Pragmatic Approach to Photodynamics: Mixed Landau-Zener Surface Hopping with Intersystem Crossing

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F20%3A43920932" target="_blank" >RIV/60461373:22340/20:43920932 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/abs/10.1021/acs.jctc.0c00512" target="_blank" >https://pubs.acs.org/doi/abs/10.1021/acs.jctc.0c00512</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.0c00512" target="_blank" >10.1021/acs.jctc.0c00512</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Pragmatic Approach to Photodynamics: Mixed Landau-Zener Surface Hopping with Intersystem Crossing

Popis výsledku v původním jazyce

Ab initio excited state photodynamical simulations have entered the mainstream in the past two decades, bringing techniques of various sophistication and computational requirements for the description of nonadiabatic transitions. We explore in this work the performance of the recently reformulated Landau-Zener surface hopping (LZSH) approach and extend it for the simultaneous treatment of internal conversion and intersystem crossing events. We studied photochemical reactions of four model molecules (cyclopropanone, methaniminium cation, cytosine, and thiophene). The calculated quantities are generally in excellent agreement with the corresponding fewest switches surface hopping simulations. Furthermore, the algorithm proved to be significantly more stable and more computationally efficient. LZSH also puts fewer constraints on the electronic structure theory as the nonadiabatic couplings are not needed. We argue that the accuracy of photodynamical simulations is in practice dominated by the electronic structure theory, and it is, therefore, legitimate to use the simplest and the most efficient technique for the treatment of nonadiabatic transitions. Copyright © 2020 American Chemical Society.

Název v anglickém jazyce

Pragmatic Approach to Photodynamics: Mixed Landau-Zener Surface Hopping with Intersystem Crossing

Popis výsledku anglicky

Ab initio excited state photodynamical simulations have entered the mainstream in the past two decades, bringing techniques of various sophistication and computational requirements for the description of nonadiabatic transitions. We explore in this work the performance of the recently reformulated Landau-Zener surface hopping (LZSH) approach and extend it for the simultaneous treatment of internal conversion and intersystem crossing events. We studied photochemical reactions of four model molecules (cyclopropanone, methaniminium cation, cytosine, and thiophene). The calculated quantities are generally in excellent agreement with the corresponding fewest switches surface hopping simulations. Furthermore, the algorithm proved to be significantly more stable and more computationally efficient. LZSH also puts fewer constraints on the electronic structure theory as the nonadiabatic couplings are not needed. We argue that the accuracy of photodynamical simulations is in practice dominated by the electronic structure theory, and it is, therefore, legitimate to use the simplest and the most efficient technique for the treatment of nonadiabatic transitions. Copyright © 2020 American Chemical Society.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA20-15825S" target="_blank" >GA20-15825S: Přesná výpočetní spektroskopie: Spojení kvantové mechaniky a statistických přístupů</a><br>

Návaznosti

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

Rok uplatnění

2020

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

16

Číslo periodika v rámci svazku

9

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

5809-5820

Kód UT WoS článku

000570012000030

EID výsledku v databázi Scopus

2-s2.0-85090507192