Treatment of Herzberg-Teller and non-Condon effects in optical spectra with Hierarchical Equations of Motion

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F18%3A10389020" target="_blank" >RIV/00216208:11320/18:10389020 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1016/j.chemphys.2018.08.026" target="_blank" >https://doi.org/10.1016/j.chemphys.2018.08.026</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.chemphys.2018.08.026" target="_blank" >10.1016/j.chemphys.2018.08.026</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Treatment of Herzberg-Teller and non-Condon effects in optical spectra with Hierarchical Equations of Motion

Popis výsledku v původním jazyce

We derive a Hierarchical Equations of Motion (HEOM) description of nonadiabatic Herzberg-Teller type coupling effects and of non-Condon effects in a system of electronic transitions interacting with intra- and inter-molecular vibrational modes. We point out analogies between the auxiliary density operators (ADOs) of the hierarchy and the terms arising from explicit description of the vibrational modes in the Hamiltonian. In comparison with the standard formulation of HEOM, our equations contain additional connections between ADOs in the hierarchy scheme, which account for the dependence of the nonadiabatic coupling elements on the vibrational coordinates. We compare absorption spectra calculated with our HEOM methodology and with explicit treatment of vibrational DOF for a dimer system in the strong resonance coupling regime. Furthermore, we show that for sufficiently strong excitonic coupling, the corresponding effects in linear absorption spectra of vibronic dimers can be captured very well by the concept of effective Huang-Rhys factors.

Název v anglickém jazyce

Treatment of Herzberg-Teller and non-Condon effects in optical spectra with Hierarchical Equations of Motion

Popis výsledku anglicky

We derive a Hierarchical Equations of Motion (HEOM) description of nonadiabatic Herzberg-Teller type coupling effects and of non-Condon effects in a system of electronic transitions interacting with intra- and inter-molecular vibrational modes. We point out analogies between the auxiliary density operators (ADOs) of the hierarchy and the terms arising from explicit description of the vibrational modes in the Hamiltonian. In comparison with the standard formulation of HEOM, our equations contain additional connections between ADOs in the hierarchy scheme, which account for the dependence of the nonadiabatic coupling elements on the vibrational coordinates. We compare absorption spectra calculated with our HEOM methodology and with explicit treatment of vibrational DOF for a dimer system in the strong resonance coupling regime. Furthermore, we show that for sufficiently strong excitonic coupling, the corresponding effects in linear absorption spectra of vibronic dimers can be captured very well by the concept of effective Huang-Rhys factors.

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

<a href="/cs/project/GA17-22160S" target="_blank" >GA17-22160S: Kvantová teorie přenosu excitační energie a pokročilé optické spektroskopie: od malých molekul ke světlosběrným systémům</a><br>

Návaznosti

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

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Chemical Physics

ISSN

0301-0104

e-ISSN

—

Svazek periodika

515

Číslo periodika v rámci svazku

November 2018

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

12

Strana od-do

129-140

Kód UT WoS článku

000454412800016

EID výsledku v databázi Scopus

2-s2.0-85053884829