What Controls the Quality of Photodynamical Simulations? Electronic Structure Versus Nonadiabatic Algorithm
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F23%3A43928093" target="_blank" >RIV/60461373:22340/23:43928093 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acs.jctc.3c00908" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jctc.3c00908</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jctc.3c00908" target="_blank" >10.1021/acs.jctc.3c00908</a>
Alternative languages
Result language
angličtina
Original language name
What Controls the Quality of Photodynamical Simulations? Electronic Structure Versus Nonadiabatic Algorithm
Original language description
The field of nonadiabatic dynamics has matured over the last decade with a range of algorithms and electronic structure methods available at the moment. While the community currently focuses more on developing and benchmarking new nonadiabatic dynamics algorithms, the underlying electronic structure controls the outcome of nonadiabatic simulations. Yet, the electronic-structure sensitivity analysis is typically neglected. In this work, we present a sensitivity analysis of the nonadiabatic dynamics of cyclopropanone to electronic structure methods and nonadiabatic dynamics algorithms. In particular, we compare wave function-based CASSCF, FOMO-CASCI, MS- and XMS-CASPT2, density-functional REKS, and semiempirical MRCI-OM3 electronic structure methods with the Landau-Zener surface hopping, fewest switches surface hopping, and ab initio multiple spawning with informed stochastic selection algorithms. The results clearly demonstrate that the electronic structure choice significantly influences the accuracy of nonadiabatic dynamics for cyclopropanone even when the potential energy surfaces exhibit qualitative and quantitative similarities. Thus, selecting the electronic structure solely on the basis of the mapping of potential energy surfaces can be misleading. Conversely, we observe no discernible differences in the performance of the nonadiabatic dynamics algorithms across the various methods. Based on the above results, we discuss the present-day practice in computational photodynamics. © 2023 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
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA23-07066S" target="_blank" >GA23-07066S: Time-dependent simulations for time-resolved electronic spectroscopies</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2023
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
1549-9626
Volume of the periodical
19
Issue of the periodical within the volume
22
Country of publishing house
US - UNITED STATES
Number of pages
12
Pages from-to
8273-8284
UT code for WoS article
001110620500001
EID of the result in the Scopus database
2-s2.0-85177999703