Critical Assessment of Curvature-Driven Surface Hopping Algorithms

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F25%3A43932626" target="_blank" >RIV/60461373:22340/25:43932626 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.jctc.5c01176" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jctc.5c01176</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.5c01176" target="_blank" >10.1021/acs.jctc.5c01176</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Critical Assessment of Curvature-Driven Surface Hopping Algorithms

Popis výsledku v původním jazyce

Trajectory surface-hopping (TSH) methods have become the most used approach in nonadiabatic molecular dynamics. The increasingly popular curvature-driven schemes represent a subset of TSH based on the implicit local diabatization of potential energy surfaces. Their appeal partly stems from compatibility with machine-learning frameworks that often provide only local PES information. Here, we critically assess the limitations of these curvature-based algorithms by examining three challenging scenarios: (i) dynamics involving more than two strongly coupled electronic states; (ii) trivial crossings; and (iii) spurious transitions arising from small discontinuities in multireference potential energy surfaces. Furthermore, we extend the Landau–Zener surface hopping (LZSH) method beyond two-state systems and introduce practical modifications to enhance its robustness. The performance is benchmarked on both low- and higher-dimensional model Hamiltonians, as well as realistic molecular systems treated with ab initio methods. While curvature-driven TSH using the explicit electronic coefficient propagation qualitatively captures the dynamics in most cases, we find no regime where it outperforms LZSH, especially when trivial crossings, multistate crossings, or discontinuities are encountered. Hence, we advocate for using a conceptually simple but solid LZSH method when nonadiabatic couplings are not available. © 2025 The Authors. Published by American Chemical Society

Název v anglickém jazyce

Critical Assessment of Curvature-Driven Surface Hopping Algorithms

Popis výsledku anglicky

Trajectory surface-hopping (TSH) methods have become the most used approach in nonadiabatic molecular dynamics. The increasingly popular curvature-driven schemes represent a subset of TSH based on the implicit local diabatization of potential energy surfaces. Their appeal partly stems from compatibility with machine-learning frameworks that often provide only local PES information. Here, we critically assess the limitations of these curvature-based algorithms by examining three challenging scenarios: (i) dynamics involving more than two strongly coupled electronic states; (ii) trivial crossings; and (iii) spurious transitions arising from small discontinuities in multireference potential energy surfaces. Furthermore, we extend the Landau–Zener surface hopping (LZSH) method beyond two-state systems and introduce practical modifications to enhance its robustness. The performance is benchmarked on both low- and higher-dimensional model Hamiltonians, as well as realistic molecular systems treated with ab initio methods. While curvature-driven TSH using the explicit electronic coefficient propagation qualitatively captures the dynamics in most cases, we find no regime where it outperforms LZSH, especially when trivial crossings, multistate crossings, or discontinuities are encountered. Hence, we advocate for using a conceptually simple but solid LZSH method when nonadiabatic couplings are not available. © 2025 The Authors. Published by American Chemical Society

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

—

Svazek periodika

21

Číslo periodika v rámci svazku

19

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

15

Strana od-do

9784-9798

Kód UT WoS článku

001572363500001

EID výsledku v databázi Scopus

2-s2.0-105018717554