Adaptive excitation frequencies in simulations of resonance Raman spectra

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00637827" target="_blank" >RIV/61388963:_____/25:00637827 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1063/5.0274585" target="_blank" >https://doi.org/10.1063/5.0274585</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0274585" target="_blank" >10.1063/5.0274585</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Adaptive excitation frequencies in simulations of resonance Raman spectra

Popis výsledku v původním jazyce

Within the Born-Oppenheimer approximation, differences of the vibrational energies are often neglected compared to the electronic ones. This leads to the Placzek approximation and the coupled-perturbed methodology, where the transition polarizabilities needed to simulate Raman spectra are calculated at an incident frequency. Within this approximation, the frequency change of the outgoing radiation is neglected, which has a little effect on the simulation of Raman and Raman optical activity spectra in the far from resonance limit. For resonance and pre-resonance, when the incident frequency is close to the energy of an electronic transition, significant error may arise. We analyze this problem and suggest a partial solution through a modification of the polarizability expressions to include a dependence on the vibrational frequencies. For model cobalt complexes, this improved formulation leads to a significant improvement of the spectral patterns.

Název v anglickém jazyce

Adaptive excitation frequencies in simulations of resonance Raman spectra

Popis výsledku anglicky

Within the Born-Oppenheimer approximation, differences of the vibrational energies are often neglected compared to the electronic ones. This leads to the Placzek approximation and the coupled-perturbed methodology, where the transition polarizabilities needed to simulate Raman spectra are calculated at an incident frequency. Within this approximation, the frequency change of the outgoing radiation is neglected, which has a little effect on the simulation of Raman and Raman optical activity spectra in the far from resonance limit. For resonance and pre-resonance, when the incident frequency is close to the energy of an electronic transition, significant error may arise. We analyze this problem and suggest a partial solution through a modification of the polarizability expressions to include a dependence on the vibrational frequencies. For model cobalt complexes, this improved formulation leads to a significant improvement of the spectral patterns.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA25-15726S" target="_blank" >GA25-15726S: Prozkoumání nových forem Ramanovy optické aktivity</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

1089-7690

Svazek periodika

163

Číslo periodika v rámci svazku

3

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

6

Strana od-do

034118

Kód UT WoS článku

001571795300002

EID výsledku v databázi Scopus

2-s2.0-105011394251