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Phase-Space Approaches to Non-Adiaba...

Bian, Xuezhi,

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Phase-Space Approaches to Non-Adiabatic Dynamics /

Record Type:	Electronic resources : Monograph/item
Title/Author:	Phase-Space Approaches to Non-Adiabatic Dynamics // Xuezhi Bian.
Author:	Bian, Xuezhi,
Description:	1 electronic resource (206 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 86-07, Section: B.
Contained By:	Dissertations Abstracts International86-07B.
Subject:	Chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=31560031
ISBN:	9798302182562

Phase-Space Approaches to Non-Adiabatic Dynamics /
Bian, Xuezhi,

Phase-Space Approaches to Non-Adiabatic Dynamics /Xuezhi Bian. - 1 electronic resource (206 pages)

Source: Dissertations Abstracts International, Volume: 86-07, Section: B.

For nearly a century, the Born-Oppenheimer (BO) framework has served as the foundation of theoretical and computational chemistry. Chemists routinely perform electronic structure calculations and construct potential energy surfaces EBO(R) as functions of nuclear position R, and then propagate molecular dynamics on one or more of those same potential energy surfaces. However, despite the vast amount of chemical intuition has been built on the BO framework, dynamics along BO potential surfaces completely ignore linear and angular momentum transfer between nuclei and electrons and even fails to conserve total linear and angular momentum in certain scenarios (e.g., when propagating on a single symmetry broken surface).In this thesis, we begin by highlighting the existing problems of adiabatic and non-adiabatic dynamics methods under the BO framework. Specifically, we demonstrate that single BO molecular dynamics must include an extra nuclear Berry force in order to conserve total angular momentum, and non-adiabatic multi-surface dynamics methods like surface hopping are not well-defined when there are spin-related interactions and electronic degeneracies. To this end, we next propose a class of phase-space approaches based on a semiclassical phase-space electronic Hamiltonian, HPS(R, P), that is parameterized by both nuclear position R and momentum P . We demonstrate that propagating dynamics on phase-space potential energy surfaces, EPS(R, P ), obtained by diagonalizing HPS(R, P) not only captures the nuclear Berry curvature effects in model systems but also correctly handles the electronic inertia effects in ab initio simulations, allowing us to study angular momentum transfer processes. Finally, we find that phase-space approaches yield much better vibrational energies when non-adiabatic effects are strong. On the basis of this data, as combined with recent results showing that phase-space approaches can recover properties completely missing in the BO framework such as electronic momentum and vibrational circular dichroism - this thesis submits that phase-space methods have great potential for advancing the study of theoretical chemistry beyond the BO framework.

English

ISBN: 9798302182562Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

Angular momentum

Phase-Space Approaches to Non-Adiabatic Dynamics /
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520 $a For nearly a century, the Born-Oppenheimer (BO) framework has served as the foundation of theoretical and computational chemistry. Chemists routinely perform electronic structure calculations and construct potential energy surfaces EBO(R) as functions of nuclear position R, and then propagate molecular dynamics on one or more of those same potential energy surfaces. However, despite the vast amount of chemical intuition has been built on the BO framework, dynamics along BO potential surfaces completely ignore linear and angular momentum transfer between nuclei and electrons and even fails to conserve total linear and angular momentum in certain scenarios (e.g., when propagating on a single symmetry broken surface).In this thesis, we begin by highlighting the existing problems of adiabatic and non-adiabatic dynamics methods under the BO framework. Specifically, we demonstrate that single BO molecular dynamics must include an extra nuclear Berry force in order to conserve total angular momentum, and non-adiabatic multi-surface dynamics methods like surface hopping are not well-defined when there are spin-related interactions and electronic degeneracies. To this end, we next propose a class of phase-space approaches based on a semiclassical phase-space electronic Hamiltonian, HPS(R, P), that is parameterized by both nuclear position R and momentum P . We demonstrate that propagating dynamics on phase-space potential energy surfaces, EPS(R, P ), obtained by diagonalizing HPS(R, P) not only captures the nuclear Berry curvature effects in model systems but also correctly handles the electronic inertia effects in ab initio simulations, allowing us to study angular momentum transfer processes. Finally, we find that phase-space approaches yield much better vibrational energies when non-adiabatic effects are strong. On the basis of this data, as combined with recent results showing that phase-space approaches can recover properties completely missing in the BO framework such as electronic momentum and vibrational circular dichroism - this thesis submits that phase-space methods have great potential for advancing the study of theoretical chemistry beyond the BO framework.
546 $a English
590 $a School code: 0175
650 4 $a Chemistry. $3 516420
650 4 $a Physical chemistry. $3 1981412
650 4 $a Computational chemistry. $3 3350019
653 $a Angular momentum
653 $a Circular dichroism
653 $a Electronic degeneracies
653 $a Theoretical chemistry
690 $a 0485
690 $a 0219
690 $a 0494
710 2 $a University of Pennsylvania. $b Chemistry. $e degree granting institution. $3 3816410
720 1 $a Subotnik, Joseph E. $e degree supervisor.
773 0 $t Dissertations Abstracts International $g 86-07B.
790 $a 0175
791 $a Ph.D.
792 $a 2024
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