Wydział Chemii

Hexu Ye

Marco Mendolicchio

Holger Kruse

Cristina Puzzarini

Małgorzata Biczysko

Vincenzo Barone

2020

Journal of Molecular Structure

1211

127933/1-127933/10

10.1016/j.molstruc.2020.127933

Naukowa

Angielski

Artykuł

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 Å for distances and 0.1° 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.

Semi-experimental, Composite scheme, Equilibrium structure, Coupled cluster, CBS, Disulfide

http://dx.doi.org/10.1016/j.molstruc.2020.127933

http://www.elsevier.com