry. So, if we can solve these equations accurately, we can use computation to predict chemistry precisely. However, for approximately 80 years after the discovery of these equations, chemists believed that they could not solve SE and DE for atoms and molecules that included many electrons. This Account reviews ideas developed over the past decade to further the goal of predictive quantum chemistry. Between 2000 and 2005, I discovered a general method of solving the SE and DE accurately. As a first inspiration, I formulated the structure of the exact wave function of the SE in a compact mathematical form. The explicit inclusion of the exact wave function's structure within the variational space allows for the calculation of the exact wave function as a solution of the variational method. Although this process sounds almost impossible, it is indeed possible, and I have published several formulations and applied them to solve the full configuration interaction (CI) with a very small number of variables. However, when I examined analytical solutions for atoms and molecules, the Hamiltonian integrals in their secular equations diverged. This singularity problem occurred in all atoms and molecules because it originates from the singularity of the Coulomb potential in their Hamiltonians. To overcome this problem, I first introduced the inverse SE and then the scaled SE. The latter simpler idea led to immediate and surprisingly accurate solution for the SEs of the hydrogen atom, helium atom, and hydrogen molecule. The free complement (FC) method, also called the free iterative CI (free ICI) method, was efficient for solving the SEs. In the FC method, the basis functions that span the exact wave function are produced by the Hamiltonian of the system and the zeroth-order wave function. These basis functions are called complement
Energy Technology Data Exchange (ETDEWEB)
Grawert, G. (Marburg Univ. (Germany, F.R.). Fachbereich 13 - Physik)
1989-01-01
The aim of the textbook now present in fifth edition is the representation of the fundamental physical concepts of the theory of quantum mechanics. It is confined to the nonrelativistic quantum mechanics; however also themes are treated which are in an extended form important just for quantum field theory up to the modern development. (orig.) With 22 figs.
Integrating Computational Chemistry into a Course in Classical Thermodynamics
Martini, Sheridan R.; Hartzell, Cynthia J.
2015-01-01
Computational chemistry is commonly addressed in the quantum mechanics course of undergraduate physical chemistry curricula. Since quantum mechanics traditionally follows the thermodynamics course, there is a lack of curricula relating computational chemistry to thermodynamics. A method integrating molecular modeling software into a semester long…
The Promise of Quantum Simulation
Muller, Richard P
2015-01-01
Quantum simulation promises to be one of the primary application of quantum computers, should one be constructed. This article briefly summarizes the history quantum simulation in light of the recent result of Wang and coworkers demonstrating calculation of the ground and excited states for a HeH+ molecule, and concludes with a discussion of why this and other recent progress in the field suggests that quantum simulation of quantum chemistry has a bright future.
Quantum Chemistry Study on Electronic Structure of Vanadium Hydride%钒氢化物电子结构的量子化学研究
Institute of Scientific and Technical Information of China (English)
李荣; 周上祺; 陈昌国; 梁国明; 刘守平; 孔纪兰
2005-01-01
利用电荷自洽离散变分Xα(SCC-DV-Xα)方法计算了钒基固溶体中钒氢反应前后钒及其氢化物(VHx,x=0,1,2)、假定原子簇模型VH*x(x=1,2)和VHx′(x=0,1)的电子结构.结果表明:钒与氢气反应生成VH时,化学效应和结构效应都使V 3d和H 1s轨道向低能量方向移动,氢化物VH中V 3d和H 1s轨道重叠最多,V-H之间的相互作用较强.VH再与氢气反应生成VH2时,结构效应使V 3d和H 1s轨道都向高能量方向移动,氢化物VH2中V 3d和H 1s轨道重叠最少,V和H之间的相互作用较弱.氢化物VH和VH2中不仅存在离子性相互作用,而且还存在共价性相互作用.结构效应导致VH2中V-H键的共价性减弱,从而导致VH2中V和H之间的相互作用减弱.氢化物VH的费米能级比VH2的低,说明VH更稳定.%The electronic structure of V and VHx(x=0, 1, 2) in vanadium-based solid solution was calculated by using self-consistent-charge discrete variational (SCC-DV-Xα) method of quantum chemistry. The results demonstrated that the interaction between V and H in VH and VH2 was not only ionic but also covalent; the V-H bond between V and H bands in hydride VH2 was weaker than that in VH. The bonds were due to interaction between the V 4s and H1s in hydride VH, and the interaction between V 4s, V 3d and H1s in VH2. Fermi energy level in VH was lower than in VH2.The results suggested that VH is more stable.
Energy Technology Data Exchange (ETDEWEB)
Zonta, Francesco [Dipartimento di Fisica e Astronomia “G. Galilei”, Università degli Studi di Padova, 35131 Padova (Italy); Mammano, Fabio, E-mail: fabio.mammano@unipd.it [Dipartimento di Fisica e Astronomia “G. Galilei”, Università degli Studi di Padova, 35131 Padova (Italy); Istituto Veneto di Medicina Molecolare, Fondazione per la Ricerca Biomedica Avanzata, 35129 Padova (Italy); Istituto CNR di Neuroscienze, 35131 Padova (Italy); Torsello, Mauro; Fortunati, Nicola [Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy); Orian, Laura, E-mail: laura.orian@unipd.it [Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy); Polimeno, Antonino [Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, 35131 Padova (Italy)
2014-02-28
Graphical abstract: - Highlights: • QM calculations show that Ca{sup 2+} binds to γGlu47 in connexin hemichannels. • Molecular models of increasing size are employed in hybrid DFT calculations. • Ca{sup 2+} binding affects the interaction between γGlu47 and Arg75, Arg184. • Ca{sup 2+} binding alters the structure in a critical region of connexin hemichannels. - Abstract: Connexin hemichannels are regulated by several gating mechanisms, some of which depend critically on the extracellular Ca{sup 2+} concentration ([Ca{sup 2+}]{sub e}). It is well established that hemichannel activity is inhibited at normal (∼1 mM) [Ca{sup 2+}]{sub e}, whereas lowering [Ca{sup 2+}]{sub e} to micromolar levels fosters hemichannel opening. Atomic force microscopy imaging shows significant and reversible changes of pore diameter at the extracellular mouth of Cx26 hemichannels exposed to different [Ca{sup 2+}]{sub e}, however, the underlying molecular mechanisms are not fully elucidated. Analysis of the crystal structure of connexin 26 (Cx26) gap junction channels, corroborated by molecular dynamics (MD) simulations, suggests that several negatively charged amino acids create a favorable environment for low-affinity Ca{sup 2+} binding within the extracellular vestibule of the Cx26 hemichannel. In particular a highly conserved glutammic acid, found in position 47 in most connexins, is thought to undergo post translational gamma carboxylation (γGlu47), and is thus likely to play an important role in Ca{sup 2+} coordination. γGlu47 may also form salt bridges with two conserved arginines (Arg75 and Arg184 in Cx26), which are considered important in stabilizing the structure of the extracellular region. Using a combination of quantum chemistry methods, we analyzed the interaction between γGlu47, Arg75 and Arg184 in a Cx26 hemichannel model both in the absence and in the presence of Ca{sup 2+}. We show that Ca{sup 2+} imparts significant local structural changes and speculate
The physical basis of chemistry
Warren, Warren S
2000-01-01
If the text you're using for general chemistry seems to lack sufficient mathematics and physics in its presentation of classical mechanics, molecular structure, and statistics, this complementary science series title may be just what you're looking for. Written for the advanced lower-division undergraduate chemistry course, The Physical Basis of Chemistry, Second Edition, offers students an opportunity to understand and enrich the understanding of physical chemistry with some quantum mechanics, the Boltzmann distribution, and spectroscopy. Posed and answered are questions concerning eve
Hayes, David M.; Mahar, Maura; Schnabel, R. Chris; Shah, Paras; Lees, Alistair J.; Jakubek, Vladimir
2007-01-01
We present a new laboratory experiment on the photochemistry of organometallic [eta][superscript 5],[eta][superscript 6]-mixed-sandwich compounds, which is suitable for both the physical chemistry and inorganic chemistry laboratory. Specifically, students use 1,10-phenanthroline to trap the intermediate formed when…
Schieber, Christine; Bestetti, Alessandra; Lim, Jet Phey; Ryan, Anneke D; Nguyen, Tich-Lam; Eldridge, Robert; White, Anthony R; Gleeson, Paul A; Donnelly, Paul S; Williams, Spencer J; Mulvaney, Paul
2012-10-15
Twinkle twinkle quantum dot: Conjugation of biomolecules to azide-modified quantum dots (QDs) through a bifunctional linker, using strain-promoted azide-alkyne cycloaddition with the QD and a squaramide linkage to the biomolecule (see scheme). Transferrin-conjugated QDs were internalized by transferrin-receptor expressing HeLa cells.
Buncel, Erwin
2015-01-01
This book introduces the concepts, theory and experimental knowledge concerning solvent effects on the rate and equilibrium of chemical reactions of all kinds. It begins with basic thermodynamics and kinetics, building on this foundation to demonstrate how a more detailed understanding of these effects may be used to aid in determination of reaction mechanisms, and to aid in planning syntheses. Consideration is given to theoretical calculations (quantum chemistry, molecular dynamics, etc.), to statistical methods (chemometrics), and to modern day concerns such as ""green"" chemistry, where ut
Goyal, Ketan; Kawai, Ryoichi
As nanotechnology advances, understanding of the thermodynamic properties of small systems becomes increasingly important. Such systems are found throughout physics, biology, and chemistry manifesting striking properties that are a direct result of their small dimensions where fluctuations become predominant. The standard theory of thermodynamics for macroscopic systems is powerless for such ever fluctuating systems. Furthermore, as small systems are inherently quantum mechanical, influence of quantum effects such as discreteness and quantum entanglement on their thermodynamic properties is of great interest. In particular, the quantum fluctuations due to quantum uncertainty principles may play a significant role. In this talk, we investigate thermodynamic properties of an autonomous quantum heat engine, resembling a quantum version of the Feynman Ratchet, in non-equilibrium condition based on the theory of open quantum systems. The heat engine consists of multiple subsystems individually contacted to different thermal environments.
Ghosh, P K
2014-01-01
Quantum mechanics, designed for advanced undergraduate and graduate students of physics, mathematics and chemistry, provides a concise yet self-contained introduction to the formal framework of quantum mechanics, its application to physical problems and the interpretation of the theory. Starting with a review of some of the necessary mathematics, the basic concepts are carefully developed in the text. After building a general formalism, detailed treatment of the standard material - the harmonic oscillator, the hydrogen atom, angular momentum theory, symmetry transformations, approximation methods, identical particle and many-particle systems, and scattering theory - is presented. The concluding chapter discusses the interpretation of quantum mechanics. Some of the important topics discussed in the book are the rigged Hilbert space, deformation quantization, path integrals, coherent states, geometric phases, decoherene, etc. This book is characterized by clarity and coherence of presentation.
Elementary and brief introduction of hadronic chemistry
Tangde, Vijay M.
2013-10-01
The discipline, today known as Quantum Chemistry for atomic and subatomic level interactions has no doubt made a significant historical contributions to the society. Despite of its significant achievements, quantum chemistry is also known for its widespread denial of insufficiencies it inherits. An Italian-American Scientist Professor Ruggero Maria Santilli during his more than five decades of dedicated and sustained research has denounced the fact that quantum chemistry is mostly based on mere nomenclatures without any quantitative scientific contents. Professor R M Santilli first formulated the iso-, geno- and hyper-mathematics [1-4] that helped in understanding numerous diversified problems and removing inadequacies in most of the established and celebrated theories of 20th century physics and chemistry. This involves the isotopic, genotopic, etc. lifting of Lie algebra that generated Lie admissible mathematics to properly describe irreversible processes. The studies on Hadronic Mechanics in general and chemistry in particular based on Santilli's mathematics[3-5] for the first time has removed the very fundamental limitations of quantum chemistry [2, 6-8]. In the present discussion, we have briefly reviewed the conceptual foundations of Hadronic Chemistry that imparts the completeness to the Quantum Chemistry via an addition of effects at distances of the order of 1 fm (only) which are assumed to be Non-linear, Non-local, Non-potential, Non-hamiltonian and thus Non-unitary and its application in development of a new chemical species called Magnecules.
Aerts, Patrick Johan Coenraad
1986-01-01
Computational Theoretical Chemnistry is a research area which, as far as electronic structure problems are concerned, encompasses essentially the development of theoretically sound, yet computionally feasable quantum mechanical models for atoms melecules and the solid state. ... Zie: Introduction
Computational Chemistry Using Modern Electronic Structure Methods
Bell, Stephen; Dines, Trevor J.; Chowdhry, Babur Z.; Withnall, Robert
2007-01-01
Various modern electronic structure methods are now days used to teach computational chemistry to undergraduate students. Such quantum calculations can now be easily used even for large size molecules.
School Science Review, 1976
1976-01-01
Described are eight chemistry experiments and demonstrations applicable to introductory chemistry courses. Activities include: measure of lattice enthalpy, Le Chatelier's principle, decarboxylation of soap, use of pocket calculators in pH measurement, and making nylon. (SL)
Hemming, Karl
2011-01-01
Recent progress in the synthesis of heterocyclic compounds is presented\\ud 2010 offered highlights in pericyclic chemistry, particularly 1,3-dipolar cycloaddition chemistry, asymmetric synthesis, gold catalysis, organocatalysis, hydroamination, C–H activation and multicomponent reactions.
The Chemistry Dashboard is part of a suite of dashboards developed by EPA to help evaluate the safety of chemicals. The Chemistry Dashboard provides access to a variety of information on over 700,000 chemicals currently in use.
Häussinger, Daniel; Pfohl, Thomas
2010-01-01
Biophysical chemistry at the Department of Chemistry, University of Basel, covers the NMR analysis of protein-protein interaction using paramagnetic tags and sophisticated microscopy techniques investigating the dynamics of biological matter.
Griffiths, J.; Rattee, I. D.
1973-01-01
Discusses the course offerings in pure color chemistry at two universities and the three main aspects of study: dyestuff chemistry, color measurement, and color application. Indicates that there exists a constant challenge to ingenuity in the subject discipline. (CC)
A quantum-quantum Metropolis algorithm.
Yung, Man-Hong; Aspuru-Guzik, Alán
2012-01-17
The classical Metropolis sampling method is a cornerstone of many statistical modeling applications that range from physics, chemistry, and biology to economics. This method is particularly suitable for sampling the thermal distributions of classical systems. The challenge of extending this method to the simulation of arbitrary quantum systems is that, in general, eigenstates of quantum Hamiltonians cannot be obtained efficiently with a classical computer. However, this challenge can be overcome by quantum computers. Here, we present a quantum algorithm which fully generalizes the classical Metropolis algorithm to the quantum domain. The meaning of quantum generalization is twofold: The proposed algorithm is not only applicable to both classical and quantum systems, but also offers a quantum speedup relative to the classical counterpart. Furthermore, unlike the classical method of quantum Monte Carlo, this quantum algorithm does not suffer from the negative-sign problem associated with fermionic systems. Applications of this algorithm include the study of low-temperature properties of quantum systems, such as the Hubbard model, and preparing the thermal states of sizable molecules to simulate, for example, chemical reactions at an arbitrary temperature.
DEFF Research Database (Denmark)
Nielsen, John
1994-01-01
An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds.......An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds....
DEFF Research Database (Denmark)
Nielsen, John
1994-01-01
An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds.......An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds....
Green, James
1964-01-01
Positronium Chemistry focuses on the methodologies, reactions, processes, and transformations involved in positronium chemistry. The publication first offers information on positrons and positronium and experimental methods, including mesonic atoms, angular correlation measurements, annihilation spectra, and statistical errors in delayed coincidence measurements. The text then ponders on positrons in gases and solids. The manuscript takes a look at the theoretical chemistry of positronium and positronium chemistry in gases. Topics include quenching, annihilation spectrum, delayed coincidence
Niaz, Mansoor
1998-01-01
Reports on a study that involves the analysis of chemistry textbooks at the college freshman level to determine the degree to which they address developments in the history and philosophy of science. Twenty-three textbooks were evaluated on eight criteria. Contains 108 references. (DDR)
Bell, Suzanne
2009-01-01
Forensic chemistry is unique among chemical sciences in that its research, practice, and presentation must meet the needs of both the scientific and the legal communities. As such, forensic chemistry research is applied and derivative by nature and design, and it emphasizes metrology (the science of measurement) and validation. Forensic chemistry has moved away from its analytical roots and is incorporating a broader spectrum of chemical sciences. Existing forensic practices are being revisited as the purview of forensic chemistry extends outward from drug analysis and toxicology into such diverse areas as combustion chemistry, materials science, and pattern evidence.
Integrating Computational Chemistry into the Physical Chemistry Curriculum
Johnson, Lewis E.; Engel, Thomas
2011-01-01
Relatively few undergraduate physical chemistry programs integrate molecular modeling into their quantum mechanics curriculum owing to concerns about limited access to computational facilities, the cost of software, and concerns about increasing the course material. However, modeling exercises can be integrated into an undergraduate course at a…
Integrating Computational Chemistry into the Physical Chemistry Curriculum
Johnson, Lewis E.; Engel, Thomas
2011-01-01
Relatively few undergraduate physical chemistry programs integrate molecular modeling into their quantum mechanics curriculum owing to concerns about limited access to computational facilities, the cost of software, and concerns about increasing the course material. However, modeling exercises can be integrated into an undergraduate course at a…
Physical Chemistry Chemical Kinetics and Reaction Mechanism
Trimm, Harold H
2011-01-01
Physical chemistry covers diverse topics, from biochemistry to materials properties to the development of quantum computers. Physical chemistry applies physics and math to problems that interest chemists, biologists, and engineers. Physical chemists use theoretical constructs and mathematical computations to understand chemical properties and describe the behavior of molecular and condensed matter. Their work involves manipulations of data as well as materials. Physical chemistry entails extensive work with sophisticated instrumentation and equipment as well as state-of-the-art computers. This
Papaphotis, Georgios; Tsaparlis, Georgios
2008-01-01
Part 2 of the findings are presented of a quantitative study (n = 125) on basic quantum chemical concepts taught at twelfth grade (age 17-18 years) in Greece. A paper-and-pencil test of fourteen questions was used that were of two kinds: five questions that tested recall of knowledge or application of algorithmic procedures (type-A questions);…
Muniz, Marc N.; Oliver-Hoyo, Maria T.
