An Effective and Automated Processing of Resonances in Vibrational Perturbation Theory Applied to Spectroscopy

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F22%3A00565506" target="_blank" >RIV/61388963:_____/22:00565506 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1021/acs.jpca.2c06460" target="_blank" >https://doi.org/10.1021/acs.jpca.2c06460</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.2c06460" target="_blank" >10.1021/acs.jpca.2c06460</a>

Jazyk výsledku

angličtina

Název v původním jazyce

An Effective and Automated Processing of Resonances in Vibrational Perturbation Theory Applied to Spectroscopy

Popis výsledku v původním jazyce

The broader availability of cost-effective methodologies like second-order vibrational perturbational theory (VPT2), also in general-purpose quantum chemical programs, has made the inclusion of anharmonic effects in vibrational calculations easier, paving the way to more accurate simulations. Combined with modern computing hardware, VPT2 can be used on relatively complex molecular systems with dozen of atoms. However, the problem of resonances and their corrections remains a critical pitfall of perturbative methods. Recent works have highlighted the sensitivity of band intensities to even subtle resonance effects, underlying the importance of a correct treatment to predict accurate spectral bandshapes. This aspect is even more critical with chiroptical spectroscopies whose signal is weak. This has motivated the present work in exploring robust methods and criteria to identify resonances not only in energy calculations but also on the transition moments. To study their performance, three molecules of representative sizes ranging from ten to several dozens of atoms were chosen. The impact of resonances, as well as the accuracy achievable once they are properly treated, is illustrated by the changes in spectral bandshapes, including chiroptical spectroscopies.

Název v anglickém jazyce

An Effective and Automated Processing of Resonances in Vibrational Perturbation Theory Applied to Spectroscopy

Popis výsledku anglicky

The broader availability of cost-effective methodologies like second-order vibrational perturbational theory (VPT2), also in general-purpose quantum chemical programs, has made the inclusion of anharmonic effects in vibrational calculations easier, paving the way to more accurate simulations. Combined with modern computing hardware, VPT2 can be used on relatively complex molecular systems with dozen of atoms. However, the problem of resonances and their corrections remains a critical pitfall of perturbative methods. Recent works have highlighted the sensitivity of band intensities to even subtle resonance effects, underlying the importance of a correct treatment to predict accurate spectral bandshapes. This aspect is even more critical with chiroptical spectroscopies whose signal is weak. This has motivated the present work in exploring robust methods and criteria to identify resonances not only in energy calculations but also on the transition moments. To study their performance, three molecules of representative sizes ranging from ten to several dozens of atoms were chosen. The impact of resonances, as well as the accuracy achievable once they are properly treated, is illustrated by the changes in spectral bandshapes, including chiroptical spectroscopies.

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

2022

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

1520-5215

Svazek periodika

126

Číslo periodika v rámci svazku

49

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

27

Strana od-do

9276-9302

Kód UT WoS článku

000892229700001

EID výsledku v databázi Scopus

2-s2.0-85143535498