A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Moller–Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr_2 dimer, exploring zeolite-catalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.

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Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

The canonical example of a quantum-mechanical two-level system is spin. The simplest picture of spin is a magnetic moment pointing up or down. The full quantum properties of spin become apparent in phenomena such as superpositions of spin states, entanglement among spins, and quantum measurements. Many of these phenomena have been observed in experiments performed on ensembles of particles with spin. Only in recent years have systems been realized in which individual electrons can be trapped and their quantum properties can be studied, thus avoiding unnecessary ensemble averaging. This review describes experiments performed with quantum dots, which are nanometer-scale boxes defined in a semiconductor host material. Quantum dots can hold a precise but tunable number of electron spins starting with 0, 1, 2, etc. Electrical contacts can be made for charge transport measurements and electrostatic gates can be used for controlling the dot potential. This system provides virtually full control over individual electrons. This new, enabling technology is stimulating research on individual spins. This review describes the physics of spins in quantum dots containing one or two electrons, from an experimentalist’s viewpoint. Various methods for extracting spin properties from experiment are presented, restricted exclusively to electrical measurements. Furthermore, experimental techniques are discussed that allow for 1 the rotation of an electron spin into a superposition of up and down, 2 the measurement of the quantum state of an individual spin, and 3 the control of the interaction between two neighboring spins by the Heisenberg exchange interaction. Finally, the physics of the relevant relaxation and dephasing mechanisms is reviewed and experimental results are compared with theories for spin-orbit and hyperfine interactions. All these subjects are directly relevant for the fields of quantum information processing and spintronics with single spins i.e., single spintronics.

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Spins in few-electron quantum dots

▪ Abstract Proton-coupled electron transfer (PCET) is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues. We review several are...

/pdf/proton-coupled-electron-transfer-3oyvp0w9qd.pdf

Proton-Coupled Electron Transfer

A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller–Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr2 dimer, exploring zeolite-catalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.

RESEARCH ARTICLE Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

This article aims to provide an introductory survey on quantum random walks. Starting from a physical effect to illustrate the main ideas we will introduce quantum random walks, review some of their properties and outline their striking differences to classical walks. We will touch upon both physical effects and computer science applications, introducing some of the main concepts and language of present day quantum information science in this context. We will mention recent developments in this new area and outline some open questions.

Quantum random walks: an introductory overview

Quantum random walks on graphs have been shown to display many interesting properties, including exponentially fast hitting times when compared with their classical counterparts. However, it is still unclear how to use these novel properties to gain an algorithmic speedup over classical algorithms. In this paper, we present a quantum search algorithm based on the quantum random-walk architecture that provides such a speedup. It will be shown that this algorithm performs an oracle search on a database of N items with $O(\sqrt{N})$ calls to the oracle, yielding a speedup similar to other quantum search algorithms. It appears that the quantum random-walk formulation has considerable flexibility, presenting interesting opportunities for development of other, possibly novel quantum algorithms.

https://arxiv.org/pdf/quant-ph/0210064.pdf

Quantum random-walk search algorithm

As originally proposed, the fewest switches surface hopping (FSSH) algorithm does not allow for decoherence between wavefunction amplitudes on different adiabatic surfaces. In this paper, we propose an inexpensive correction to standard FSSH dynamics wherein we explicitly model the decoherence of nuclear wave packets on distinct electronic surfaces. Our augmented fewest switches surface hopping approach is conceptually simple and, thus far, it has allowed us to capture several key features of the exact quantum results. Two points in particular merit attention. First, we obtain the correct branching ratios when a quantum particle passes through more than one region of nonadiabatic coupling. Second, our formalism provides a new and natural approach for rescaling nuclear momenta after a surface hop. Both of these features should become increasingly important as surface hopping schemes are applied to higher-dimensional problems.

A new approach to decoherence and momentum rescaling in the surface hopping algorithm.

Nonadiabatic coupling of nuclear motion to electronic excitations at metal surfaces is believed to influence a host of important chemical processes and has generated a great deal of experimental and theoretical interest. We applied a recently developed theoretical framework to examine the nature and importance of nonadiabatic behavior in a system that has been extensively studied experimentally: the scattering of vibrationally excited nitric oxide molecules from a Au(111) surface. We conclude that the nonadiabatic transition rate depends strongly on both the N-O internuclear separation and the molecular orientation and, furthermore, that molecule-surface forces can steer the molecule into strong-coupling configurations. This mechanism elucidates key features of the experiments and provides several testable predictions regarding the dependence of vibrational energy transfer on the initial vibrational energy, molecular orientation, and incident angle.

https://science.sciencemag.org/content/sci/326/5954/829.full.pdf

Dynamical steering and electronic excitation in NO scattering from a gold surface.

Recent experiments have shown convincing evidence for nonadiabatic energy transfer from adsorbate degrees of freedom to surface electrons during the interaction of molecules with metal surfaces. In this paper, we propose an independent-electron surface hopping algorithm for the simulation of nonadiabatic gas-surface dynamics. The transfer of energy to electron-hole pair excitations of the metal is successfully captured by hops between electronic adiabats. The algorithm is able to account for the creation of multiple electron-hole pairs in the metal due to nonadiabatic transitions. Detailed simulations of the vibrational relaxation of nitric oxide on a gold surface, employing a multistate potential energy surface fit to density functional theory calculations, confirm that our algorithm can capture the underlying physics of the inelastic scattering process.

Nonadiabatic dynamics at metal surfaces: Independent-electron surface hopping

For a system which undergoes electron or energy transfer in a polar solvent, we define the diabatic states to be the initial and final states of the system, before and after the nonequilibrium transfer process. We consider two models for the system-solvent interactions: A solvent which is linearly polarized in space and a solvent which responds linearly to the system. From these models, we derive two new schemes for obtaining diabatic states from ab initio calculations of the isolated system in the absence of solvent. These algorithms resemble standard approaches for orbital localization, namely, the Boys and Edmiston-Ruedenberg (ER) formalisms. We show that Boys localization is appropriate for describing electron transfer [Subotnik et al., J. Chem. Phys. 129, 244101 (2008)] while ER describes both electron and energy transfer. Neither the Boys nor the ER methods require definitions of donor or acceptor fragments and both are computationally inexpensive. We investigate one chemical example, the case of oligomethylphenyl-3, and we provide attachment/detachment plots whereby the ER diabatic states are seen to have localized electron-hole pairs.

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Neil Shenvi

Papers

Quantum random-walk search algorithm

A new approach to decoherence and momentum rescaling in the surface hopping algorithm.

Dynamical steering and electronic excitation in NO scattering from a gold surface.

Nonadiabatic dynamics at metal surfaces: Independent-electron surface hopping

The initial and final states of electron and energy transfer processes: diabatization as motivated by system-solvent interactions.