2014-01-01
We report a novel educational activity designed to teach quantum mechanical tunneling to upper-division undergraduate students in the context of nanochemistry. The activity is based on a theoretical framework for analogy and is split into three parts that are linked pedagogically through the framework: classical ball-and-ramp system, tunneling…
Green, William P.; Trotochaud, Alan; Sherman, Julia; Kazerounian, Kazem; Faraclas, Elias W.
2009-01-01
The quantization of electronic energy levels in atoms is foundational to a mechanistic explanation of the periodicity of elemental properties and behavior. This paper presents a hands-on, guided inquiry approach to teaching this concept as part of a broader treatment of quantum mechanics, and as a foundation for an understanding of chemical…
Green, William P.; Trotochaud, Alan; Sherman, Julia; Kazerounian, Kazem; Faraclas, Elias W.
2009-01-01
The quantization of electronic energy levels in atoms is foundational to a mechanistic explanation of the periodicity of elemental properties and behavior. This paper presents a hands-on, guided inquiry approach to teaching this concept as part of a broader treatment of quantum mechanics, and as a foundation for an understanding of chemical…
Energy Technology Data Exchange (ETDEWEB)
NONE
2003-08-15
This book with sixteen chapter explains organic chemistry on linkage isomerism such as alkane, cycloalkane, alkene, aromatic compounds, stereo selective isomerization, aromatic compounds, stereo selective isomerization, organic compounds, stereo selective isomerization, organic halogen compound, alcohol, ether, aldehyde and ketone, carboxylic acid, dicarboxylic acid, fat and detergent, amino, carbohydrate, amino acid and protein, nucleotide and nucleic acid and spectroscopy, a polymer and medical chemistry. Each chapter has introduction structure and characteristic and using of organic chemistry.
2000-01-01
Computational chemistry has come of age. With significant strides in computer hardware and software over the last few decades, computational chemistry has achieved full partnership with theory and experiment as a tool for understanding and predicting the behavior of a broad range of chemical, physical, and biological phenomena. The Nobel Prize award to John Pople and Walter Kohn in 1998 highlighted the importance of these advances in computational chemistry. With massively parallel computers ...
Federal Laboratory Consortium — Chemistry technology experts at NCATS engage in a variety of innovative translational research activities, including:Design of bioactive small molecules.Development...
Robinett, R W
2004-01-01
The numerical prediction, theoretical analysis, and experimental verification of the phenomenon of wave packet revivals in quantum systems has flourished over the last decade and a half. Quantum revivals are characterized by initially localized quantum states which have a short-term, quasi-classical time evolution, which then can spread significantly over several orbits, only to reform later in the form of a quantum revival in which the spreading reverses itself, the wave packet relocalizes, and the semi-classical periodicity is once again evident. Relocalization of the initial wave packet into a number of smaller copies of the initial packet (`minipackets' or `clones') is also possible, giving rise to fractional revivals. Systems exhibiting such behavior are a fundamental realization of time-dependent interference phenomena for bound states with quantized energies in quantum mechanics and are therefore of wide interest in the physics and chemistry communities. We review the theoretical machinery of quantum w...
Physical chemistry II essentials
REA, The Editors of
1992-01-01
REA's Essentials provide quick and easy access to critical information in a variety of different fields, ranging from the most basic to the most advanced. As its name implies, these concise, comprehensive study guides summarize the essentials of the field covered. Essentials are helpful when preparing for exams, doing homework and will remain a lasting reference source for students, teachers, and professionals. Physical Chemistry II includes reaction mechanisms, theoretical approaches to chemical kinetics, gravitational work, electrical and magnetic work, surface work, kinetic theory, collisional and transport properties of gases, statistical mechanics, matter and waves, quantum mechanics, and rotations and vibrations of atoms and molecules.
Höfener, Sebastian; Trumm, Michael; Koke, Carsten; Heuser, Johannes; Ekström, Ulf; Skerencak-Frech, Andrej; Schimmelpfennig, Bernd; Panak, Petra J
2016-03-21
We report a combined computational and experimental study to investigate the UV/vis spectra of 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine (BTP) ligands in solution. In order to study molecules in solution using theoretical methods, force-field parameters for the ligand-water interaction are adjusted to ab initio quantum chemical calculations. Based on these parameters, molecular dynamics (MD) simulations are carried out from which snapshots are extracted as input to quantum chemical excitation-energy calculations to obtain UV/vis spectra of BTP ligands in solution using time-dependent density functional theory (TDDFT) employing the Tamm-Dancoff approximation (TDA). The range-separated CAM-B3LYP functional is used to avoid large errors for charge-transfer states occurring in the electronic spectra. In order to study environment effects with theoretical methods, the frozen-density embedding scheme is applied. This computational procedure allows to obtain electronic spectra calculated at the (range-separated) DFT level of theory in solution, revealing solvatochromic shifts upon solvation of up to about 0.6 eV. Comparison to experimental data shows a significantly improved agreement compared to vacuum calculations and enables the analysis of relevant excitations for the line shape in solution.
The Physics of Quantum Computation
Falci, Giuseppe; Paladino, Elisabette
2015-10-01
Quantum Computation has emerged in the past decades as a consequence of down-scaling of electronic devices to the mesoscopic regime and of advances in the ability of controlling and measuring microscopic quantum systems. QC has many interdisciplinary aspects, ranging from physics and chemistry to mathematics and computer science. In these lecture notes we focus on physical hardware, present day challenges and future directions for design of quantum architectures.
Meyer, Ralf; Pototschnig, Johann V.; Hauser, Andreas W.; Ernst, Wolfgang E.
2016-06-01
Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. The preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. On the theoretical side, highly accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. Particularly problematic is the correct description of potential features at large intermolecular distances. Franck-Condon overlap integrals for nuclear wavefunctions in barely bound vibrational states are extremely sensitive to inaccuracies of the potential at long range. In this study, we compare the predictions of common, wavefunction-based ab initio techniques for a known de-excitation mechanism in alkali-alkaline earth dimers. It is the aim to analyze the predictive power of these methods for a preliminary evaluation of potential cooling mechanisms in heteronuclear open shell systems which offer the experimentalist an electric as well as a magnetic handle for manipulation. The series of X-Sr molecules, with X = Li, Na, K and Rb, has been chosen for a direct comparison. Quantum degenerate mixtures of Rb and Sr have already been produced, making this combination very promising for the production of ultracold molecules. B. Pasquiou, A. Bayerle, S. M. Tzanova, S. Stellmer, J. Szczepkowski, M. Parigger, R. Grimm, and F. Schreck, Phys. Rev. A, 2013, 88, 023601
Baron, Mark; Gonzalez-Rodriguez, Jose; Stevens, Gary; Gray, Nathan; Atherton, Thomas; Winn, Joss
2010-01-01
Teaching and Learning resources for the 1st Year Introductory Chemistry course (Forensic Science). 30 credits. These are Open Educational Resources (OER), made available for re-use under a Creative Commons license.
Fahlman, Bradley D
2011-01-01
The 2nd edition of Materials Chemistry builds on the strengths that were recognized by a 2008 Textbook Excellence Award from the Text and Academic Authors Association (TAA). Materials Chemistry addresses inorganic-, organic-, and nano-based materials from a structure vs. property treatment, providing a suitable breadth and depth coverage of the rapidly evolving materials field. The 2nd edition continues to offer innovative coverage and practical perspective throughout. After briefly defining materials chemistry and its history, seven chapters discuss solid-state chemistry, metals, semiconducting materials, organic "soft" materials, nanomaterials, and materials characterization. All chapters have been thoroughly updated and expanded with, for example, new sections on ‘soft lithographic’ patterning, ‘click chemistry’ polymerization, nanotoxicity, graphene, as well as many biomaterials applications. The polymer and ‘soft’ materials chapter represents the largest expansion for the 2nd edition. Each ch...
Chemical and Engineering News, 1979
1979-01-01
Provides a brief review of the latest developments in nuclear chemistry. Nuclear research today is directed toward increased activity in radiopharmaceuticals and formation of new isotopes by high-energy, heavy-ion collisions. (Author/BB)
Institute of Scientific and Technical Information of China (English)
2011-01-01
@@ Cansisting of eight scientists from the State Key Laboratory of Physical Chemistry of Solid Surfaces and Xiamen University, this creative research group is devoted to the research of cluster chemistry and creation of nanomaterials.After three-year hard work, the group scored a series of encouraging progresses in synthesis of clusters with special structures, including novel fullerenes, fullerene-like metal cluster compounds as well as other related nanomaterials, and their properties study.
Energy Technology Data Exchange (ETDEWEB)
Collison, Melanie
2011-05-15
Green chemistry is the science of chemistry used in a way that will not use or create hazardous substances. Dr. Rui Resendes is working in this field at GreenCentre Canada, an offshoot of PARTEQ Innovations in Kingston, Ontario. GreenCentre's preliminary findings suggest their licensed product {sup S}witchable Solutions{sup ,} featuring 3 classes of solvents and a surfactant, may be useful in bitumen oil sands extraction.
Perspectives on Computational Organic Chemistry
Streitwieser, Andrew
2009-01-01
The author reviews how his early love for theoretical organic chemistry led to experimental research and the extended search for quantitative correlations between experiment and quantum calculations. The experimental work led to ion pair acidities of alkali-organic compounds and most recently to equilibria and reactions of lithium and cesium enolates in THF. This chemistry is now being modeled by ab initio calculations. An important consideration is the treatment of solvation in which coordination of the alkali cation with the ether solvent plays a major role. PMID:19518150
Theoretical chemistry advances and perspectives
Eyring, Henry
1980-01-01
Theoretical Chemistry: Advances and Perspectives, Volume 5 covers articles concerning all aspects of theoretical chemistry. The book discusses the mean spherical approximation for simple electrolyte solutions; the representation of lattice sums as Mellin-transformed products of theta functions; and the evaluation of two-dimensional lattice sums by number theoretic means. The text also describes an application of contour integration; a lattice model of quantum fluid; as well as the computational aspects of chemical equilibrium in complex systems. Chemists and physicists will find the book usef
Physical chemistry a very short introduction
Atkins, Peter
2014-01-01
With the development of a variety of exciting new areas of research involving computational chemistry, nano- and smart materials, and applications of the recently discovered graphene, there can be no doubt that physical chemistry is a vitally important field. It is also perceived as the most daunting branch of chemistry, being necessarily grounded in physics and mathematics and drawing as it does on quantum mechanics, thermodynamics, and statistical thermodynamics. With his typical clarity and hardly a formula in sight, Peter Atkins' Very Short Introduction explores the contributions physical chemistry has made to all branches of chemistry. Providing insight into its central concepts Atkins reveals the cultural contributions physical chemistry has made to our understanding of the natural world.
Ito, Kengo; Tsutsumi, Yu; Date, Yasuhiro; Kikuchi, Jun
2016-04-15
The abundant observation of chemical fragment information for molecular complexities is a major advantage of biological NMR analysis. Thus, the development of a novel technique for NMR signal assignment and metabolite identification may offer new possibilities for exploring molecular complexities. We propose a new signal assignment approach for metabolite mixtures by assembling H-H, H-C, C-C, and Q-C fragmental information obtained by multidimensional NMR, followed by the application of graph and network theory. High-speed experiments and complete automatic signal assignments were achieved for 12 combined mixtures of (13)C-labeled standards. Application to a (13)C-labeled seaweed extract showed 66 H-C, 60 H-H, 326 C-C, and 28 Q-C correlations, which were successfully assembled to 18 metabolites by the automatic assignment. The validity of automatic assignment was supported by quantum chemical calculations. This new approach can predict entire metabolite structures from peak networks of biological extracts.
Energy Technology Data Exchange (ETDEWEB)
Liao, Q.-Q., E-mail: liaoqq1971@yahoo.com.cn [Key Lab of Shanghai Colleges and Universities for Electric Power Corrosion Control and Applied Electrochemistry, Shanghai Engineering Research Center of Energy-Saving in Heat Exchange Systems, Shanghai University of Electric Power, Shanghai 200090 (China); Yue, Z.-W.; Yang, D. [Key Lab of Shanghai Colleges and Universities for Electric Power Corrosion Control and Applied Electrochemistry, Shanghai Engineering Research Center of Energy-Saving in Heat Exchange Systems, Shanghai University of Electric Power, Shanghai 200090 (China); Wang, Z.-H. [Department of Chemistry, Tongji University, Shanghai 200092 (China); Li, Z.-H. [Department of Chemistry, Fudan University, Shanghai 200433 (China); Ge, H.-H. [Key Lab of Shanghai Colleges and Universities for Electric Power Corrosion Control and Applied Electrochemistry, Shanghai Engineering Research Center of Energy-Saving in Heat Exchange Systems, Shanghai University of Electric Power, Shanghai 200090 (China); Li, Y.-J. [Department of Chemistry, Tongji University, Shanghai 200092 (China)
2011-07-29
Ammonium pyrrolidine dithiocarbamate (APDTC) monolayer was self-assembled on fresh copper surface obtained after oxidation-reduction cycle treatment in 0.1 mol L{sup -1} potassium chloride solution at ambient temperature. The APDTC self-assembled monolayer (SAM) on copper surface was investigated by surface enhanced Raman scattering spectroscopy and the results show that APDTC SAM is chemisorbed on copper surface by its sulfur atoms with perpendicular orientation. The optimum immersing period for SAM formation is 4 h at 0.01 mol L{sup -1} concentration of APDTC. The impedance results indicate that APDTC SAM has good corrosion inhibition effects for copper in 0.5 mol L{sup -1} hydrochloric acid solution and its maximum inhibition efficiency could reach 95%. Quantum chemical calculations show that APDTC has relatively small {Delta}E between the highest occupied molecular orbital and the lowest unoccupied molecular orbital and large negative charge in its two sulfur atoms, which facilitate formation of an insulating Cu/APDTC film on copper surface.
Ünal, Arslan; Eren, Bilge; Eren, Erdal
2013-10-01
Photophysical properties of the azo-hydrazone tautomerism of Eriochrome Blue Black B (1-(1-hydroxy-2-naphthylazo)-2-naphthol-4-sulphonic acid) in DMF, MeCN and water were investigated using UV-visible spectroscopy and quantum chemical calculations. The optimized molecular structure parameters, relative energies, mole fractions, electronic absorption spectra and HOMO-LUMO energies for possible stable tautomeric forms of EBB were theoretically calculated by using hybrid density functional theory, (B3LYP) methods with 6-31G(d) basis set level and polarizable continuum model (PCM) for solvation effect. The effects of varying pH-, dye concentration-, solvent-, temperature-, and time-dependences on the UV-vis spectra of Eriochrome Blue Black B were also investigated experimentally. The calculations showed that the dye exhibited acid-base, azo-hydrazone and aggregate equilibria in DMF solution, while the most probably preferred form in MeCN solution was azo form. Thermodynamic parameters of dimerization reaction in DMF solution proved that entropy was the driving force of this reaction.
Jing, Yu; Chen, Ji; Chen, Li; Su, Wenrou; Liu, Yu; Li, Deqian
2017-03-30
Heavy rare earths (HREs), namely Ho(3+), Er(3+), Tm(3+), Yb(3+) and Lu(3+), are rarer and more exceptional than light rare earths, due to the stronger extraction capacity for 100 000 extractions. Therefore, their incomplete stripping and high acidity of stripping become problems for HRE separation by organophosphoric extractants. However, the theories of extractant structure-performance relationship and molecular design method of novel HRE extractants are still not perfect. Beyond the coordination chemistry of the HRE-extracted complex, the extractant dimer dissociation, acid ionization, and complexation behaviors can be crucial to HRE extraction and reactivity of ionic species for understanding and further improving the extraction performance. To address the above issues, three primary fundamental processes, including extractant dimer dissociation, acid ionization, and HRE complexation, were identified and investigated systematically. The intrinsic extraction performances of HRE cations with four acidic organophosphoric extractants (P507, P204, P227 and Cyanex 272) were studied by using relativistic energy-consistent 4f core pseudopotentials, combined with density functional theory and a solvation model. Four acidic organophosphoric extractants have been qualified quantitatively from microscopic structures to chemical properties. It has been found that the Gibbs free energy changes of the overall extraction process (sequence: P204 > P227 > P507 > Cyanex 272) and their differences as a function of HREs (sequence: Ho/Er > Er/Tm > Tm/Yb > Yb/Lu) are in good agreement with the experimental maximum extraction capacities and separation factors. These results could provide an important approach to evaluate HRE extractants by the comprehensive consideration of dimer dissociation, acid ionization, and complexation processes. This paper also demonstrates the importance of the P-O bond, the P-C bond, isomer substituent, and solvation effects on the structure
Wojnárovits, L.
Ionizing radiation causes chemical changes in the molecules of the interacting medium. The initial molecules change to new molecules, resulting in changes of the physical, chemical, and eventually biological properties of the material. For instance, water decomposes to its elements H2 and O2. In polymers, degradation and crosslinking take place. In biopolymers, e.g., DNS strand breaks and other alterations occur. Such changes are to be avoided in some cases (radiation protection), however, in other cases they are used for technological purposes (radiation processing). This chapter introduces radiation chemistry by discussing the sources of ionizing radiation (radionuclide sources, machine sources), absorption of radiation energy, techniques used in radiation chemistry research, and methods of absorbed energy (absorbed dose) measurements. Radiation chemistry of different classes of inorganic (water and aqueous solutions, inorganic solids, ionic liquids (ILs)) and organic substances (hydrocarbons, halogenated compounds, polymers, and biomolecules) is discussed in concise form together with theoretical and experimental backgrounds. An essential part of the chapter is the introduction of radiation processing technologies in the fields of polymer chemistry, food processing, and sterilization. The application of radiation chemistry to nuclear technology and to protection of environment (flue gas treatment, wastewater treatment) is also discussed.
