Critical Assessment of Curvature-Driven Surface Hopping Algorithms
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Critical Assessment of Curvature-Driven Surface Hopping Algorithms
Original language description
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
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Chemical Theory and Computation
ISSN
1549-9618
e-ISSN
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Volume of the periodical
21
Issue of the periodical within the volume
19
Country of publishing house
US - UNITED STATES
Number of pages
15
Pages from-to
9784-9798
UT code for WoS article
001572363500001
EID of the result in the Scopus database
2-s2.0-105018717554