The challenging equilibrium structure of HSSH: Another success of the rotational spectroscopy / quantum chemistry synergism

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68081707%3A_____%2F20%3A00524576" target="_blank" >RIV/68081707:_____/20:00524576 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/pii/S002228602030257X?via%3Dihub" target="_blank" >https://www.sciencedirect.com/science/article/pii/S002228602030257X?via%3Dihub</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.molstruc.2020.127933" target="_blank" >10.1016/j.molstruc.2020.127933</a>

Jazyk výsledku

angličtina

Název v původním jazyce

The challenging equilibrium structure of HSSH: Another success of the rotational spectroscopy / quantum chemistry synergism

Popis výsledku v původním jazyce

The simplest molecule with a disulfide bond, hydrogen disulfide (HSSH), represents an ideal test model for the determination of accurate gas-phase equilibrium structures for molecules containing third-row elements. First, pure theoretical composite schemes based on the coupled-cluster (CC) theory, which take into account the extrapolation to the complete basis set limit, core-valence correlation contributions, higher excitations in the CC expansion, and relativistic effects, allow for calculating accurate reference geometrical parameters. Second, using experimental vibrational ground-state rotational constants for a set of isotopologues, in conjunction with vibrational corrections based on second-order vibrational perturbation theory formulation and the recently developed Molecular Structure Refinement (MSR) software, we have determined the semi-experimental (SE) equilibrium structure of HSSH. The comparison of SE parameters with the computational best estimates shows an agreement within 0.001 A for distances and 0.1 degrees for angles, thus further validating the SE approach as cost-effective, provided that the required experimental data are available. Together with the intrinsic interest of HSSH, also in connection with astrochemistry, highly accurate structural properties of a prototypical disulfide bond can serve as references for future studies of larger molecules of biological interest containing this challenging moiety. (C) 2020 Published by Elsevier B.V.

Název v anglickém jazyce

The challenging equilibrium structure of HSSH: Another success of the rotational spectroscopy / quantum chemistry synergism

Popis výsledku anglicky

The simplest molecule with a disulfide bond, hydrogen disulfide (HSSH), represents an ideal test model for the determination of accurate gas-phase equilibrium structures for molecules containing third-row elements. First, pure theoretical composite schemes based on the coupled-cluster (CC) theory, which take into account the extrapolation to the complete basis set limit, core-valence correlation contributions, higher excitations in the CC expansion, and relativistic effects, allow for calculating accurate reference geometrical parameters. Second, using experimental vibrational ground-state rotational constants for a set of isotopologues, in conjunction with vibrational corrections based on second-order vibrational perturbation theory formulation and the recently developed Molecular Structure Refinement (MSR) software, we have determined the semi-experimental (SE) equilibrium structure of HSSH. The comparison of SE parameters with the computational best estimates shows an agreement within 0.001 A for distances and 0.1 degrees for angles, thus further validating the SE approach as cost-effective, provided that the required experimental data are available. Together with the intrinsic interest of HSSH, also in connection with astrochemistry, highly accurate structural properties of a prototypical disulfide bond can serve as references for future studies of larger molecules of biological interest containing this challenging moiety. (C) 2020 Published by Elsevier B.V.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/EF15_003%2F0000477" target="_blank" >EF15_003/0000477: Strukturní gymnastika nukleových kyselin: od molekulárních principů přes biologické funkce k terapeutickým cílům.</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

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

Název periodika

Journal of Molecular Structure

ISSN

0022-2860

e-ISSN

—

Svazek periodika

1211

Číslo periodika v rámci svazku

JUL 5 2020

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

10

Strana od-do

127933

Kód UT WoS článku

000526086200044

EID výsledku v databázi Scopus

2-s2.0-85082396462