Gu, Wenliang; Gong, Suqin; Zhou, Yunlong; Xia, Yunsheng
2017-04-15
We herein present an effective and versatile platform for ratiometric sensing of metabolites using intrinsically dual-emitting ZnS:Mn(2+) quantum dots (QDs) as sole reporter. To avoid notoriously non-specific interactions, a special triple-layer "filter screen" around the inorganic QD core is rationally constructed, which is made of oleic acid, cetyltrimethyl ammonium bromide and bio-enzymes. In the presence of the analytes, the in-situ enzymatic H2O2 molecules diffuse and pass through the "filter screen" along the molecule interspace, which then reacts with the inorganic core and leads to more dramatically quenching of the Mn(2+) emission. The ratiometric signal readout is so distinct that can be observed by naked eyes (from orange to violet). In contrast, various coexisting bio-molecules, due to larger size, are well prevented from penetrating the filter screen by steric hindrance effect. So, various potential interfering substances do not disturb the assay. Under optimal conditions, five kinds of the corresponding substrates, namely glucose, cholesterol, lactate, xanthine and uric acid are well quantified by the emission intensity ratio of I470/I615, and the linear ranges are 0.1-200µM, 0.1-200µM, 1-200µM, 1-200µM and 1-200µM, respectively. The detection limits can even reach quasi-picomole levels. Because of favorable analytical performances (excellent selectivity, appropriate sensitivity and broad linear range), the proposed system can direct assay the analytes in blood without any sample pre-treatment.
Park, Jung Jin; Lacerda, Silvia H De Paoli; Stanley, Scott K; Vogel, Brandon M; Kim, Sangcheol; Douglas, Jack F; Raghavan, Dharmaraj; Karim, Alamgir
2009-01-06
We investigate the utility of Langmuir adsorption measurements for characterizing nanoparticle-substrate interactions. Spherical CdSe/ZnS core-shell nanoparticles were chosen as representative particles because of their widespread use in biological labeling measurements and their relatively monodisperse dimensions. In particular, the quantum dots were functionalized with 11-mercaptoundecanoic acid, and we utilized an amine-terminated self-assembled monolayer (SAM) as a model substrate. SAMs with different end-groups (-CH(3) and -COOH) were also considered to contrast with the adsorption behavior on the amine-terminated SAM substrates. We followed the kinetics of nanoparticle adsorption on the aminosilane layer by quartz crystal microgravimetry (QCM) over a range of particle concentrations and determined the corresponding Langmuir adsorption isotherms. Analysis of both equilibrium adsorption and kinetic adsorption data allowed us to determine a consistent value of the Langmuir adsorption equilibrium constant for the amine-terminated SAM at room temperature (K(L) approximately 2.7 (micromol/L)(-1)), providing a useful characterization of the nanoparticle-substrate interaction. The effect of varying solution pH on Langmuir adsorption was also investigated in order to gain insight into the role of electrostatic interactions on nanoparticle adsorption. The equilibrium extent of adsorption was found to be maximum at about pH 7. These changes of nanoparticle adsorption were further quantified and validated by X-ray photoelectron spectroscopy (XPS) and confocal fluorescence microscopy measurements. We conclude that Langmuir adsorption measurements provide a promising approach for quantifying nanoparticle-substrate interactions.
Handbook of heterocyclic chemistry
National Research Council Canada - National Science Library
Katritzky, Alan R
2010-01-01
... Heterocyclic Chemistry I (1984) Comprehensive Heterocyclic Chemistry II (1996) Comprehensive Heterocyclic Chemistry III (2008) Comprehensive Organic Functional Group Transformations I (1995) Compreh...
Quantum Effects in Biological Systems
2016-01-01
Since the last decade the study of quantum mechanical phenomena in biological systems has become a vibrant field of research. Initially sparked by evidence of quantum effects in energy transport that is instrumental for photosynthesis, quantum biology asks the question of how methods and models from quantum theory can help us to understand fundamental mechanisms in living organisms. This approach entails a paradigm change challenging the related disciplines: The successful framework of quantum theory is taken out of its low-temperature, microscopic regimes and applied to hot and dense macroscopic environments, thereby extending the toolbox of biology and biochemistry at the same time. The Quantum Effects in Biological Systems conference is a platform for researchers from biology, chemistry and physics to present and discuss the latest developments in the field of quantum biology. After meetings in Lisbon (2009), Harvard (2010), Ulm (2011), Berkeley (2012), Vienna (2013), Singapore (2014) and Florence (2015),...
Superheavy Elements Challenge Experimental and Theoretical Chemistry
Zvára, I
2003-01-01
When reflecting on the story of superheavy elements, the an experimenter, acknowledges the role, which the predictions of nuclear and chemical theories have played in ongoing studies. Today, the problems of major interest for experimental chemistry are the studies of elements 112 and 114 including their chemical identification. Advanced quantum chemistry calculations of atoms and molecules would be of much help. First experiments with element 112 evidence that the metal is much more volatile and inert than mercury.
Selected new developments in computational chemistry.
Darden, T A; Bartolotti, L; Pedersen, L G
1996-01-01
Molecular dynamics is a general technique for simulating the time-dependent properties of molecules and their environments. Quantum mechanics, as applied to molecules or clusters of molecules, provides a prescription for predicting properties exactly (in principle). It is reasonable to expect that both will have a profound effect on our understanding of environmental chemistry in the future. In this review, we consider several recent advances and applications in computational chemistry. Images Figure 1. PMID:8722111
Williams, Martha; Roberson, Luke; Caraccio, Anne
2010-01-01
This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.
Problems in structural inorganic chemistry
Li, Wai-Kee; Mak, Thomas Chung Wai; Mak, Kendrew Kin Wah
2013-01-01
This book consists of over 300 problems (and their solutions) in structural inorganic chemistry at the senior undergraduate and beginning graduate level. The topics covered comprise Atomic and Molecular Electronic States, Atomic Orbitals, Hybrid Orbitals, Molecular Symmetry, Molecular Geometry and Bonding, Crystal Field Theory, Molecular Orbital Theory, Vibrational Spectroscopy, and Crystal Structure. The central theme running through these topics is symmetry, molecular or crystalline. The problems collected in this volume originate in examination papers and take-home assignments that have been part of the teaching of the book's two senior authors' at The Chinese University of Hong Kong over the past four decades. The authors' courses include Chemical Bonding, Elementary Quantum Chemistry, Advanced Inorganic Chemistry, X-Ray Crystallography, etc. The problems have been tested by generations of students taking these courses.
Sullivan, P. Teal; Carsten Conner, L. D.; Guthrie, Mareca; Pompea, Stephen; Tsurusaki, Blakely K.; Tzou, Carrie
2017-01-01
This article describes a chemistry/art activity that originated in an National Science Foundation--funded two-week STEAM (Science, Technology, Engineering, Art, and Math) academy for grade 4-6 girls. The authors recommend using this investigation in conjunction with other activities focusing on chemical change as a step toward fulfilling the…
Quantum Chemistry Study on Cluster NixZry (x:y=1∶2 or 2∶1)%NixZry(x:y=1∶2或2∶1)团簇的量子化学研究
Institute of Scientific and Technical Information of China (English)
董昆明; 王艺平; 林梦海; 莫亦荣; 吴玮; 张乾二
2001-01-01
According to chemical bond theory and topological principle, 46 non-crystalline clusters NixZry (x:y=1∶2 or 2∶1, x+y≤9) have been examined and optimized by using quantum chemistry ab initio method. The calculation results show that for NixZry (x:y=1∶2) the lower-symmetry plane configurations are more stable than solid tri-prism configuration, and for NixZry (x:y=2∶1) it is reverse. The difference may be due to diverse valence electrons of transition metals∶ There is only 4 valence electrons in zirconium, so it enjoys at plane configuration of lower coordination number, and nickel (4d23d8) more fits to solid configuration.%根据化学键理论和拓扑学原理，设计了非晶态团簇NixZry(x:y=1∶2 或2∶1, x+y≤9)的几十种可能的构型，并应用量子化学从头算方法对它们的几何构型进行了优化，分析比较了这些构型的能量和稳定性。结果表明对于NixZry(x:y=1∶2)低对称性的平面构型最稳定，而NixZry(x:y=2∶1)三棱柱构型最稳定。这可能是由于两者外层价电子的数量差异所致： Zr仅有4个价电子，较适宜配位数低的平面构型，而Ni（4s23d8)，更适宜立体构型。
Strzalko, Tekla; Wartski, Lya; Corset, Jacques; Castellà-Ventura, Martine; Froment, Françoise
2012-08-01
Mechanisms of alkylation by PhCH(2)Cl or CH(3)I in THF and of deuteriation by DCl (4 N in D(2)O) in THF or THF-toluene of lithiated phenylacetonitrile monoanions and dianions obtained with LHMDS, LDA, or n-BuLi are studied by vibrational and NMR spectroscopy and quantum chemistry calculations. Dialkylation of the three dilithio dianions generated with n-BuLi (2.0-2.7 equiv, THF-hexane) depends on their structure: N-lithio (PhCCNLi)(-)Li(+) and (C,N)-dilithio PhCLiCNLi dianions afford PhCR(2)CN (R = PhCH(2), CH(3)) from the intermediate N-lithio monoalkylated monoanion PhCRCNLi 10; C-lithio dianion (PhCLiCN)(-)Li(+) leads to a carbenoid species, the C-lithio monoalkylated nitrile PhCLiRCN 11, which either eliminates carbene Ph-C-R and different LiCN species or isomerizes to PhCRCNLi in the presence of LiX (X = Cl, I). Dialkylation or dideuteriation of monoanions (monomers, dimers, and heterodimers [PhCHCNLi·LiR'], R' = (SiMe(3))(2)N, (i-Pr)(2)N) obtained with LHMDS or LDA (2.4 equiv, THF) proceeds via a sequential mechanism involving monometalation-monoalkylation (or monodeuteriation) reactions. Some carbene and (LiCNLi)(+) are also observed, and explained by another mechanism implying the C-lithio monoalkylated monoanion PhCLiRCN 9 in the presence of LiX. These results show the ambiphilic behavior of PhCLiRCN as a carbenoid (11) or a carbanion (9) and the importance of LiX formed in situ in the first alkylation step.
Quantum Chemistry Study on Paralytic Shellfish Poisoning Toxins%麻痹性贝毒素生物毒性的量子化学研究
Institute of Scientific and Technical Information of China (English)
张永清; 刁宁
2011-01-01
Quantum chemical descriptors computed with density functional theory at the B3LYP/6-31G (d) level and the modified ant colony algorithm with amended Cp statistical quantity as an objective function were used to set up QSAR models for the natural logarithm of semi-lethal doses of 17 paralytic shellfish poisoning (PSP) toxins. The model with high correlation coefficients (R2=0.968) and a high cross-validation test result (q2=0.858) shows that the model has high precision and good prediction capacity. The jackknife method is also used to test the model's stability and reliability. Among the descriptors investigated, the eigenvalue of the highest occupied molecular orbital plays the most important role in the lethal dose of PSP toxins, and the next highest occupied molecular orbital plays an important role in the medium lethal dose of PSP toxins. Thus it is concluded that the interaction of molecular orbitals and the molecule's reactivity have decisive influence on the biotoxicity of PSP toxins.%运用密度泛函(DFT)理论在B3LYP/6-31G(d)水平下计算了17种麻痹性贝毒素的量子化学结构描述符,采用修正Cp统计量为目标函数的改进蚁群算法进行变量选择,建立了麻痹性贝毒素的半数致死浓度与其量化参数之间的QSAR模型;模型的决定系数R2为0.968,交叉验证系数q2为0.858,表明模型具备良好的拟合效果和较好的预测能力;同时使用"jackknife法"检验模型,相关系数R有16个落在0.982-0.987之间,占总数的94.1%,表明模型具有较强的稳健性.在所考察的诸多参数中,分子最高占有轨道特征值EHOMO对麻痹性贝类毒素的半数致死剂量影响最大,其次为分子的次高占据轨道能量ENHOMO,说明分子的轨道相互作用和反应活性对麻痹性贝毒素的生物毒性具有决定性的影响.
Li, Shu-Shen; Long, Gui-lu; Bai, Feng-Shan; Feng, Song-Lin; Zheng, Hou-Zhi
2001-01-01
Quantum computing is a quickly growing research field. This article introduces the basic concepts of quantum computing, recent developments in quantum searching, and decoherence in a possible quantum dot realization.
Industrial chemistry engineering
Energy Technology Data Exchange (ETDEWEB)
NONE
1993-01-15
This book on industrial chemistry engineering is divided in two parts. The first part deals with industrial chemistry, inorganic industrial chemistry, organic industrial chemistry, analytical chemistry and practical questions. The last parts explain the chemical industry, a unit parts and thermodynamics in chemical industry and reference. It reveals the test subjects for the industrial chemistry engineering with a written examination and practical skill.
Dori, Yehudit Judy; Dangur, Vered; Avargil, Shirly; Peskin, Uri
2014-01-01
Chemistry students in Israel have two options for studying chemistry: basic or honors (advanced placement). For instruction in high school honors chemistry courses, we developed a module focusing on abstract topics in quantum mechanics: Chemistry--From the Nanoscale to Microelectronics. The module adopts a visual-conceptual approach, which…
Dori, Yehudit Judy; Dangur, Vered; Avargil, Shirly; Peskin, Uri
2014-01-01
Chemistry students in Israel have two options for studying chemistry: basic or honors (advanced placement). For instruction in high school honors chemistry courses, we developed a module focusing on abstract topics in quantum mechanics: Chemistry--From the Nanoscale to Microelectronics. The module adopts a visual-conceptual approach, which…
The formalisms of quantum mechanics an introduction
David, Francois
2015-01-01
These lecture notes present a concise and introductory, yet as far as possible coherent, view of the main formalizations of quantum mechanics and of quantum field theories, their interrelations and their theoretical foundations. The “standard” formulation of quantum mechanics (involving the Hilbert space of pure states, self-adjoint operators as physical observables, and the probabilistic interpretation given by the Born rule) on one hand, and the path integral and functional integral representations of probabilities amplitudes on the other, are the standard tools used in most applications of quantum theory in physics and chemistry. Yet, other mathematical representations of quantum mechanics sometimes allow better comprehension and justification of quantum theory. This text focuses on two of such representations: the algebraic formulation of quantum mechanics and the “quantum logic” approach. Last but not least, some emphasis will also be put on understanding the relation between quantum physics and ...
Arnold, J. O.
1987-01-01
With the advent of supercomputers, modern computational chemistry algorithms and codes, a powerful tool was created to help fill NASA's continuing need for information on the properties of matter in hostile or unusual environments. Computational resources provided under the National Aerodynamics Simulator (NAS) program were a cornerstone for recent advancements in this field. Properties of gases, materials, and their interactions can be determined from solutions of the governing equations. In the case of gases, for example, radiative transition probabilites per particle, bond-dissociation energies, and rates of simple chemical reactions can be determined computationally as reliably as from experiment. The data are proving to be quite valuable in providing inputs to real-gas flow simulation codes used to compute aerothermodynamic loads on NASA's aeroassist orbital transfer vehicles and a host of problems related to the National Aerospace Plane Program. Although more approximate, similar solutions can be obtained for ensembles of atoms simulating small particles of materials with and without the presence of gases. Computational chemistry has application in studying catalysis, properties of polymers, all of interest to various NASA missions, including those previously mentioned. In addition to discussing these applications of computational chemistry within NASA, the governing equations and the need for supercomputers for their solution is outlined.
Bioscience methodologies in physical chemistry an engineering and molecular approach
D'Amore, Alberto
2013-01-01
The field of bioscience methodologies in physical chemistry stands at the intersection of the power and generality of classical and quantum physics with the minute molecular complexity of chemistry and biology. This book provides an application of physical principles in explaining and rationalizing chemical and biological phenomena. It does not stick to the classical topics that are conventionally considered as part of physical chemistry; instead it presents principles deciphered from a modern point of view, which is the strength of this book.
Quantum-enhanced absorption refrigerators
Correa, Luis A; Alonso, Daniel; Adesso, Gerardo
2014-01-01
Thermodynamics is a branch of science blessed by an unparalleled combination of generality of scope and formal simplicity. Based on few natural assumptions together with the four laws, it sets the boundaries between possible and impossible in macroscopic aggregates of matter. This triggered groundbreaking achievements in physics, chemistry and engineering over the last two centuries. Close analogues of those fundamental laws are now being established at the level of individual quantum systems, thus placing limits on the operation of quantum-mechanical devices. Here we study quantum absorption refrigerators, which are driven by heat rather than external work. We establish thermodynamic performance bounds for these machines and investigate their quantum origin. We also show how those bounds may be pushed beyond what is classically achievable, by suitably tailoring the environmental fluctuations via quantum reservoir engineering techniques. Such superefficient quantum-enhanced cooling realises a promising step t...
Quantum Distinction: Quantum Distinctiones!
Zeps, Dainis
2009-01-01
10 pages; How many distinctions, in Latin, quantum distinctiones. We suggest approach of anthropic principle based on anthropic reference system which should be applied equally both in theoretical physics and in mathematics. We come to principle that within reference system of life subject of mathematics (that of thinking) should be equated with subject of physics (that of nature). For this reason we enter notions of series of distinctions, quantum distinction, and argue that quantum distinct...
Molecular electromagnetism a computational chemistry approach
Sauer, Stephan P A
2011-01-01
A textbook for a one-semester course for students in chemistry physics and nanotechnology, this book examines the interaction of molecules with electric and magnetic fields as, for example in light. The book provides the necessary background knowledge for simulating these interactions on computers with modern quantum chemical software.
Theoretical chemistry periodicities in chemistry and biology
Eyring, Henry
1978-01-01
Theoretical Chemistry: Periodicities in Chemistry and Biology, Volume 4 covers the aspects of theoretical chemistry. The book discusses the stably rotating patterns of reaction and diffusion; the chemistry of inorganic systems exhibiting nonmonotonic behavior; and population cycles. The text also describes the mathematical modeling of excitable media in neurobiology and chemistry; oscillating enzyme reactions; and oscillatory properties and excitability of the heart cell membrane. Selected topics from the theory of physico-chemical instabilities are also encompassed. Chemists, mechanical engin
Mortimer, Robert G
2008-01-01
In this third edition, core applications have been added along with more recent developments in the theories of chemical reaction kinetics and molecular quantum mechanics, as well as in the experimental study of extremely rapid chemical reactions.* Fully revised concise edition covering recent developments in the field* Supports student learning with step by step explanation of fundamental principles, an appropriate level of math rigor, and pedagogical tools to aid comprehension* Encourages readers to apply theory in practical situations
Directory of Open Access Journals (Sweden)
Luiz Carlos Gomide Freitas
1999-04-01
Full Text Available A résumé of the evolution of quantum chemistry methodologies is presented. The pioneering contributions of John A. Pople and Water Kohn, the 1998 Nobel Prize Laureates in Chemistry, to the development of quantum chemistry computational methods for studying the properties of molecules and their interaction is discussed.
