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Journal ArticleDOI

Molecular dynamics with electronic transitions

John C. Tully
- 15 Jul 1990 - 
- Vol. 93, Iss: 2, pp 1061-1071
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TLDR
In this article, a method for carrying out molecular dynamics simulations of processes that involve electronic transitions is proposed, where the time dependent electronic Schrodinger equation is solved self-consistently with the classical mechanical equations of motion of the atoms.
Abstract
A method is proposed for carrying out molecular dynamics simulations of processes that involve electronic transitions. The time dependent electronic Schrodinger equation is solved self‐consistently with the classical mechanical equations of motion of the atoms. At each integration time step a decision is made whether to switch electronic states, according to probabilistic ‘‘fewest switches’’ algorithm. If a switch occurs, the component of velocity in the direction of the nonadiabatic coupling vector is adjusted to conserve energy. The procedure allows electronic transitions to occur anywhere among any number of coupled states, governed by the quantum mechanical probabilities. The method is tested against accurate quantal calculations for three one‐dimensional, two‐state models, two of which have been specifically designed to challenge any such mixed classical–quantal dynamical theory. Although there are some discrepancies, initial indications are encouraging. The model should be applicable to a wide variety of gas‐phase and condensed‐phase phenomena occurring even down to thermal energies.

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On the dynamics of coupled Bohmian and phase-space variables: a new hybrid quantum-classical approach.

TL;DR: Partial hydrodynamic moments are introduced, the dynamics of which is determined by a hierarchy of equations derived from the quantum Liouville equation, and a trajectory representation in a hybrid hydrod dynamic-Liouvillian phase space is introduced.
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Quasi-diabatic representations of adiabatic potential energy surfaces coupled by conical intersections including bond breaking: a more general construction procedure and an analysis of the diabatic representation.

TL;DR: Extensions of a promising method for representing the nuclear coordinate dependence of the energies, energy gradients, and derivative couplings of N(state) adiabatic electronic states coupled by conical intersections are described and analyzed.
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Modeling ultrafast exciton deactivation in oligothiophenes via nonadiabatic dynamics.

TL;DR: These data agree with the self-localization mechanism observed for poly(3-hexylthiophene) (P3HT) and shed light on the complex exciton relaxation dynamics occurring in π-conjugated oligomers of potential interest for optoelectronic applications.
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Semiclassical Tunneling Rates from Ab Initio Molecular Dynamics

TL;DR: In this article, a new ab initio semiclassical technique for investigating tunneling effects is proposed, which incorporates tunneling effect into first principles molecular dynamics and applies it to the intramolecular proton transfer in malonaldehyde.
References
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Journal ArticleDOI

Trajectory Surface Hopping Approach to Nonadiabatic Molecular Collisions: The Reaction of H+ with D2

TL;DR: In this article, an extension of the classical trajectory approach is proposed that may be useful in treating many types of nonadiabatic molecular collisions, where nuclei are assumed to move classically on a single potential energy surface until an avoided surface crossing or other region of large NDE coupling is reached.
Journal ArticleDOI

A fourier method solution for the time dependent Schrödinger equation as a tool in molecular dynamics

TL;DR: In this paper, a new method is presented for the solution of the time dependent SchrBdinger equation in its application to physical and chemical molecular phenomena, which is based on discretizing space and time on a grid, and using the Fourier method to produce both spatial derivatives, and second order differencing for time derivatives.
Book

Mathematical methods for digital computers

TL;DR: This is the book that many people in the world waiting for to publish, mathematical methods for digital computers, and the book lovers are really curious to see how this book is actually.
BookDOI

Dynamics of Molecular Collisions

TL;DR: In this paper, the potential energy surfaces and their effect on collision processes are discussed. But the authors focus on the nonadiabatic processes in collision theory and not on the classical trajectories of trajectories.
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