Scaling-up VPT2: A feasible route to include anharmonic correction on large molecules.

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F24%3A00582939" target="_blank" >RIV/61388963:_____/24:00582939 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1016/j.saa.2024.123969" target="_blank" >https://doi.org/10.1016/j.saa.2024.123969</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.saa.2024.123969" target="_blank" >10.1016/j.saa.2024.123969</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Scaling-up VPT2: A feasible route to include anharmonic correction on large molecules.

Popis výsledku v původním jazyce

Vibrational analysis plays a crucial role in the investigation of molecular systems. Though methodologies like second-order vibrational perturbation theory (VPT2) have paved the way to more accurate simulations, the computational cost remains a difficult barrier to overcome when the molecular size increases. Building upon recent advances in the identification of resonances, we propose an approach making anharmonic simulations possible for large-size systems, typically unreachable by standard means. This relies on the fact that, often, only portions of the whole spectra are of actual interest. Therefore, the anharmonic corrections can be included selectively on subsets of normal modes directly related to the regions of interest. Starting from the VPT2 equations, we evaluate rigorously and systematically the impact of the truncated anharmonic treatment onto simulations. The limit and feasibility of the reduced-dimensionality approach are detailed, starting on a smaller model system. The methodology is then challenged on the IR absorption and vibrational circular dichroism spectra of an organometallic complex in three different spectral ranges.

Název v anglickém jazyce

Scaling-up VPT2: A feasible route to include anharmonic correction on large molecules.

Popis výsledku anglicky

Vibrational analysis plays a crucial role in the investigation of molecular systems. Though methodologies like second-order vibrational perturbation theory (VPT2) have paved the way to more accurate simulations, the computational cost remains a difficult barrier to overcome when the molecular size increases. Building upon recent advances in the identification of resonances, we propose an approach making anharmonic simulations possible for large-size systems, typically unreachable by standard means. This relies on the fact that, often, only portions of the whole spectra are of actual interest. Therefore, the anharmonic corrections can be included selectively on subsets of normal modes directly related to the regions of interest. Starting from the VPT2 equations, we evaluate rigorously and systematically the impact of the truncated anharmonic treatment onto simulations. The limit and feasibility of the reduced-dimensionality approach are detailed, starting on a smaller model system. The methodology is then challenged on the IR absorption and vibrational circular dichroism spectra of an organometallic complex in three different spectral ranges.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

Spectrochimica Acta Part A-Molecular and Biomolecular Spectroscopy

ISSN

1386-1425

e-ISSN

1873-3557

Svazek periodika

311

Číslo periodika v rámci svazku

April

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

18

Strana od-do

123969

Kód UT WoS článku

001180684900001

EID výsledku v databázi Scopus

2-s2.0-85184151088