Welcome to Quantum Science and Technology
Thew, Rob
2016-03-01
Quantum information science and related technologies now involve thousands of researchers worldwide, cutting across physics, chemistry, engineering, bioscience, applied mathematics and computer science, extending from fundamental science to novel applications and industry. This situation defines the scope and mission of Quantum Science and Technology, a new IOP journal serving the interests of this multidisciplinary field by publishing research of the highest quality and impact.
Institute of Scientific and Technical Information of China (English)
张志坚; 邝代治; 张复兴; 蒋伍玖
2013-01-01
间苯二甲酸与三苯基氢氧化锡反应，合成了标题化合物，经元素分析、1H NMR 和 IR 表征，通过 X 射线衍射方法测定了化合物的晶体结构。该化合物晶体学参数：单斜晶系，空间群为 P21/n，晶胞参数：a=1.06210(3) nm，b=2.64095(6) nm，c=1.37498(4) nm，α=90°，β=103.1210(10)°，γ=90°，V =3.75606(17) nm3，Z=4，Dc=1.526 g/cm3，µ(MoKα)=1.371 mm-1， F(000)=1716，and R1=0.0257，wR2=0.0601；中心锡原子呈四配位畸变四面体构型。利用量子化学 G98W 软件，在 Lanl2dz 基组对化合物的稳定性、前沿分子轨道组成及能量进行研究。% The title complex, Bis(triphenyltin) m-Phthalate, has been synthesized by the reaction of triphenytin Hydroxide with m-phthalic acid and characterized by IR, 1H NMR spectra and elemental analysis. The crystal structure has been determined by X-ray diffraction. Crystal data for this complex: monoclinic system, space group P21/n with a =1.06210(3) nm, b =2.64095(6) nm, c =1.37498(4) nm, α=90°,β=103.1210(10)°, γ=90°, V=3.75606(17) nm3, Z=4, Dc= 1.526g/cm3, µ(MoKα) = 1.371 mm-1, F(000) =1716, and R1 =0.0257, wR2=0.0601. The crystal structure shows that the central Sn atom is four-coordinated to assume a distorted tetrahedral configuration. The study on title complex has been performed, with quantum chemistry calculation by means of G98W package and taking Lanl2dz basis set. The stabilities of the complex, the orbital energies and composition characteristics some frontier molecular orbital have been investigated.
Desai, KR
2008-01-01
The surface Chemistry of a material as a whole is crucially dependent upon the Nature and type of surfaces exposed on crystallites. It is therefore vitally important to independently Study different, well - defined surfaces through surface analytical techniques. In addition to composition and structure of surface, the subject also provides information on dynamic light scattering, micro emulsions, colloid Stability control and nanostructures. The present book endeavour to bring before the reader that the understanding and exploitation of Solid state phenomena depended largely on the ability to
Coherent Dynamics of Complex Quantum Systems
Akulin, Vladimir M
2006-01-01
A large number of modern problems in physics, chemistry, and quantum electronics require a consideration of population dynamics in complex multilevel quantum systems. The purpose of this book is to provide a systematic treatment of these questions and to present a number of exactly solvable problems. It considers the different dynamical problems frequently encountered in different areas of physics from the same perspective, based mainly on the fundamental ideas of group theory and on the idea of ensemble average. Also treated are concepts of complete quantum control and correction of decoherence induced errors that are complementary to the idea of ensemble average. "Coherent Dynamics of Complex Quantum Systems" is aimed at senior-level undergraduate students in the areas of Atomic, Molecular, and Laser Physics, Physical Chemistry, Quantum Optics and Quantum Informatics. It should help them put particular problems in these fields into a broader scientific context and thereby take advantage of the well-elabora...
Introduction to quantum mechanics a time-dependent perspective
Tannor, David J
2007-01-01
"Introduction to Quantum Mechanics" covers quantum mechanics from a time-dependent perspective in a unified way from beginning to end. Intended for upper-level undergraduate and graduate courses this text will change the way people think about and teach quantum mechanics in chemistry and physics departments.
Simple Perturbation Example for Quantum Chemistry.
Goodfriend, P. L.
1985-01-01
Presents a simple example that illustrates various aspects of the Rayleigh-Schrodinger perturbation theory. The example is a particularly good one because it is straightforward and can be compared with both the exact solution and with experimental data. (JN)
Graph theory data for topological quantum chemistry
Vergniory, M. G.; Elcoro, L.; Wang, Zhijun; Cano, Jennifer; Felser, C.; Aroyo, M. I.; Bernevig, B. Andrei; Bradlyn, Barry
2017-08-01
Topological phases of noninteracting particles are distinguished by the global properties of their band structure and eigenfunctions in momentum space. On the other hand, group theory as conventionally applied to solid-state physics focuses only on properties that are local (at high-symmetry points, lines, and planes) in the Brillouin zone. To bridge this gap, we have previously [Bradlyn et al., Nature (London) 547, 298 (2017), 10.1038/nature23268] mapped the problem of constructing global band structures out of local data to a graph construction problem. In this paper, we provide the explicit data and formulate the necessary algorithms to produce all topologically distinct graphs. Furthermore, we show how to apply these algorithms to certain "elementary" band structures highlighted in the aforementioned reference, and thus we identified and tabulated all orbital types and lattices that can give rise to topologically disconnected band structures. Finally, we show how to use the newly developed bandrep program on the Bilbao Crystallographic Server to access the results of our computation.
Energy Technology Data Exchange (ETDEWEB)
Robinett, R.W
2004-03-01
The numerical prediction, theoretical analysis, and experimental verification of the phenomenon of wave packet revivals in quantum systems has flourished over the last decade and a half. Quantum revivals are characterized by initially localized quantum states which have a short-term, quasi-classical time evolution, which then can spread significantly over several orbits, only to reform later in the form of a quantum revival in which the spreading reverses itself, the wave packet relocalizes, and the semi-classical periodicity is once again evident. Relocalization of the initial wave packet into a number of smaller copies of the initial packet ('minipackets' or 'clones') is also possible, giving rise to fractional revivals. Systems exhibiting such behavior are a fundamental realization of time-dependent interference phenomena for bound states with quantized energies in quantum mechanics and are therefore of wide interest in the physics and chemistry communities. We review the theoretical machinery of quantum wave packet construction leading to the existence of revivals and fractional revivals, in systems with one (or more) quantum number(s), as well as discussing how information on the classical period and revival time is encoded in the energy eigenvalue spectrum. We discuss a number of one-dimensional model systems which exhibit revival behavior, including the infinite well, the quantum bouncer, and others, as well as several two-dimensional integrable quantum billiard systems. Finally, we briefly review the experimental evidence for wave packet revivals in atomic, molecular, and other systems, and related revival phenomena in condensed matter and optical systems.
Robinett, R. W.
2004-03-01
The numerical prediction, theoretical analysis, and experimental verification of the phenomenon of wave packet revivals in quantum systems has flourished over the last decade and a half. Quantum revivals are characterized by initially localized quantum states which have a short-term, quasi-classical time evolution, which then can spread significantly over several orbits, only to reform later in the form of a quantum revival in which the spreading reverses itself, the wave packet relocalizes, and the semi-classical periodicity is once again evident. Relocalization of the initial wave packet into a number of smaller copies of the initial packet (‘minipackets’ or ‘clones’) is also possible, giving rise to fractional revivals. Systems exhibiting such behavior are a fundamental realization of time-dependent interference phenomena for bound states with quantized energies in quantum mechanics and are therefore of wide interest in the physics and chemistry communities. We review the theoretical machinery of quantum wave packet construction leading to the existence of revivals and fractional revivals, in systems with one (or more) quantum number(s), as well as discussing how information on the classical period and revival time is encoded in the energy eigenvalue spectrum. We discuss a number of one-dimensional model systems which exhibit revival behavior, including the infinite well, the quantum bouncer, and others, as well as several two-dimensional integrable quantum billiard systems. Finally, we briefly review the experimental evidence for wave packet revivals in atomic, molecular, and other systems, and related revival phenomena in condensed matter and optical systems.
Why Teach Environmental Chemistry?
Gardner, Marjorie H.
1974-01-01
Discusses the importance of teaching environmental chemistry in secondary school science classes, and outlines five examples of environmental chemistry problems that focus on major concepts of chemistry and have critical implications for human survival and well-being. (JR)
Science Update: Inorganic Chemistry
Rawls, Rebecca
1978-01-01
This first in a series of articles describing the state of the art of various branches of chemistry reviews inorganic chemistry, including bioinorganic, photochemistry, organometallic, and solid state chemistries. (SL)
Fundamentals of quantum mechanics
House, J E
2017-01-01
Fundamentals of Quantum Mechanics, Third Edition is a clear and detailed introduction to quantum mechanics and its applications in chemistry and physics. All required math is clearly explained, including intermediate steps in derivations, and concise review of the math is included in the text at appropriate points. Most of the elementary quantum mechanical models-including particles in boxes, rigid rotor, harmonic oscillator, barrier penetration, hydrogen atom-are clearly and completely presented. Applications of these models to selected “real world” topics are also included. This new edition includes many new topics such as band theory and heat capacity of solids, spectroscopy of molecules and complexes (including applications to ligand field theory), and small molecules of astrophysical interest.
Chang, Mou-Hsiung
2015-01-01
The classical probability theory initiated by Kolmogorov and its quantum counterpart, pioneered by von Neumann, were created at about the same time in the 1930s, but development of the quantum theory has trailed far behind. Although highly appealing, the quantum theory has a steep learning curve, requiring tools from both probability and analysis and a facility for combining the two viewpoints. This book is a systematic, self-contained account of the core of quantum probability and quantum stochastic processes for graduate students and researchers. The only assumed background is knowledge of the basic theory of Hilbert spaces, bounded linear operators, and classical Markov processes. From there, the book introduces additional tools from analysis, and then builds the quantum probability framework needed to support applications to quantum control and quantum information and communication. These include quantum noise, quantum stochastic calculus, stochastic quantum differential equations, quantum Markov semigrou...
Steane, A M
1998-01-01
The subject of quantum computing brings together ideas from classical information theory, computer science, and quantum physics. This review aims to summarise not just quantum computing, but the whole subject of quantum information theory. It turns out that information theory and quantum mechanics fit together very well. In order to explain their relationship, the review begins with an introduction to classical information theory and computer science, including Shannon's theorem, error correcting codes, Turing machines and computational complexity. The principles of quantum mechanics are then outlined, and the EPR experiment described. The EPR-Bell correlations, and quantum entanglement in general, form the essential new ingredient which distinguishes quantum from classical information theory, and, arguably, quantum from classical physics. Basic quantum information ideas are described, including key distribution, teleportation, data compression, quantum error correction, the universal quantum computer and qua...
Environmental chemistry. Seventh edition
Energy Technology Data Exchange (ETDEWEB)
Manahan, S.E. [Univ. of Missouri, Columbia, MO (United States)
1999-11-01
This book presents a basic understanding of environmental chemistry and its applications. In addition to providing updated materials in this field, the book emphasizes the major concepts essential to the practice of environmental chemistry. Topics of discussion include the following: toxicological chemistry; toxicological chemistry of chemical substances; chemical analysis of water and wastewater; chemical analysis of wastes and solids; air and gas analysis; chemical analysis of biological materials and xenobiotics; fundamentals of chemistry; and fundamentals of organic chemistry.
Klemperer, William
2011-01-01
The discovery of polar polyatomic molecules in higher-density regions of the interstellar medium by means of their rotational emission detected by radioastronomy has changed our conception of the universe from essentially atomic to highly molecular. We discuss models for molecule formation, emphasizing the general lack of thermodynamic equilibrium. Detailed chemical kinetics is needed to understand molecule formation as well as destruction. Ion molecule reactions appear to be an important class for the generally low temperatures of the interstellar medium. The need for the intrinsically high-quality factor of rotational transitions to definitively pin down molecular emitters has been well established by radioastronomy. The observation of abundant molecular ions both positive and, as recently observed, negative provides benchmarks for chemical kinetic schemes. Of considerable importance in guiding our understanding of astronomical chemistry is the fact that the larger molecules (with more than five atoms) are all organic.
Gosson, Maurice A. de
2012-01-01
Quantum blobs are the smallest phase space units of phase space compatible with the uncertainty principle of quantum mechanics and having the symplectic group as group of symmetries. Quantum blobs are in a bijective correspondence with the squeezed coherent states from standard quantum mechanics, of which they are a phase space picture. This allows us to propose a substitute for phase space in quantum mechanics. We study the relationship between quantum blobs with a certain class of level set...
Science Update: Inorganic Chemistry.
Rawls, Rebecca
1981-01-01
Describes areas of inorganic chemistry which have changed dramatically in the past year or two, including photochemistry, electrochemistry, organometallic complexes, inorganic reaction theory, and solid state chemistry. (DS)
Federal Laboratory Consortium — Description/History: Chemistry laboratory The Advanced Chemistry Laboratory (ACL) is a unique facility designed for working with the most super toxic compounds known...
Nonlinear Dynamics In Quantum Physics -- Quantum Chaos and Quantum Instantons
Kröger, H.
2003-01-01
We discuss the recently proposed quantum action - its interpretation, its motivation, its mathematical properties and its use in physics: quantum mechanical tunneling, quantum instantons and quantum chaos.
Nonlinear Dynamics In Quantum Physics -- Quantum Chaos and Quantum Instantons
Kröger, H.
2003-01-01
We discuss the recently proposed quantum action - its interpretation, its motivation, its mathematical properties and its use in physics: quantum mechanical tunneling, quantum instantons and quantum chaos.
Proceedings of the international symposium on quantum biology and quantum pharmacology
Energy Technology Data Exchange (ETDEWEB)
Loewdin, P.O.; Oehrn, N.Y.; Sabin, J.R.; Zerner, M.C. (eds.)
1988-01-01
The document contains 22 papers on various aspects of quantum chemistry in biology. Topics include: the structure and function of photoreceptors, molecular design, simulation of proteins and nucleic acids using quantum mechanics and molecular mechanics, microscopic electrostatics and hydration phenomena, protein foldings, and protein relaxation. (TEM)
Institute of Scientific and Technical Information of China (English)
徐亚荣; 沈本贤; 徐新良; 朱庆才
2011-01-01
With the catalytic alkylation of methyl-thiophene and 2-methybutene-2 as the model reaction, the alkylation mechanism and the orientation effect of thiophenes in FCC gasoline were theoretically studied by ab initio quantum chemistry. LST/QST/CG was used to search the transition state to prove the feasibility and specific path of 2'-carbonium to 3'-carbornium by rearrangement. The results showed that the energy of 3 -carbonium was lower than that of 2'-carbonium, reaction active energy released by 2'-carbonium rearrangement to 3'-carbonium was only 19. 74 kj/mol, meaning that the rearrangement was a exothermic process. Alkylation reaction of 2-methyl-thiophene was typical electrophilic substitution reaction. The geometry structures of reactants, intermediates, transition states and products were optimized by searching for transient with LST/QST/CG. Energy of transition TS1 with R and IM as starting point was - 2. 072 X 106 kj/mol, with only virtual frequency of 132 cm-1. Energy of transition TS2 with IM and P as starting point was -2.071X106 kj/mol , with only virtual frequency of 128. 9 cm-1.%以各种甲基噻吩与2-甲基丁烯-2在催化剂作用下的烷基化反应为模型反应,对FCC汽油的噻吩类硫化物的定位效应和烷基化反应机理进行了从头算的量子化学研究.采用LST/QST/CG进行过渡态搜索,验证仲正碳离子进行重排转变为叔正碳离子的可行性和具体途径.结果表明,计算得到的叔正碳离子的能量低于仲正碳离子的,仲正碳离子重排为叔正碳离子是放热过程,该反应的能垒仅19.74 kJ/mol.2-甲基噻吩的烷基化反应是典型的亲电取代反应,对中间体IM及产物P进行结构优化,以分子复合物R和IM为起点进行LST/QST/CG过渡态搜索,所得过渡态TS1经优化后的几何构型的能量为-2.072×106 kJ/mol,在132 cm-1有唯一的虚频;以IM和P为起点进行LST/QST/CG过渡态搜索,所得过渡态TS2经优化后的能量为-2.071×106 k
Ihly, Rachelle
2014-01-01
This thesis explores the understanding of the chemistry and physics of colloidal quantum dots for practical solar energy photoconversion. Solar cell devices that make use of PbS quantum dots generally rely on constant and unchanged optical properties such that band gap energies remain tuned within the device. The design and development of unique experiments to ascertain mechanisms of optical band gap shifts occurring in PbS quantum dot thin-films exposed to air are discussed. The systematic s...
Lanzagorta, Marco
2011-01-01
This book offers a concise review of quantum radar theory. Our approach is pedagogical, making emphasis on the physics behind the operation of a hypothetical quantum radar. We concentrate our discussion on the two major models proposed to date: interferometric quantum radar and quantum illumination. In addition, this book offers some new results, including an analytical study of quantum interferometry in the X-band radar region with a variety of atmospheric conditions, a derivation of a quantum radar equation, and a discussion of quantum radar jamming.This book assumes the reader is familiar w
de Gosson, Maurice A
2011-01-01
Quantum blobs are the smallest phase space units of phase space compatible with the uncertainty principle of quantum mechanics and having the symplectic group as group of symmetries. Quantum blobs are in a bijective correspondence with the squeezed coherent states from standard quantum mechanics, of which they are a phase space picture. This allows us to propose a substitute for phase space in quantum mechanics. We study the relationship between quantum blobs with a certain class of level sets defined by Fermi for the purpose of representing geometrically quantum states.
