Erratum: “How to recover Marcus theory with fewest switches surface hopping: Add just a touch of decoherence” [J. Chem. Phys. 137, 22A513 (2012)]

Landry, Brian R.; Subotnik, Joseph E.

doi:10.1063/1.4769287

Cited by 27 publications

(51 citation statements)

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“…29,50 By this limit, as discussed in Ref. 28, we imply that the system is formed of heavy nuclei moving with small velocities but which are still allowed to hop between diabatic surfacesan inherently quantum effect.…”

Section: Modified Initial Distributionsmentioning

confidence: 82%

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Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory

Richardson

Thoss

2014

The Journal of Chemical Physics

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Quantum mechanical canonical rate theory: A new approach based on the reactive flux and numerical analytic continuation methods J. Chem. Phys. 112, 2605 (2000); 10.1063/1.480834Erratum: "A unified framework for quantum activated rate processes. II. The nonadiabatic limit" [J. Chem. Phys. 106, 1769 There is currently much interest in the development of improved trajectory-based methods for the simulation of nonadiabatic processes in complex systems. An important goal for such methods is the accurate calculation of the rate constant over a wide range of electronic coupling strengths and it is often the nonadiabatic, weak-coupling limit, which being far from the Born-Oppenheimer regime, provides the greatest challenge to current methods. We show that in this limit there is an inherent sign problem impeding further development which originates from the use of the usual quantum flux correlation functions, which can be very oscillatory at short times. From linear response theory, we derive a modified flux correlation function for the calculation of nonadiabatic reaction rates, which still rigorously gives the correct result in the long-time limit regardless of electronic coupling strength, but unlike the usual formalism is not oscillatory in the weak-coupling regime. In particular, a trajectory simulation of the modified correlation function is naturally initialized in a region localized about the crossing of the potential energy surfaces. In the weak-coupling limit, a simple link can be found between the dynamics initialized from this transition-state region and an generalized quantum goldenrule transition-state theory, which is equivalent to Marcus theory in the classical harmonic limit. This new correlation function formalism thus provides a platform on which a wide variety of dynamical simulation methods can be built aiding the development of accurate nonadiabatic rate theories applicable to complex systems. © 2014 AIP Publishing LLC. [http://dx

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Section: Modified Initial Distributionsmentioning

confidence: 82%

“…A significant failure of the standard implementation 28 in the context of this work is that rates do not obey the correct 2 dependence in the goldenrule limit. 29 However, the method is simple to perform and to couple with on-the-fly electronic-structure calculations such that it has gained a high popularity.…”

Section: Introductionmentioning

confidence: 99%

Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory

Richardson

Thoss

2014

The Journal of Chemical Physics

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“…58 A number of workers have introduced procedures for including decoherence, but there is still active discussion about this issue. [59][60][61][62][63][64][65][66] A third important concern with treating some degrees of freedom classically and others quantum mechanically is properly incorporating detailed balance. It is well known that a quantum system driven by a finite temperature classical system will eventually approach infinite temperature; energy passes artificially from the classical to the quantum subsystem.…”

Section: Dynamicsmentioning

confidence: 99%

Perspective: Nonadiabatic dynamics theory

Tully

2012

The Journal of Chemical Physics

548

589

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Nonadiabatic dynamics-nuclear motion evolving on multiple potential energy surfaces-has captivated the interest of chemists for decades. Exciting advances in experimentation and theory have combined to greatly enhance our understanding of the rates and pathways of nonadiabatic chemical transformations. Nevertheless, there is a growing urgency for further development of theories that are practical and yet capable of reliable predictions, driven by fields such as solar energy, interstellar and atmospheric chemistry, photochemistry, vision, single molecule electronics, radiation damage, and many more. This Perspective examines the most significant theoretical and computational obstacles to achieving this goal, and suggests some possible strategies that may prove fruitful.

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“…Multiconfiguration schemes, such as Tully's surface hopping, are in general required to account for bifurcation paths with entaglement [45,46]. Although the undeniable success of these mixed approaches to describe many nonadiabatic phenomena, some limitations arise when quantum nuclear effects such as tunneling [47], decoherence [48] or interferences [49] occur. Only the so-called quantum wave packet methods [50][51][52] provide a complete description of nuclear quantum effects, although their computational cost becomes rapidly unaffordable with the size of the system.…”

Section: Nonadiabatic Molecular Dynamicsmentioning

confidence: 99%

Applied Bohmian mechanics

et al. 2014

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Abstract. Bohmian mechanics provides an explanation of quantum phenomena in terms of point-like particles guided by wave functions. This review focuses on the use of nonrelativistic Bohmian mechanics to address practical problems, rather than on its interpretation. Although the Bohmian and standard quantum theories have different formalisms, both give exactly the same predictions for all phenomena. Fifteen years ago, the quantum chemistry community began to study the practical usefulness of Bohmian mechanics. Since then, the scientific community has mainly applied it to study the (unitary) evolution of single-particle wave functions, either by developing efficient quantum trajectory algorithms or by providing a trajectorybased explanation of complicated quantum phenomena. Here we present a large list of examples showing how the Bohmian formalism provides a useful solution in different forefront research fields for this kind of problems (where the Bohmian and the quantum hydrodynamic formalisms coincide). In addition, this work also emphasizes that the Bohmian formalism can be a useful tool in other types of (nonunitary and nonlinear) quantum problems where the influence of the environment or the nonsimulated degrees of freedom are relevant. This review contains also examples on the use of the Bohmian formalism for the many-body problem, decoherence and measurement processes. The ability of the Bohmian formalism to analyze this last type of problems for (open) quantum systems remains mainly unexplored by the scientific community. The authors of this review are convinced that the final status of the Bohmian theory among the scientific community will be greatly influenced by its potential success in those types of problems that present nonunitary and/or nonlinear quantum evolutions. A brief introduction of the Bohmian formalism and some of its extensions are presented in the last part of this review.

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Erratum: “How to recover Marcus theory with fewest switches surface hopping: Add just a touch of decoherence” [J. Chem. Phys. 137, 22A513 (2012)]

Cited by 27 publications

References 1 publication

Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory

Non-oscillatory flux correlation functions for efficient nonadiabatic rate theory

Perspective: Nonadiabatic dynamics theory

Applied Bohmian mechanics

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