Wu, L A; Wu, Lian-Ao; Lidar, Daniel
2005-01-01
Quantum computation and communication offer unprecedented advantages compared to classical information processing. Currently, quantum communication is moving from laboratory prototypes into real-life applications. When quantum communication networks become more widespread it is likely that they will be subject to attacks by hackers, virus makers, and other malicious intruders. Here we introduce the concept of "quantum malware" to describe such human-made intrusions. We offer a simple solution for storage of quantum information in a manner which protects quantum networks from quantum malware.
Scalable Quantum Simulation of Molecular Energies
O'Malley, P J J; Kivlichan, I D; Romero, J; McClean, J R; Barends, R; Kelly, J; Roushan, P; Tranter, A; Ding, N; Campbell, B; Chen, Y; Chen, Z; Chiaro, B; Dunsworth, A; Fowler, A G; Jeffrey, E; Megrant, A; Mutus, J Y; Neill, C; Quintana, C; Sank, D; Vainsencher, A; Wenner, J; White, T C; Coveney, P V; Love, P J; Neven, H; Aspuru-Guzik, A; Martinis, J M
2015-01-01
We report the first electronic structure calculation performed on a quantum computer without exponentially costly precompilation. We use a programmable array of superconducting qubits to compute the energy surface of molecular hydrogen using two distinct quantum algorithms. First, we experimentally execute the unitary coupled cluster method using the variational quantum eigensolver. Our efficient implementation predicts the correct dissociation energy to within chemical accuracy of the numerically exact result. Next, we experimentally demonstrate the canonical quantum algorithm for chemistry, which consists of Trotterization and quantum phase estimation. We compare the experimental performance of these approaches to show clear evidence that the variational quantum eigensolver is robust to certain errors, inspiring hope that quantum simulation of classically intractable molecules may be viable in the near future.
Elucidating reaction mechanisms on quantum computers.
Reiher, Markus; Wiebe, Nathan; Svore, Krysta M; Wecker, Dave; Troyer, Matthias
2017-07-18
With rapid recent advances in quantum technology, we are close to the threshold of quantum devices whose computational powers can exceed those of classical supercomputers. Here, we show that a quantum computer can be used to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical computer simulations used to probe these reaction mechanisms, to significantly increase their accuracy and enable hitherto intractable simulations. Our resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. Our results demonstrate that quantum computers will be able to tackle important problems in chemistry without requiring exorbitant resources.
Quantum simulations with photons and polaritons merging quantum optics with condensed matter physics
2017-01-01
This book reviews progress towards quantum simulators based on photonic and hybrid light-matter systems, covering theoretical proposals and recent experimental work. Quantum simulators are specially designed quantum computers. Their main aim is to simulate and understand complex and inaccessible quantum many-body phenomena found or predicted in condensed matter physics, materials science and exotic quantum field theories. Applications will include the engineering of smart materials, robust optical or electronic circuits, deciphering quantum chemistry and even the design of drugs. Technological developments in the fields of interfacing light and matter, especially in many-body quantum optics, have motivated recent proposals for quantum simulators based on strongly correlated photons and polaritons generated in hybrid light-matter systems. The latter have complementary strengths to cold atom and ion based simulators and they can probe for example out of equilibrium phenomena in a natural driven-dissipative sett...
Scarani, Valerio; Iblisdir, Sofyan; Gisin, Nicolas; Acin, Antonio
2005-01-01
The impossibility of perfectly copying (or cloning) an arbitrary quantum state is one of the basic rules governing the physics of quantum systems. The processes that perform the optimal approximate cloning have been found in many cases. These "quantum cloning machines" are important tools for studying a wide variety of tasks, e.g. state estimation and eavesdropping on quantum cryptography. This paper provides a comprehensive review of quantum cloning machines (both for discrete-dimensional an...
Entangled Systems New Directions in Quantum Physics
Audretsch, Jürgen
2007-01-01
An introductory textbook for advanced students of physics, chemistry and computer science, covering an area of physics that has lately witnessed rapid expansion. The topics treated here include quantum information, quantum communication, quantum computing, teleportation and hidden parameters, thus imparting not only a well-founded understanding of quantum theory as such, but also a solid basis of knowledge from which readers can follow the rapid development of the topic or delve deeper into a more specialized branch of research. Commented recommendations for further reading as well as end-of-chapter problems help the reader to quickly access the theoretical basics of future key technologies
Quantum CPU and Quantum Algorithm
Wang, An Min
1999-01-01
Making use of an universal quantum network -- QCPU proposed by me\\upcite{My1}, it is obtained that the whole quantum network which can implement some the known quantum algorithms including Deutsch algorithm, quantum Fourier transformation, Shor's algorithm and Grover's algorithm.
Quantum Computer Games: Quantum Minesweeper
Gordon, Michal; Gordon, Goren
2010-01-01
The computer game of quantum minesweeper is introduced as a quantum extension of the well-known classical minesweeper. Its main objective is to teach the unique concepts of quantum mechanics in a fun way. Quantum minesweeper demonstrates the effects of superposition, entanglement and their non-local characteristics. While in the classical…
Quantum Computer Games: Quantum Minesweeper
Gordon, Michal; Gordon, Goren
2010-01-01
The computer game of quantum minesweeper is introduced as a quantum extension of the well-known classical minesweeper. Its main objective is to teach the unique concepts of quantum mechanics in a fun way. Quantum minesweeper demonstrates the effects of superposition, entanglement and their non-local characteristics. While in the classical…
Atmospheric and aerosol chemistry
Energy Technology Data Exchange (ETDEWEB)
McNeill, V. Faye [Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering; Ariya, Parisa A. (ed.) [McGill Univ. Montreal, QC (Canada). Dept. of Chemistry; McGill Univ. Montreal, QC (Canada). Dept. of Atmospheric and Oceanic Sciences
2014-09-01
This series presents critical reviews of the present position and future trends in modern chemical research. Short and concise reports on chemistry, each written by the world renowned experts. Still valid and useful after 5 or 10 years. More information as well as the electronic version of the whole content available at: springerlink.com. Christian George, Barbara D'Anna, Hartmut Herrmann, Christian Weller, Veronica Vaida, D. J. Donaldson, Thorsten Bartels-Rausch, Markus Ammann Emerging Areas in Atmospheric Photochemistry. Lisa Whalley, Daniel Stone, Dwayne Heard New Insights into the Tropospheric Oxidation of Isoprene: Combining Field Measurements, Laboratory Studies, Chemical Modelling and Quantum Theory. Neil M. Donahue, Allen L. Robinson, Erica R. Trump, Ilona Riipinen, Jesse H. Kroll Volatility and Aging of Atmospheric Organic Aerosol. P. A. Ariya, G. Kos, R. Mortazavi, E. D. Hudson, V. Kanthasamy, N. Eltouny, J. Sun, C. Wilde Bio-Organic Materials in the Atmosphere and Snow: Measurement and Characterization V. Faye McNeill, Neha Sareen, Allison N. Schwier Surface-Active Organics in Atmospheric Aerosols.
Industrial Chemistry and School Chemistry: Making Chemistry Studies More Relevant
Hofstein, Avi; Kesner, Miri
2006-01-01
In this paper, we present the development and implementation over the period of more than 15 years of learning materials focusing on industrial chemistry as the main theme. The work was conducted in the Department of Science Teaching at the Weizmann Institute of Science, Israel. The project's general goal was to teach chemistry concepts in the…
Algorithms versus architectures for computational chemistry
Partridge, H.; Bauschlicher, C. W., Jr.
1986-01-01
The algorithms employed are computationally intensive and, as a result, increased performance (both algorithmic and architectural) is required to improve accuracy and to treat larger molecular systems. Several benchmark quantum chemistry codes are examined on a variety of architectures. While these codes are only a small portion of a typical quantum chemistry library, they illustrate many of the computationally intensive kernels and data manipulation requirements of some applications. Furthermore, understanding the performance of the existing algorithm on present and proposed supercomputers serves as a guide for future programs and algorithm development. The algorithms investigated are: (1) a sparse symmetric matrix vector product; (2) a four index integral transformation; and (3) the calculation of diatomic two electron Slater integrals. The vectorization strategies are examined for these algorithms for both the Cyber 205 and Cray XMP. In addition, multiprocessor implementations of the algorithms are looked at on the Cray XMP and on the MIT static data flow machine proposed by DENNIS.
From Matter to Life:Chemistry?Chemistry!
Institute of Scientific and Technical Information of China (English)
Jean-Marie; LEHN
2007-01-01
1 Results Animate as well as inanimate matter,living organisms as well as materials,are formed of molecules and of the organized entities resulting from the interaction of molecules with each other.Chemistry provides the bridge between the molecules of inanimate matter and the highly complex molecular architectures and systems which make up living organisms. Synthetic chemistry has developed a very powerful set of methods for constructing ever more complex molecules.Supramolecular chemistry seeks to con...
Green chemistry: A tool in Pharmaceutical Chemistry
Smita Talaviya; Falguni Majumdar
2012-01-01
Green chemistry expresses an area of research developing from scientific discoveries about pollution awareness and it utilizes a set of principles that reduces or eliminates the use or generation of hazardous substances in all steps of particular synthesis or process. Chemists and medicinal scientists can greatly reduce the risk to human health and the environment by following all the valuable principles of green chemistry. The most simple and direct way to apply green chemistry in pharmaceut...
Pfeiffer, P.; Egusquiza, I. L.; di Ventra, M.; Sanz, M.; Solano, E.
2016-07-01
Technology based on memristors, resistors with memory whose resistance depends on the history of the crossing charges, has lately enhanced the classical paradigm of computation with neuromorphic architectures. However, in contrast to the known quantized models of passive circuit elements, such as inductors, capacitors or resistors, the design and realization of a quantum memristor is still missing. Here, we introduce the concept of a quantum memristor as a quantum dissipative device, whose decoherence mechanism is controlled by a continuous-measurement feedback scheme, which accounts for the memory. Indeed, we provide numerical simulations showing that memory effects actually persist in the quantum regime. Our quantization method, specifically designed for superconducting circuits, may be extended to other quantum platforms, allowing for memristor-type constructions in different quantum technologies. The proposed quantum memristor is then a building block for neuromorphic quantum computation and quantum simulations of non-Markovian systems.
A gist of comprehensive review of hadronic chemistry and its applications
Energy Technology Data Exchange (ETDEWEB)
Tangde, Vijay M. [Post Graduate Teaching Department of Chemistry, Rashtrasant Tukadoji Maharaj Nagpur University, Amravati Road Campus, NAGPUR - 440 033, India, Email: vijaytn6@gmail.com (India)
2015-03-10
20{sup th} century theories of Quantum Mechanics and Quantum Chemistry are exactly valid only when considered to represent the atomic structures. While considering the more general aspects of atomic combinations these theories fail to explain all the related experimental data from first unadulterated axiomatic principles. According to Quantum Chemistry two valence electrons should repel each other and as such there is no mathematical representation of a strong attractive forces between such valence electrons. In view of these and other insufficiencies of Quantum Chemistry, an Italian-American Scientist Professor Ruggero Maria Santilli during his more than five decades of dedicated and sustained research has denounced the fact that quantum chemistry is mostly based on mere nomenclatures. Professor R M Santilli first formulated the iso-, geno- and hyper- mathematics [1, 2, 3, 4] that helped in understanding numerous diversified problems and removing inadequacies in most of the established and celebrated theories of 20th century physics and chemistry. This involves the isotopic, genotopic, etc. lifting of Lie algebra that generated Lie admissible mathematics to properly describe irreversible processes. The studies on Hadronic Mechanics in general and chemistry in particular based on Santilli’s mathematics[3, 4, 5] for the first time has removed the very fundamental limitations of quantum chemistry [2, 6, 7, 8]. In the present discussion, a comprehensive review of Hadronic Chemistry is presented that imparts the completeness to the Quantum Chemistry via an addition of effects at distances of the order of 1 fm (only) which are assumed to be Non-linear, Non-local, Non-potential, Non-hamiltonian and thus Non-unitary, stepwise successes of Hadronic Chemistry and its application in development of a new chemical species called Magnecules.
Peptide-Decorated Tunable-Fluorescence Graphene Quantum Dots.
Sapkota, Bedanga; Benabbas, Abdelkrim; Lin, Hao-Yu Greg; Liang, Wentao; Champion, Paul; Wanunu, Meni
2017-03-22
We report here the synthesis of graphene quantum dots with tunable size, surface chemistry, and fluorescence properties. In the size regime 15-35 nm, these quantum dots maintain strong visible light fluorescence (mean quantum yield of 0.64) and a high two-photon absorption (TPA) cross section (6500 Göppert-Mayer units). Furthermore, through noncovalent tailoring of the chemistry of these quantum dots, we obtain water-stable quantum dots. For example, quantum dots with lysine groups bind strongly to DNA in solution and inhibit polymerase-based DNA strand synthesis. Finally, by virtue of their mesoscopic size, the quantum dots exhibit good cell permeability into living epithelial cells, but they do not enter the cell nucleus.
Kinetics and Product Channels in Combustion Chemistry
Energy Technology Data Exchange (ETDEWEB)
Hershberger, John F. [North Dakota State Univ., Fargo, ND (United States)
2017-02-28
We report study of the chemical kinetics and/or photochemistry of several chemical reactions of potential interest in understanding the gas phase combustion chemistry of nitrogen-containing molecules. Studies completed during the final grant period include determination of quantum yields of the photolysis of HCNO, fulminic acid, a kinetics and product channel study of the reaction of CN radicals with methyl bromide, and study of the products of the reaction of hydroxymethyl radical with nitric oxide.
Chattaraj, Pratim Kumar
2010-01-01
The application of quantum mechanics to many-particle systems has been an active area of research in recent years as researchers have looked for ways to tackle difficult problems in this area. The quantum trajectory method provides an efficient computational technique for solving both stationary and time-evolving states, encompassing a large area of quantum mechanics. Quantum Trajectories brings the expertise of an international panel of experts who focus on the epistemological significance of quantum mechanics through the quantum theory of motion.Emphasizing a classical interpretation of quan
Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry.
Lehn, Jean-Marie
2012-01-01
Supramolecular chemistry aims at implementing highly complex chemical systems from molecular components held together by non-covalent intermolecular forces and effecting molecular recognition, catalysis and transport processes. A further step consists in the investigation of chemical systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, thus behaving as programmed chemical systems. Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and the resulting ability of supramolecular species to exchange their constituents. The same holds for molecular chemistry when the molecular entity contains covalent bonds that may form and break reversibility, so as to allow a continuous change in constitution by reorganization and exchange of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels.CDC introduces a paradigm shift with respect to constitutionally static chemistry. The latter relies on design for the generation of a target entity, whereas CDC takes advantage of dynamic diversity to allow variation and selection. The implementation of selection in chemistry introduces a fundamental change in outlook. Whereas self-organization by design strives to achieve full control over the output molecular or supramolecular entity by explicit programming, self-organization with selection operates on dynamic constitutional diversity in response to either internal or external factors to achieve adaptation.The merging of the features: -information and programmability, -dynamics and reversibility, -constitution and structural diversity, points to the emergence of adaptive and evolutive chemistry, towards a chemistry of complex matter.
Concepts and methods in modern theoretical chemistry statistical mechanics
Ghosh, Swapan Kumar
2013-01-01
Concepts and Methods in Modern Theoretical Chemistry: Statistical Mechanics, the second book in a two-volume set, focuses on the dynamics of systems and phenomena. A new addition to the series Atoms, Molecules, and Clusters, this book offers chapters written by experts in their fields. It enables readers to learn how concepts from ab initio quantum chemistry and density functional theory (DFT) can be used to describe, understand, and predict chemical dynamics. This book covers a wide range of subjects, including discussions on the following topics: Time-dependent DFT Quantum fluid dynamics (QF
Advanced fuel chemistry for advanced engines.
Energy Technology Data Exchange (ETDEWEB)
Taatjes, Craig A.; Jusinski, Leonard E.; Zador, Judit; Fernandes, Ravi X.; Miller, James A.
2009-09-01
Autoignition chemistry is central to predictive modeling of many advanced engine designs that combine high efficiency and low inherent pollutant emissions. This chemistry, and especially its pressure dependence, is poorly known for fuels derived from heavy petroleum and for biofuels, both of which are becoming increasingly prominent in the nation's fuel stream. We have investigated the pressure dependence of key ignition reactions for a series of molecules representative of non-traditional and alternative fuels. These investigations combined experimental characterization of hydroxyl radical production in well-controlled photolytically initiated oxidation and a hybrid modeling strategy that linked detailed quantum chemistry and computational kinetics of critical reactions with rate-equation models of the global chemical system. Comprehensive mechanisms for autoignition generally ignore the pressure dependence of branching fractions in the important alkyl + O{sub 2} reaction systems; however we have demonstrated that pressure-dependent 'formally direct' pathways persist at in-cylinder pressures.
Controlling a quantum gas of polar molecules in an optical lattice
2016-01-01
The production of molecules from dual species atomic quantum gases has enabled experiments that employ molecules at nanoKelvin temperatures. As a result, every degree of freedom of these molecules is in a well-defined quantum state and exquisitely controlled. These ultracold molecules open a new world of precision quantum chemistry in which quantum statistics, quantum partial waves, and even many-body correlations can play important roles. Moreover, to investigate the strongly correlated phys...
Quantum robots and quantum computers
Energy Technology Data Exchange (ETDEWEB)
Benioff, P.
1998-07-01
Validation of a presumably universal theory, such as quantum mechanics, requires a quantum mechanical description of systems that carry out theoretical calculations and systems that carry out experiments. The description of quantum computers is under active development. No description of systems to carry out experiments has been given. A small step in this direction is taken here by giving a description of quantum robots as mobile systems with on board quantum computers that interact with different environments. Some properties of these systems are discussed. A specific model based on the literature descriptions of quantum Turing machines is presented.
Energy Technology Data Exchange (ETDEWEB)
Zurek, Wojciech H [Los Alamos National Laboratory
2008-01-01
Quantum Darwinism - proliferation, in the environment, of multiple records of selected states of the system (its information-theoretic progeny) - explains how quantum fragility of individual state can lead to classical robustness of their multitude.
Putz, Volkmar
2015-01-01
We consider ways of conceptualizing, rendering and perceiving quantum music, and quantum art in general. Thereby we give particular emphasis to its non-classical aspects, such as coherent superposition and entanglement.
Institute of Scientific and Technical Information of China (English)
无
2000-01-01
@@Chinese Journal of Chemistry is an international journal published in English by the Chinese Chemical Society with its editorial office hosted by Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.
Federal Laboratory Consortium — Description/History: Chemistry laboratoryThe Advanced Chemistry Laboratory (ACL) is a unique facility designed for working with the most super toxic compounds known...
Organometallic Chemistry of Molybdenum.
Lucas, C. Robert; Walsh, Kelly A.
1987-01-01
Suggests ways to avoid some of the problems students have learning the principles of organometallic chemistry. Provides a description of an experiment used in a third-year college chemistry laboratory on molybdenum. (TW)
Environmental chemistry: Volume A
Energy Technology Data Exchange (ETDEWEB)
Yen, T.F.
1999-08-01
This is an extensive introduction to environmental chemistry for engineering and chemical professionals. The contents of Volume A include a brief review of basic chemistry prior to coverage of litho, atmo, hydro, pedo, and biospheres.
Denio, Allen A.
1980-01-01
Relates pottery making to chemistry by providing chemical information about clay, its origin, composition, properties, and changes that occur during firing; also describes glaze compositions, examples of redox chemistry, salt glazing, crystalline glazes, and problems in toxicity. (CS)
Green chemistry: A tool in Pharmaceutical Chemistry
Directory of Open Access Journals (Sweden)
Smita Talaviya
2012-07-01
Full Text Available Green chemistry expresses an area of research developing from scientific discoveries about pollution awareness and it utilizes a set of principles that reduces or eliminates the use or generation of hazardous substances in all steps of particular synthesis or process. Chemists and medicinal scientists can greatly reduce the risk to human health and the environment by following all the valuable principles of green chemistry. The most simple and direct way to apply green chemistry in pharmaceuticals is to utilize eco-friendly, non-hazardous, reproducible and efficient solvents and catalysts in synthesis of drug molecules, drug intermediates and in researches involving synthetic chemistry. Microwave synthesis is also an important tool of green chemistry by being an energy efficient process.
Cheon, T
2004-01-01
We show that the U(2) family of point interactions on a line can be utilized to provide the U(2) family of qubit operations for quantum information processing. Qubits are realized as localized states in either side of the point interaction which represents a controllable gate. The manipulation of qubits proceeds in a manner analogous to the operation of an abacus. Keywords: quantum computation, quantum contact interaction, quantum wire
Esteban Guevara
2006-01-01
The relationships between game theory and quantum mechanics let us propose certain quantization relationships through which we could describe and understand not only quantum but also classical, evolutionary and the biological systems that were described before through the replicator dynamics. Quantum mechanics could be used to explain more correctly biological and economical processes and even it could encloses theories like games and evolutionary dynamics. This could make quantum mechanics a...
2008-01-01
Quantum Nanomechanics is the emerging field which pertains to the mechanical behavior of nanoscale systems in the quantum domain. Unlike the conventional studies of vibration of molecules and phonons in solids, quantum nanomechanics is defined as the quantum behavior of the entire mechanical structure, including all of its constituents--the atoms, the molecules, the ions, the electrons as well as other excitations. The relevant degrees of freedom of the system are described by macroscopic var...
Quantum simulations with ultracold atoms in optical lattices.
Gross, Christian; Bloch, Immanuel
2017-09-08
Quantum simulation, a subdiscipline of quantum computation, can provide valuable insight into difficult quantum problems in physics or chemistry. Ultracold atoms in optical lattices represent an ideal platform for simulations of quantum many-body problems. Within this setting, quantum gas microscopes enable single atom observation and manipulation in large samples. Ultracold atom-based quantum simulators have already been used to probe quantum magnetism, to realize and detect topological quantum matter, and to study quantum systems with controlled long-range interactions. Experiments on many-body systems out of equilibrium have also provided results in regimes unavailable to the most advanced supercomputers. We review recent experimental progress in this field and comment on future directions. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.
Sarathy, Mani
2014-10-01
, also emphasizing advanced engine concepts. Research results addressing combustion reaction mechanisms have been reported based on results from pyrolysis and oxidation reactors, shock tubes, rapid compression machines, and research engines. This work is complemented by the development of detailed combustion models with the support of chemical kinetics and quantum chemistry. This paper seeks to provide an introduction to and overview of recent results on alcohol combustion by highlighting pertinent aspects of this rich and rapidly increasing body of information. As such, this paper provides an initial source of references and guidance regarding the present status of combustion experiments on alcohols and models of alcohol combustion. © 2014 Elsevier Ltd. All rights reserved.
Energy Technology Data Exchange (ETDEWEB)
Mun, Seok Sik
2005-02-15
This book deals with organic chemistry experiments, it is divided five chapters, which have introduction, the way to write the experiment report and safety in the laboratory, basic experiment technic like recrystallization and extraction, a lot of organic chemistry experiments such as fischer esterification, ester hydrolysis, electrophilic aromatic substitution, aldol reaction, benzoin condensation, wittig reaction grignard reaction, epoxidation reaction and selective reduction. The last chapter introduces chemistry site on the internet and way to find out reference on chemistry.
Fehr, S.
2010-01-01
Quantum cryptography makes use of the quantum-mechanical behavior of nature for the design and analysis of cryptographic schemes. Optimally (but not always), quantum cryptography allows for the design of cryptographic schemes whose security is guaranteed solely by the laws of nature. This is in shar
Symmetry of intramolecular quantum dynamics
Burenin, Alexander V
2012-01-01
The main goal of this book is to give a systematic description of intramolecular quantum dynamics on the basis of only the symmetry principles. In this respect, the book has no analogs in the world literature. The obtained models lead to a simple, purely algebraic, scheme of calculation and are rigorous in the sense that their correctness is limited only to the correct choice of symmetry of the internal dynamics. The book is basically intended for scientists working in the field of molecular spectroscopy, quantum and structural chemistry.
American Association for Clinical Chemistry
... older adolescents and adults. Read more IN CLINICAL CHEMISTRY Eliminating Wild-Type DNA in Liquid Biopsies Researchers ... Online Harmonization.net Commission on Accreditation in Clinical Chemistry American Board of Clinical Chemistry Clinical Chemistry Trainee ...
Green Chemistry and Education.
Hjeresen, Dennis L.; Schutt, David L.; Boese, Janet M.
2000-01-01
Many students today are profoundly interested in the sustainability of their world. Introduces Green Chemistry and its principles with teaching materials. Green Chemistry is the use of chemistry for pollution prevention and the design of chemical products and processes that are environmentally benign. (ASK)
Berry, Martyn
1999-01-01
Describes a Chemistry and Art project developed for secondary students and teachers sponsored by the National Gallery and The Royal Society of Chemistry in the United Kingdom. Discusses aspects of the techniques used in creating five paintings as well as the chemistry involved in their making, deterioration, conservation, and restoration.…
Green Chemistry and Education.
Hjeresen, Dennis L.; Schutt, David L.; Boese, Janet M.
2000-01-01
Many students today are profoundly interested in the sustainability of their world. Introduces Green Chemistry and its principles with teaching materials. Green Chemistry is the use of chemistry for pollution prevention and the design of chemical products and processes that are environmentally benign. (ASK)
Physical chemistry of surfaces
Energy Technology Data Exchange (ETDEWEB)
Adamson, A.
1990-01-01
This book covers surface chemistry and selected aspects f colloid chemistry. The text covers such areas as structure and thermodynamics of liquid interfaces; electrical aspects of surface chemistry; microscopy and spectroscopy of solid interfaces; nucleation; contact angle; adsorption from solution; friction and adhesion; lubrication; and chemisorption and catalysis.
Quantum Operations as Quantum States
Arrighi, P; Arrighi, Pablo; Patricot, Christophe
2004-01-01
In this article we formalize the correspondence between quantum states and quantum operations, and harness its consequences. This correspondence was already implicit in Choi's proof of the operator sum representation of Completely Positive-preserving linear maps; we go further and show that all of the important theorems concerning quantum operations can be derived as simple corollaries of those concerning quantum states. As we do so the discussion first provides an elegant and original review of the main features of quantum operations. Next (in the second half of the paper) we search for more results to arise from the correspondence. Thus we propose a factorizability condition and an extremal trace-preservedness condition for quantum operations, give two novel Schmidt-type decompositions of bipartite pure states and two interesting composition laws for which the set of quantum operations and quantum states remain stable. The latter enables us to define a group structure upon the set of totally entangled state...
Quantum memory in quantum cryptography
Mor, T
1999-01-01
[Shortened abstract:] This thesis investigates the importance of quantum memory in quantum cryptography, concentrating on quantum key distribution schemes. In the hands of an eavesdropper -- a quantum memory is a powerful tool, putting in question the security of quantum cryptography; Classical privacy amplification techniques, used to prove security against less powerful eavesdroppers, might not be effective when the eavesdropper can keep quantum states for a long time. In this work we suggest a possible direction for approaching this problem. We define strong attacks of this type, and show security against them, suggesting that quantum cryptography is secure. We start with a complete analysis regarding the information about a parity bit (since parity bits are used for privacy amplification). We use the results regarding the information on parity bits to prove security against very strong eavesdropping attacks, which uses quantum memories and all classical data (including error correction codes) to attack th...
A quantum–quantum Metropolis algorithm
Yung, Man-Hong; Aspuru-Guzik, Alan
2012-01-01
The classical Metropolis sampling method is a cornerstone of many statistical modeling applications that range from physics, chemistry, and biology to economics. This method is particularly suitable for sampling the thermal distributions of classical systems. The challenge of extending this method to the simulation of arbitrary quantum systems is that, in general, eigenstates of quantum Hamiltonians cannot be obtained efficiently with a classical computer. However, this challenge can be overc...
Zurek, Wojciech Hubert
2009-03-01
Quantum Darwinism describes the proliferation, in the environment, of multiple records of selected states of a quantum system. It explains how the quantum fragility of a state of a single quantum system can lead to the classical robustness of states in their correlated multitude; shows how effective `wave-packet collapse' arises as a result of the proliferation throughout the environment of imprints of the state of the system; and provides a framework for the derivation of Born's rule, which relates the probabilities of detecting states to their amplitudes. Taken together, these three advances mark considerable progress towards settling the quantum measurement problem.
Quantum entanglement and quantum operation
Institute of Scientific and Technical Information of China (English)
无
2008-01-01
It is a simple introduction to quantum entanglement and quantum operations. The authors focus on some applications of quantum entanglement and relations between two-qubit entangled states and unitary operations. It includes remote state preparation by using any pure entangled states, nonlocal operation implementation using entangled states, entanglement capacity of two-qubit gates and two-qubit gates construction.
Birdi, K S
2013-01-01
Surface chemistry plays an important role in everyday life, as the basis for many phenomena as well as technological applications. Common examples range from soap bubbles, foam, and raindrops to cosmetics, paint, adhesives, and pharmaceuticals. Additional areas that rely on surface chemistry include modern nanotechnology, medical diagnostics, and drug delivery. There is extensive literature on this subject, but most chemistry books only devote one or two chapters to it. Surface Chemistry Essentials fills a need for a reference that brings together the fundamental aspects of surface chemistry w
Horodecki, R; Horodecki, M; Horodecki, K; Horodecki, Ryszard; Horodecki, Pawel; Horodecki, Michal; Horodecki, Karol
2007-01-01
All our former experience with application of quantum theory seems to say: {\\it what is predicted by quantum formalism must occur in laboratory}. But the essence of quantum formalism - entanglement, recognized by Einstein, Podolsky, Rosen and Schr\\"odinger - waited over 70 years to enter to laboratories as a new resource as real as energy. This holistic property of compound quantum systems, which involves nonclassical correlations between subsystems, is a potential for many quantum processes, including ``canonical'' ones: quantum cryptography, quantum teleportation and dense coding. However, it appeared that this new resource is very complex and difficult to detect. Being usually fragile to environment, it is robust against conceptual and mathematical tools, the task of which is to decipher its rich structure. This article reviews basic aspects of entanglement including its characterization, detection, distillation and quantifying. In particular, the authors discuss various manifestations of entanglement via ...
Weaver, Nik
2010-01-01
We define a "quantum relation" on a von Neumann algebra M \\subset B(H) to be a weak* closed operator bimodule over its commutant M'. Although this definition is framed in terms of a particular representation of M, it is effectively representation independent. Quantum relations on l^\\infty(X) exactly correspond to subsets of X^2, i.e., relations on X. There is also a good definition of a "measurable relation" on a measure space, to which quantum relations partially reduce in the general abelian case. By analogy with the classical setting, we can identify structures such as quantum equivalence relations, quantum partial orders, and quantum graphs, and we can generalize Arveson's fundamental work on weak* closed operator algebras containing a masa to these cases. We are also able to intrinsically characterize the quantum relations on M in terms of families of projections in M \\otimes B(l^2).
The New Color of Chemistry: Green Chemistry
Directory of Open Access Journals (Sweden)
Zuhal GERÇEK
2012-01-01
Full Text Available Green chemistry which is the new application of chemistry rules provides solutions to problems that mankind is faced with climate changes, sustainable agriculture, energy, toxics, depletion of natural sources e.g. designing new chemicals and processes that production and utilization of hazardous matters. So, it is the indispensible tool for sustainable development. Current and future chemists should consider the human health and ecological issues in their professional life. In order to provide a solution for this requirement, green chemistry rules and under standings should be primarily taken in the university curriculum and at all educational levels.
New frontiers for quantum gases of polar molecules
Moses, Steven A.; Covey, Jacob P.; Miecnikowski, Matthew T.; Jin, Deborah S.; Ye, Jun
2017-01-01
Compared to atoms, molecules possess additional degrees of freedom that can be exploited in fundamental tests, ultracold chemistry, and engineering new quantum phases in many-body systems. Here, we review the recent progress in creating and manipulating ultracold bialkali molecules to study quantum gases of polar molecules.
Cedeno, David L.; Jones, Marjorie A.; Friesen, Jon A.; Wirtz, Mark W.; Rios, Luz Amalia; Ocampo, Gonzalo Taborda
2010-01-01
At the Universidad de Caldas, Manizales, Colombia, we used their new computer facilities to introduce chemistry graduate students to biochemical database mining and quantum chemistry calculations using freeware. These hands-on workshops allowed the students a strong introduction to easily accessible software and how to use this software to begin…
Quantum Games and Quantum Discord
Nawaz, Ahmad
2010-01-01
We quantize prisoners dilemma and chicken game by our generalized quantization scheme to explore the role of quantum discord in quantum games. In order to establish this connection we use Werner-like state as an initial state of the game. In this quantization scheme measurement can be performed in entangled as well as in product basis. For the measurement in entangled basis the dilemma in both the games can be resolved by separable states with non-zero quantum discord. Similarly for product basis measurement the payoffs are quantum mechanical only for nonzero values of quantum discord.
Quantum Dots in a Polymer Composite: A Convenient Particle-in-a-Box Laboratory Experiment
Rice, Charles V.; Giffin, Guinevere A.
2008-01-01
Semiconductor quantum dots are at the forefront of materials science chemistry with applications in biological imaging and photovoltaic technologies. We have developed a simple laboratory experiment to measure the quantum-dot size from fluorescence spectra. A major roadblock of quantum-dot based exercises is the particle synthesis and handling;…
The New Color of Chemistry: Green Chemistry
Zuhal GERÇEK
2012-01-01
Green chemistry which is the new application of chemistry rules provides solutions to problems that mankind is faced with climate changes, sustainable agriculture, energy, toxics, depletion of natural sources e.g. designing new chemicals and processes that production and utilization of hazardous matters. So, it is the indispensible tool for sustainable development. Current and future chemists should consider the human health and ecological issues in their professional life. In order to provid...
Critical Missing Equation of Quantum Physics for Understanding Atomic Structures
Huang, Xiaofei
2013-01-01
This paper presents an optimization approach to explain why and how a quantum system evolves from an arbitrary initial state to a stationary state, satisfying the time-independent Schr\\"{o}dinger equation. It also points out the inaccuracy of this equation, which is critial important in quantum mechanics and quantum chemistry, due to a fundamental flaw in it conflicting with the physical reality. The some directions are suggested on how to modify the equation to fix the problem
Critical Missing Equation of Quantum Physics for Understanding Atomic Structures
Huang, Xiaofei
2015-01-01
This paper presents an optimization approach to explain why and how a quantum system evolves from an arbitrary initial state to a stationary state, satisfying the time-independent Schr\\"{o}dinger equation. It also points out the inaccuracy of this equation, which is critial important in quantum mechanics and quantum chemistry, due to a fundamental flaw in it conflicting with the physical reality. The some directions are suggested on how to modify the equation to fix the problem
An Integrated, Statistical Molecular Approach to the Physical Chemistry Curriculum
Cartier, Stephen F.
2009-01-01
As an alternative to the "thermodynamics first" or "quantum first" approaches to the physical chemistry curriculum, the statistical definition of entropy and the Boltzmann distribution are introduced in the first days of the course and the entire two-semester curriculum is then developed from these concepts. Once the tools of statistical mechanics…
An Integrated, Statistical Molecular Approach to the Physical Chemistry Curriculum
Cartier, Stephen F.
2009-01-01
As an alternative to the "thermodynamics first" or "quantum first" approaches to the physical chemistry curriculum, the statistical definition of entropy and the Boltzmann distribution are introduced in the first days of the course and the entire two-semester curriculum is then developed from these concepts. Once the tools of statistical mechanics…
Deep learning for computational chemistry.
Goh, Garrett B; Hodas, Nathan O; Vishnu, Abhinav
2017-06-15
The rise and fall of artificial neural networks is well documented in the scientific literature of both computer science and computational chemistry. Yet almost two decades later, we are now seeing a resurgence of interest in deep learning, a machine learning algorithm based on multilayer neural networks. Within the last few years, we have seen the transformative impact of deep learning in many domains, particularly in speech recognition and computer vision, to the extent that the majority of expert practitioners in those field are now regularly eschewing prior established models in favor of deep learning models. In this review, we provide an introductory overview into the theory of deep neural networks and their unique properties that distinguish them from traditional machine learning algorithms used in cheminformatics. By providing an overview of the variety of emerging applications of deep neural networks, we highlight its ubiquity and broad applicability to a wide range of challenges in the field, including quantitative structure activity relationship, virtual screening, protein structure prediction, quantum chemistry, materials design, and property prediction. In reviewing the performance of deep neural networks, we observed a consistent outperformance against non-neural networks state-of-the-art models across disparate research topics, and deep neural network-based models often exceeded the "glass ceiling" expectations of their respective tasks. Coupled with the maturity of GPU-accelerated computing for training deep neural networks and the exponential growth of chemical data on which to train these networks on, we anticipate that deep learning algorithms will be a valuable tool for computational chemistry. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.
Theoretical and quantum mechanics fundamentals for chemists
Ivanov, Stefan
2006-01-01
Provides the basics of theoretical and quantum mechanics in one place and emphasizes the continuity between themUniquely presented to be used for self-taught courses covering theoretical and quantum mechanicsEach chapter includes a detailed outline, a summary, self-assessment questions for which answers can be found in the textInvaluable for chemistry undergraduate and graduate students, chemists, other non-physical scientists, engineering students of modern techniques and technology, specialists who need a better understanding of quantum mechanics.
Gilbert, Gerald; Hamrick, Michael
2013-01-01
This book provides a detailed account of the theory and practice of quantum cryptography. Suitable as the basis for a course in the subject at the graduate level, it crosses the disciplines of physics, mathematics, computer science and engineering. The theoretical and experimental aspects of the subject are derived from first principles, and attention is devoted to the practical development of realistic quantum communications systems. The book also includes a comprehensive analysis of practical quantum cryptography systems implemented in actual physical environments via either free-space or fiber-optic cable quantum channels. This book will be a valuable resource for graduate students, as well as professional scientists and engineers, who desire an introduction to the field that will enable them to undertake research in quantum cryptography. It will also be a useful reference for researchers who are already active in the field, and for academic faculty members who are teaching courses in quantum information s...
Arrighi, P
2003-01-01
Alice communicates with words drawn uniformly amongst $\\{\\ket{j}\\}_{j=1..n}$, the canonical orthonormal basis. Sometimes however Alice interleaves quantum decoys $\\{\\frac{\\ket{j}+i\\ket{k}}{\\sqrt{2}}\\}$ between her messages. Such pairwise superpositions of possible words cannot be distinguished from the message words. Thus as malevolent Eve observes the quantum channel, she runs the risk of damaging the superpositions (by causing a collapse). At the receiving end honest Bob, whom we assume is warned of the quantum decoys' distribution, checks upon their integrity with a measurement. The present work establishes, in the case of individual attacks, the tradeoff between Eve's information gain (her chances, if a message word was sent, of guessing which) and the disturbance she induces (Bob's chances, if a quantum decoy was sent, to detect tampering). Besides secure channel protocols, quantum decoys seem a powerful primitive for constructing n-dimensional quantum cryptographic applications. Moreover the methods emp...
Busch, Paul; Pellonpää, Juha-Pekka; Ylinen, Kari
2016-01-01
This is a book about the Hilbert space formulation of quantum mechanics and its measurement theory. It contains a synopsis of what became of the Mathematical Foundations of Quantum Mechanics since von Neumann’s classic treatise with this title. Fundamental non-classical features of quantum mechanics—indeterminacy and incompatibility of observables, unavoidable measurement disturbance, entanglement, nonlocality—are explicated and analysed using the tools of operational quantum theory. The book is divided into four parts: 1. Mathematics provides a systematic exposition of the Hilbert space and operator theoretic tools and relevant measure and integration theory leading to the Naimark and Stinespring dilation theorems; 2. Elements develops the basic concepts of quantum mechanics and measurement theory with a focus on the notion of approximate joint measurability; 3. Realisations offers in-depth studies of the fundamental observables of quantum mechanics and some of their measurement implementations; and 4....
2010-03-04
efficient or less costly than their classical counterparts. A large-scale quantum computer is certainly an extremely ambi- tious goal, appearing to us...outperform the largest classical supercomputers in solving some specific problems important for data encryption. In the long term, another application...which the quantum computer depends, causing the quantum mechanically destructive process known as decoherence . Decoherence comes in several forms
Hughes, R J; Dyer, P L; Luther, G G; Morgan, G L; Schauer, M M; Hughes, Richard J; Dyer, P; Luther, G G; Morgan, G L; Schauer, M
1995-01-01
Quantum cryptography is a new method for secret communications offering the ultimate security assurance of the inviolability of a Law of Nature. In this paper we shall describe the theory of quantum cryptography, its potential relevance and the development of a prototype system at Los Alamos, which utilises the phenomenon of single-photon interference to perform quantum cryptography over an optical fiber communications link.
Miller, Tierney C.; Richardson, John N.; Kegerreis, Jeb S.
2016-01-01
This manuscript presents an exercise that utilizes mathematical software to explore Fourier transforms in the context of model quantum mechanical systems, thus providing a deeper mathematical understanding of relevant information often introduced and treated as a "black-box" in analytical chemistry courses. The exercise is given to…
Quantum Process in Living Cells
Finkel, Robert W
2012-01-01
Quantum effects have been confirmed in photosynthesis and other biological phenomena. Here we explore the idea of a cooperative quantum process in cells and introduce a model based on coherent waves of established ultrafast energy transfers in water. We compute wave speed, ~156 km/s, and wavelength, ~9.3 nm, and determine that the waves retain local coherence. Diverse numerical applications lend support to the hypothesis that rapid energy transfers in water are characteristic of living cells. Close agreements are found for the dipole moment of water dimers, microwave radiation on yeast, and the Kleiber law of metabolic rates. We find a sphere with diameter ~20 nm is a lower bound for life in this theory. The quantum properties of the model suggest that cellular chemistry favors reactions that support perpetuation of the energy waves
Energy Technology Data Exchange (ETDEWEB)
Rodgers, P
1998-03-01
There is more to information than a string of ones and zeroes the ability of ''quantum bits'' to be in two states at the same time could revolutionize information technology. In the mid-1930s two influential but seemingly unrelated papers were published. In 1935 Einstein, Podolsky and Rosen proposed the famous EPR paradox that has come to symbolize the mysteries of quantum mechanics. Two years later, Alan Turing introduced the universal Turing machine in an enigmatically titled paper, On computable numbers, and laid the foundations of the computer industry one of the biggest industries in the world today. Although quantum physics is essential to understand the operation of transistors and other solid-state devices in computers, computation itself has remained a resolutely classical process. Indeed it seems only natural that computation and quantum theory should be kept as far apart as possible surely the uncertainty associated with quantum theory is anathema to the reliability expected from computers? Wrong. In 1985 David Deutsch introduced the universal quantum computer and showed that quantum theory can actually allow computers to do more rather than less. The ability of particles to be in a superposition of more than one quantum state naturally introduces a form of parallelism that can, in principle, perform some traditional computing tasks faster than is possible with classical computers. Moreover, quantum computers are capable of other tasks that are not conceivable with their classical counterparts. Similar breakthroughs in cryptography and communication followed. (author)
Quantum Networks for Generating Arbitrary Quantum States
Kaye, Phillip; Mosca, Michele
2004-01-01
Quantum protocols often require the generation of specific quantum states. We describe a quantum algorithm for generating any prescribed quantum state. For an important subclass of states, including pure symmetric states, this algorithm is efficient.
Orbital interactions in chemistry
Albright, Thomas A; Whangbo, Myung-Hwan
2013-01-01
Explains the underlying structure that unites all disciplines in chemistry Now in its second edition, this book explores organic, organometallic, inorganic, solid state, and materials chemistry, demonstrating how common molecular orbital situations arise throughout the whole chemical spectrum. The authors explore the relationships that enable readers to grasp the theory that underlies and connects traditional fields of study within chemistry, thereby providing a conceptual framework with which to think about chemical structure and reactivity problems. Orbital Interactions
Quantum chemical studies of estrogenic compounds
Quantum chemical methods are potent tools to provide information on the chemical structure and electronic properties of organic molecules. Modern computational chemistry methods have provided a great deal of insight into the binding of estrogenic compounds to estrogenic receptors (ER), an important ...
Science Update: Analytical Chemistry.
Worthy, Ward
1980-01-01
Briefly discusses new instrumentation in the field of analytical chemistry. Advances in liquid chromatography, photoacoustic spectroscopy, the use of lasers, and mass spectrometry are also discussed. (CS)
Kolopajlo, Larry
2017-02-01
This chapter attempts to show how the practice of chemistry teaching and learning is enriched by the incorporation of green chemistry (GC) into lectures and labs. To support this viewpoint, evidence from a wide range of published papers serve as a cogent argument that GC attracts and engages both science and nonscience students, enhances chemistry content knowledge, and improves the image of the field, while preparing the world for a sustainable future. Published pedagogy associated with green and sustainable chemistry is critically reviewed and discussed.
Elements of environmental chemistry
National Research Council Canada - National Science Library
Hites, R. A; Raff, Jonathan D
2012-01-01
.... Extensively revised, updated, and expanded, this second edition includes new chapters on atmospheric chemistry, climate change, and polychlorinated biphenyls and dioxins, and brominated flame retardants...
Quantum physics without quantum philosophy
Energy Technology Data Exchange (ETDEWEB)
Duerr, Detlef [Muenchen Univ. (Germany). Mathematisches Inst.; Goldstein, Sheldon [Rutgers State Univ., Piscataway, NJ (United States). Dept. of Mathematics; Zanghi, Nino [Genova Univ. (Italy); Istituto Nazionale Fisica Nucleare, Genova (Italy)
2013-02-01
Integrates and comments on the authors' seminal papers in the field. Emphasizes the natural way in which quantum phenomena emerge from the Bohmian picture. Helps to answer many of the objections raised to Bohmian quantum mechanics. Useful overview and summary for newcomers and students. It has often been claimed that without drastic conceptual innovations a genuine explanation of quantum interference effects and quantum randomness is impossible. This book concerns Bohmian mechanics, a simple particle theory that is a counterexample to such claims. The gentle introduction and other contributions collected here show how the phenomena of non-relativistic quantum mechanics, from Heisenberg's uncertainty principle to non-commuting observables, emerge from the Bohmian motion of particles, the natural particle motion associated with Schroedinger's equation. This book will be of value to all students and researchers in physics with an interest in the meaning of quantum theory as well as to philosophers of science.
Academic Training: The World of Quantum Matter
Françoise Benz
2006-01-01
2005-2006 ACADEMIC TRAINING PROGRAMME LECTURE SERIES 23, 24, 25, 26 January 2006 from 11:00 to 12:00 - Main Auditorium, bldg. 500 The World of Quantum Matter M. WEIDEMUELLER / Albert-Ludwigs-Universität Freiburg In my lecture series, I will present the recent spectacular advances in the field of quantum gases and macroscopic quantum physics. A variety of subjects will be covered including Bose condensates and degenerate Fermi gases, ultracold molecules and chemistry near absolute zero, Rydberg gases, single-atom manipulation, quantum information processing, as well as applications of cold atoms as precision targets. The topics of the lectures are: Physics near absolute zero Bose condensation and Fermi degeneracy Molecules, Rydberg gases and other exotic species Single-atom manipulation, quantum information processing and ultracold atoms as targets in storage rings. ENSEIGNEMENT ACADEMIQUE ACADEMIC TRAINING Françoise Benz 73127 academic.training@cern.ch If you wish to participate in one of the f...
Community Detection in Quantum Complex Networks
Faccin, Mauro; Johnson, Tomi; Biamonte, Jacob; Bergholm, Ville
2013-01-01
Determining community structure in interacting systems, ranging from technological to social, from biological to chemical, is a topic of central importance in the study of networks. Extending this concept to apply to quantum systems represents an open challenge and a crucial missing component towards a theory of complex networks based on quantum mechanics. Here we accomplish this goal by introducing methods for identifying the community structure of a network governed by quantum dynamics. To illustrate our approach we turn to a host of examples, including a naturally occurring light-harvesting network, where from first principles we determine a consistent community structure. In certain regimes the communities we determine agree with a partitioning currently done by hand in the quantum chemistry literature. In other regimes, we uncover a new community structure. The difference stems from defining measures to determine distances between nodes in quantum systems, and then determining optimal modularity. Merging...
Quantum entanglement and quantum operation
Institute of Scientific and Technical Information of China (English)
2008-01-01
It is a simple introduction to quantum entanglement and quantum operations.The authors focus on some applications of quantum entanglement and relations between two-qubit entangled states and unitary operations.It includes remote state preparation by using any pure entangled states,nonlocal operation implementation using entangled states,entanglement capacity of two-qubit gates and two-qubit gates construction.
Quantum Physics Without Quantum Philosophy
Dürr, Detlef; Zanghì, Nino
2013-01-01
It has often been claimed that without drastic conceptual innovations a genuine explanation of quantum interference effects and quantum randomness is impossible. This book concerns Bohmian mechanics, a simple particle theory that is a counterexample to such claims. The gentle introduction and other contributions collected here show how the phenomena of non-relativistic quantum mechanics, from Heisenberg's uncertainty principle to non-commuting observables, emerge from the Bohmian motion of particles, the natural particle motion associated with Schrödinger's equation. This book will be of value to all students and researchers in physics with an interest in the meaning of quantum theory as well as to philosophers of science.
Abrams, D.; Williams, C.
1999-01-01
This thesis describes several new quantum algorithms. These include a polynomial time algorithm that uses a quantum fast Fourier transform to find eigenvalues and eigenvectors of a Hamiltonian operator, and that can be applied in cases for which all know classical algorithms require exponential time.
Manning, Phillip
2011-01-01
The study of quantum theory allowed twentieth-century scientists to examine the world in a new way, one that was filled with uncertainties and probabilities. Further study also led to the development of lasers, the atomic bomb, and the computer. This exciting new book clearly explains quantum theory and its everyday uses in our world.
Sastry, R R
1999-01-01
The infinite dimensional generalization of the quantum mechanics of extended objects, namely, the quantum field theory of extended objects is employed to address the hitherto nonrenormalizable gravitational interaction following which the cosmological constant problem is addressed. The response of an electron to a weak gravitational field (linear approximation) is studied and the order $\\alpha$ correction to the magnetic gravitational moment is computed.
Coined quantum walks on percolation graphs
Energy Technology Data Exchange (ETDEWEB)
Leung, Godfrey; Knott, Paul; Bailey, Joe; Kendon, Viv, E-mail: V.Kendon@leeds.ac.uk [School of Physics and Astronomy, University of Leeds, Leeds LS2 9JT (United Kingdom)
2010-12-15
Quantum walks, both discrete (coined) and continuous time, form the basis of several quantum algorithms and have been used to model processes such as transport in spin chains and quantum chemistry. The enhanced spreading and mixing properties of quantum walks compared with their classical counterparts have been well studied on regular structures and also shown to be sensitive to defects and imperfections in the lattice. As a simple example of a disordered system, we consider percolation lattices, in which edges or sites are randomly missing, interrupting the progress of the quantum walk. We use numerical simulation to study the properties of coined quantum walks on these percolation lattices in one and two dimensions. In one dimension (the line), we introduce a simple notion of quantum tunnelling and determine how this affects the properties of the quantum walk as it spreads. On two-dimensional percolation lattices, we show how the spreading rate varies from linear in the number of steps down to zero as the percolation probability decreases towards the critical point. This provides an example of fractional scaling in quantum-walk dynamics.
Community Detection in Quantum Complex Networks
Faccin, Mauro; Migdał, Piotr; Johnson, Tomi H.; Bergholm, Ville; Biamonte, Jacob D.
2014-10-01
Determining community structure is a central topic in the study of complex networks, be it technological, social, biological or chemical, static or in interacting systems. In this paper, we extend the concept of community detection from classical to quantum systems—a crucial missing component of a theory of complex networks based on quantum mechanics. We demonstrate that certain quantum mechanical effects cannot be captured using current classical complex network tools and provide new methods that overcome these problems. Our approaches are based on defining closeness measures between nodes, and then maximizing modularity with hierarchical clustering. Our closeness functions are based on quantum transport probability and state fidelity, two important quantities in quantum information theory. To illustrate the effectiveness of our approach in detecting community structure in quantum systems, we provide several examples, including a naturally occurring light-harvesting complex, LHCII. The prediction of our simplest algorithm, semiclassical in nature, mostly agrees with a proposed partitioning for the LHCII found in quantum chemistry literature, whereas our fully quantum treatment of the problem uncovers a new, consistent, and appropriately quantum community structure.
Hadjiivanov, Ludmil
2015-01-01
Expository paper providing a historical survey of the gradual transformation of the "philosophical discussions" between Bohr, Einstein and Schr\\"odinger on foundational issues in quantum mechanics into a quantitative prediction of a new quantum effect, its experimental verification and its proposed (and loudly advertised) applications. The basic idea of the 1935 paper of Einstein-Podolsky-Rosen (EPR) was reformulated by David Bohm for a finite dimensional spin system. This allowed John Bell to derive his inequalities that separate the prediction of quantum entanglement from its possible classical interpretation. We reproduce here their later (1971) version, reviewing on the way the generalization (and mathematical derivation) of Heisenberg's uncertainty relations (due to Weyl and Schr\\"odinger) needed for the passage from EPR to Bell. We also provide an improved derivation of the quantum theoretic violation of Bell's inequalities. Soon after the experimental confirmation of the quantum entanglement (culminati...
Richter, Johannes; Farnell, Damian; Bishop, Raymod
2004-01-01
The investigation of magnetic systems where quantum effects play a dominant role has become a very active branch of solid-state-physics research in its own right. The first three chapters of the "Quantum Magnetism" survey conceptual problems and provide insights into the classes of systems considered, namely one-dimensional, two-dimensional and molecular magnets. The following chapters introduce the methods used in the field of quantum magnetism, including spin wave analysis, exact diagonalization, quantum field theory, coupled cluster methods and the Bethe ansatz. The book closes with a chapter on quantum phase transitions and a contribution that puts the wealth of phenomena into the context of experimental solid-state physics. Closing a gap in the literature, this volume is intended both as an introductory text at postgraduate level and as a modern, comprehensive reference for researchers in the field.
Pearsall, Thomas P
2017-01-01
This textbook employs a pedagogical approach that facilitates access to the fundamentals of Quantum Photonics. It contains an introductory description of the quantum properties of photons through the second quantization of the electromagnetic field, introducing stimulated and spontaneous emission of photons at the quantum level. Schrödinger’s equation is used to describe the behavior of electrons in a one-dimensional potential. Tunneling through a barrier is used to introduce the concept of nonlocality of an electron at the quantum level, which is closely-related to quantum confinement tunneling, resonant tunneling, and the origin of energy bands in both periodic (crystalline) and aperiodic (non-crystalline) materials. Introducing the concepts of reciprocal space, Brillouin zones, and Bloch’s theorem, the determination of electronic band structure using the pseudopotential method is presented, allowing direct computation of the band structures of most group IV, group III-V, and group II-VI semiconducto...
Kiefer, Claus
2012-01-01
The search for a quantum theory of the gravitational field is one of the great open problems in theoretical physics. This book presents a self-contained discussion of the concepts, methods and applications that can be expected in such a theory. The two main approaches to its construction - the direct quantisation of Einstein's general theory of relativity and string theory - are covered. Whereas the first attempts to construct a viable theory for the gravitational field alone, string theory assumes that a quantum theory of gravity will be achieved only through a unification of all the interactions. However, both employ the general method of quantization of constrained systems, which is described together with illustrative examples relevant for quantum gravity. There is a detailed presentation of the main approaches employed in quantum general relativity: path-integral quantization, the background-field method and canonical quantum gravity in the metric, connection and loop formulations. The discussion of stri...
Rae, Alastair I M
2016-01-01
A Thorough Update of One of the Most Highly Regarded Textbooks on Quantum Mechanics Continuing to offer an exceptionally clear, up-to-date treatment of the subject, Quantum Mechanics, Sixth Edition explains the concepts of quantum mechanics for undergraduate students in physics and related disciplines and provides the foundation necessary for other specialized courses. This sixth edition builds on its highly praised predecessors to make the text even more accessible to a wider audience. It is now divided into five parts that separately cover broad topics suitable for any general course on quantum mechanics. New to the Sixth Edition * Three chapters that review prerequisite physics and mathematics, laying out the notation, formalism, and physical basis necessary for the rest of the book * Short descriptions of numerous applications relevant to the physics discussed, giving students a brief look at what quantum mechanics has made possible industrially and scientifically * Additional end-of-chapter problems with...
Quantum Computation Toward Quantum Gravity
Zizzi, P. A.
2001-08-01
The aim of this paper is to enlighten the emerging relevance of Quantum Information Theory in the field of Quantum Gravity. As it was suggested by J. A. Wheeler, information theory must play a relevant role in understanding the foundations of Quantum Mechanics (the "It from bit" proposal). Here we suggest that quantum information must play a relevant role in Quantum Gravity (the "It from qubit" proposal). The conjecture is that Quantum Gravity, the theory which will reconcile Quantum Mechanics with General Relativity, can be formulated in terms of quantum bits of information (qubits) stored in space at the Planck scale. This conjecture is based on the following arguments: a) The holographic principle, b) The loop quantum gravity approach and spin networks, c) Quantum geometry and black hole entropy. From the above arguments, as they stand in the literature, it follows that the edges of spin networks pierce the black hole horizon and excite curvature degrees of freedom on the surface. These excitations are micro-states of Chern-Simons theory and account of the black hole entropy which turns out to be a quarter of the area of the horizon, (in units of Planck area), in accordance with the holographic principle. Moreover, the states which dominate the counting correspond to punctures of spin j = 1/2 and one can in fact visualize each micro-state as a bit of information. The obvious generalization of this result is to consider open spin networks with edges labeled by the spin -1/ 2 representation of SU(2) in a superposed state of spin "on" and spin "down." The micro-state corresponding to such a puncture will be a pixel of area which is "on" and "off" at the same time, and it will encode a qubit of information. This picture, when applied to quantum cosmology, describes an early inflationary universe which is a discrete version of the de Sitter universe.
Henson, R.; Stumbles, A.
1977-01-01
The relationship between mathematics and chemistry has been changing rapidly in recent years. Some chemistry teachers have experienced difficulties in their teaching with the introduction of modern mathematics in the schools. Some suggestions for reinforcing the concepts and language of modern mathematics are put forth. (Author/MA)
Pekdag, Bulent; Le Marechal, Jean-Francois
2010-01-01
This article reviews numerous studies on chemistry movies. Movies, or moving pictures, are important elements of multimedia and signify a privileged or motivating means of presenting knowledge. Studies on chemistry movies show that the first movie productions in this field were devoted to university lectures or documentaries. Shorter movies were…
Physical Chemistry of Molecular
Institute of Scientific and Technical Information of China (English)
2011-01-01
@@ Established in 2009, the group consists of six researchers and more than 70 research assistants and graduate students from the CAS Key Laboratory of Molecular Nanostructures and Nanotechnologies at the CAS Institute of Chemistry.Its research focuses on the physical chemistry involved in molecular assembly, molecular nanostructures, functional nanomaterials and conceptual nano-devices.
Exercises in Computational Chemistry
DEFF Research Database (Denmark)
Spanget-Larsen, Jens
2016-01-01
A selection of HyperChem© PC-exercises in computational chemistry. Answers to most questions are appended (Roskilde University 2014-16).......A selection of HyperChem© PC-exercises in computational chemistry. Answers to most questions are appended (Roskilde University 2014-16)....
DEFF Research Database (Denmark)
Josephsen, Jens
The present preliminary text is a short thematic presentation in biological inorganic chemistry meant to illustrate general and inorganic (especially coordination) chemistry in biochemistry. The emphasis is on molecular models to explain features of the complicated mechanisms essential to breathing...
Bioorganic and bioinorganic chemistry.
Constable, Edwin C; Housecroft, Catherine E; Creus, Marc; Gademann, Karl; Giese, Bernd; Ward, Thomas R; Woggon, Wolf D; Chougnet, Antoinette
2010-01-01
The interdisciplinary projects in bioinorganic and bioorganic chemistry of the Department of Chemistry, University of Basel led to the preparation of new systems that mimic biologically important processes and to the discovery of compounds from natural sources which are very promising with respect to medical applications. The advances in these areas are reported here.
Exercises in Computational Chemistry
DEFF Research Database (Denmark)
Spanget-Larsen, Jens
2016-01-01
A selection of HyperChem© PC-exercises in computational chemistry. Answers to most questions are appended (Roskilde University 2014-16).......A selection of HyperChem© PC-exercises in computational chemistry. Answers to most questions are appended (Roskilde University 2014-16)....
Chemistry in Microfluidic Channels
Chia, Matthew C.; Sweeney, Christina M.; Odom, Teri W.
2011-01-01
General chemistry introduces principles such as acid-base chemistry, mixing, and precipitation that are usually demonstrated in bulk solutions. In this laboratory experiment, we describe how chemical reactions can be performed in a microfluidic channel to show advanced concepts such as laminar fluid flow and controlled precipitation. Three sets of…
Energy Technology Data Exchange (ETDEWEB)
Schulz, W.W.
1976-01-01
Essential features of the descriptive chemistry of americium are reviewed. Chapter titles are: discovery, atomic and nuclear properties, collateral reading, production and uses, chemistry in aqueous solution, metal, alloys, and compounds, and, recovery, separation, purification. Author and subject indexes are included. (JCB)
Recent computational chemistry
Energy Technology Data Exchange (ETDEWEB)
Onishi, Taku [Department of Chemistry for Materials, and The Center of Ultimate Technology on nano-Electronics, Mie University (Japan); Center for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo (Norway)
2015-12-31
Now we can investigate quantum phenomena for the real materials and molecules, and can design functional materials by computation, due to the previous developments of quantum theory and calculation methods. As there still exist the limit and problem in theory, the cooperation between theory and computation is getting more important to clarify the unknown quantum mechanism, and discover more efficient functional materials. It would be next-generation standard. Finally, our theoretical methodology for boundary solid is introduced.
Recent computational chemistry
Onishi, Taku
2015-12-01
Now we can investigate quantum phenomena for the real materials and molecules, and can design functional materials by computation, due to the previous developments of quantum theory and calculation methods. As there still exist the limit and problem in theory, the cooperation between theory and computation is getting more important to clarify the unknown quantum mechanism, and discover more efficient functional materials. It would be next-generation standard. Finally, our theoretical methodology for boundary solid is introduced.
Biosynthetic inorganic chemistry.
Lu, Yi
2006-08-25
Inorganic chemistry and biology can benefit greatly from each other. Although synthetic and physical inorganic chemistry have been greatly successful in clarifying the role of metal ions in biological systems, the time may now be right to utilize biological systems to advance coordination chemistry. One such example is the use of small, stable, easy-to-make, and well-characterized proteins as ligands to synthesize novel inorganic compounds. This biosynthetic inorganic chemistry is possible thanks to a number of developments in biology. This review summarizes the progress in the synthesis of close models of complex metalloproteins, followed by a description of recent advances in using the approach for making novel compounds that are unprecedented in either inorganic chemistry or biology. The focus is mainly on synthetic "tricks" learned from biology, as well as novel structures and insights obtained. The advantages and disadvantages of this biosynthetic approach are discussed.
Photodissociation of ultracold diatomic strontium molecules with quantum state control.
McDonald, M; McGuyer, B H; Apfelbeck, F; Lee, C-H; Majewska, I; Moszynski, R; Zelevinsky, T
2016-07-07
Chemical reactions at ultracold temperatures are expected to be dominated by quantum mechanical effects. Although progress towards ultracold chemistry has been made through atomic photoassociation, Feshbach resonances and bimolecular collisions, these approaches have been limited by imperfect quantum state selectivity. In particular, attaining complete control of the ground or excited continuum quantum states has remained a challenge. Here we achieve this control using photodissociation, an approach that encodes a wealth of information in the angular distribution of outgoing fragments. By photodissociating ultracold (88)Sr2 molecules with full control of the low-energy continuum, we access the quantum regime of ultracold chemistry, observing resonant and nonresonant barrier tunnelling, matter-wave interference of reaction products and forbidden reaction pathways. Our results illustrate the failure of the traditional quasiclassical model of photodissociation and instead are accurately described by a quantum mechanical model. The experimental ability to produce well-defined quantum continuum states at low energies will enable high-precision studies of long-range molecular potentials for which accurate quantum chemistry models are unavailable, and may serve as a source of entangled states and coherent matter waves for a wide range of experiments in quantum optics.
Photodissociation of ultracold diatomic strontium molecules with quantum state control
McDonald, M.; McGuyer, B. H.; Apfelbeck, F.; Lee, C.-H.; Majewska, I.; Moszynski, R.; Zelevinsky, T.
2016-07-01
Chemical reactions at ultracold temperatures are expected to be dominated by quantum mechanical effects. Although progress towards ultracold chemistry has been made through atomic photoassociation, Feshbach resonances and bimolecular collisions, these approaches have been limited by imperfect quantum state selectivity. In particular, attaining complete control of the ground or excited continuum quantum states has remained a challenge. Here we achieve this control using photodissociation, an approach that encodes a wealth of information in the angular distribution of outgoing fragments. By photodissociating ultracold 88Sr2 molecules with full control of the low-energy continuum, we access the quantum regime of ultracold chemistry, observing resonant and nonresonant barrier tunnelling, matter-wave interference of reaction products and forbidden reaction pathways. Our results illustrate the failure of the traditional quasiclassical model of photodissociation and instead are accurately described by a quantum mechanical model. The experimental ability to produce well-defined quantum continuum states at low energies will enable high-precision studies of long-range molecular potentials for which accurate quantum chemistry models are unavailable, and may serve as a source of entangled states and coherent matter waves for a wide range of experiments in quantum optics.
Click Chemistry-Mediated Nanosensors for Biochemical Assays
Chen, Yiping; Xianyu, Yunlei; Wu, Jing; Yin, Binfeng; Jiang, Xingyu
2016-01-01
Click chemistry combined with functional nanoparticles have drawn increasing attention in biochemical assays because they are promising in developing biosensors with effective signal transformation/amplification and straightforward signal readout for clinical diagnostic assays. In this review, we focus on the latest advances of biochemical assays based on Cu (I)-catalyzed 1, 3-dipolar cycloaddition of azides and alkynes (CuAAC)-mediated nanosensors, as well as the functionalization of nanoprobes based on click chemistry. Nanoprobes including gold nanoparticles, quantum dots, magnetic nanoparticles and carbon nanomaterials are covered. We discuss the advantages of click chemistry-mediated nanosensors for biochemical assays, and give perspectives on the development of click chemistry-mediated approaches for clinical diagnosis and other biomedical applications. PMID:27217831
Click Chemistry-Mediated Nanosensors for Biochemical Assays.
Chen, Yiping; Xianyu, Yunlei; Wu, Jing; Yin, Binfeng; Jiang, Xingyu
2016-01-01
Click chemistry combined with functional nanoparticles have drawn increasing attention in biochemical assays because they are promising in developing biosensors with effective signal transformation/amplification and straightforward signal readout for clinical diagnostic assays. In this review, we focus on the latest advances of biochemical assays based on Cu (I)-catalyzed 1, 3-dipolar cycloaddition of azides and alkynes (CuAAC)-mediated nanosensors, as well as the functionalization of nanoprobes based on click chemistry. Nanoprobes including gold nanoparticles, quantum dots, magnetic nanoparticles and carbon nanomaterials are covered. We discuss the advantages of click chemistry-mediated nanosensors for biochemical assays, and give perspectives on the development of click chemistry-mediated approaches for clinical diagnosis and other biomedical applications.
Solving the quantum brachistochrone equation through differential geometry
You, Chenglong; Wilde, Mark; Dowling, Jonathan; Wang, Xiaoting
2016-05-01
The ability of generating a particular quantum state, or model a physical quantum device by exploring quantum state transfer, is important in many applications such as quantum chemistry, quantum information processing, quantum metrology and cooling. Due to the environmental noise, a quantum device suffers from decoherence causing information loss. Hence, completing the state-generation task in a time-optimal way can be considered as a straightforward method to reduce decoherence. For a quantum system whose Hamiltonian has a fixed type and a finite energy bandwidth, it has been found that the time-optimal quantum evolution can be characterized by the quantum brachistochrone equation. In addition, the brachistochrone curve is found to have a geometric interpretation: it is the limit of a one-parameter family of geodesics on a sub-Riemannian model. Such geodesic-brachistochrone connection provides an efficient numerical method to solve the quantum brachistochrone equation. In this work, we will demonstrate this numerical method by studying the time-optimal state-generating problem on a given quantum spin system. We also find that the Pareto weighted-sum optimization turns out to be a simple but efficient method in solving the quantum time-optimal problems. We would like to acknowledge support from NSF under Award No. CCF-1350397.
Discovering Chemistry With Natural Bond Orbitals
Weinhold, Frank
2012-01-01
This book explores chemical bonds, their intrinsic energies, and the corresponding dissociation energies which are relevant in reactivity problems. It offers the first book on conceptual quantum chemistry, a key area for understanding chemical principles and predicting chemical properties. It presents NBO mathematical algorithms embedded in a well-tested and widely used computer program (currently, NBO 5.9). While encouraging a "look under the hood" (Appendix A), this book mainly enables students to gain proficiency in using the NBO program to re-express complex wavefunctions in terms of intui
Flow chemistry meets advanced functional materials.
Myers, Rebecca M; Fitzpatrick, Daniel E; Turner, Richard M; Ley, Steven V
2014-09-22
Flow chemistry and continuous processing techniques are beginning to have a profound impact on the production of functional materials ranging from quantum dots, nanoparticles and metal organic frameworks to polymers and dyes. These techniques provide robust procedures which not only enable accurate control of the product material's properties but they are also ideally suited to conducting experiments on scale. The modular nature of flow and continuous processing equipment rapidly facilitates reaction optimisation and variation in function of the products. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Cariolaro, Gianfranco
2015-01-01
This book demonstrates that a quantum communication system using the coherent light of a laser can achieve performance orders of magnitude superior to classical optical communications Quantum Communications provides the Masters and PhD signals or communications student with a complete basics-to-applications course in using the principles of quantum mechanics to provide cutting-edge telecommunications. Assuming only knowledge of elementary probability, complex analysis and optics, the book guides its reader through the fundamentals of vector and Hilbert spaces and the necessary quantum-mechanical ideas, simply formulated in four postulates. A turn to practical matters begins with and is then developed by: · development of the concept of quantum decision, emphasizing the optimization of measurements to extract useful information from a quantum system; · general formulation of a transmitter–receiver system · particular treatment of the most popular quantum co...
Art in Chemistry; Chemistry in Art.
Greenberg, Barbara R.; Patterson, Dianne
High school teachers are often challenged to motivate students who have little or no interest in a subject and are bored with traditional instruction. This unique book is designed to help educators make chemistry classes more interesting and links art curriculum to practical applications, integrating the two subjects through scores of hands-on…
Korean Kimchi Chemistry: A Multicultural Chemistry Connection
Murfin, Brian
2009-01-01
Connecting science with different cultures is one way to interest students in science, to relate science to their lives, and at the same time to broaden their horizons in a variety of ways. In the lesson described here, students make kimchi, a delicious and popular Korean dish that can be used to explore many important chemistry concepts,…
Quantum Information Processing in the Radical-Pair Mechanism
Mouloudakis, K
2016-01-01
Radical-ion-pair reactions, central for understanding the avian magnetic compass and spin transport in photosynthetic reaction centers, were recently shown to be a fruitful paradigm of the new synthesis of quantum information science with biological processes. We here show that the master equation so far constituting the theoretical foundation of spin chemistry violates fundamental bounds for the entropy of quantum systems, in particular the Ozawa bound. In contrast, a recently developed theory based on quantum measurements, quantum coherence measures and quantum retrodiction, thus exemplifying the paradigm of quantum biology, satisfies the Ozawa bound as well as the Lanford-Robinson bound on information extraction. By considering the quantum information extracted during the reaction we unravel new magnetic-field effects not conveyed by reaction yields.