Computational Structures and SAPT Interaction Energies of HXeSH···H2Y (Y=O or S) Complexes

Abstract

Ab initio calculations of the structures, vibrational spectra and supermolecular and symmetry-adapted perturbation theory (SAPT) interaction energies of the HXeOH and HXeSH complexes with H2O and H2S molecules are presented. Two minima already reported in the literature were reproduced and ten new ones were found together with some transition states. All complexes show blue shift in Xe–H stretching mode upon complexation. The computed spectra suggest that it should be possible to detect and distinguish the complexes experimentally. The structures where H2O or H2S is the proton-donor were found to be the most stable for all complex compositions. The SAPT analysis shows significant differences between the complexes with H2O and H2S indicating much larger dispersion and exchange contributions in the complexes with H2S.

Molecular Recognition, Transient Chirality and Sulfur Hydrogen Bonding in the Benzyl Mercaptan Dimer

“…84% smaller than in the benzyl alcohol dimer (−42.1 kJ mol −1 ) [43], reflecting the weaker thiol H-bond. Additional insight into the nature of the thiol hydrogen bond is obtained from the attractive contributions to the energy decomposition [67,68]. The largest attractive contributor in the benzyl mercaptan dimer is dispersive (54%) but in smaller proportion than in the thiophenol dimer (60%) and with larger electrostatic participation (34% vs. 29-31% in thiophenol).…”

Complexes of HXeY with HX (Y, X = F, Cl, Br, I): Symmetry-Adapted Perturbation Theory Study and Anharmonic Vibrational Analysis

“…Some of the investigated structures were previously reported and studied experimentally and computationally [ 13 , 14 , 34 , 36 , 38 , 40 ]. Zhang et al [ 15 ] recently studied the H-Xe bonding in all these structures, except 2a and 3a, for Y and X = Cl, Br, I.…”

“…Indeed, xenon forms a large number of compounds and complexes compared to other noble-gas elements, including the HXeY family of compounds: among these, the HXeOH molecule has been studied extensively [ 10 , 14 , 17 , 18 , 19 , 31 ]. The different properties of other complexes have also received considerable attention, both experimentally and computationally: the reported studies include HXeCl/Br/I⋯H O [ 32 , 33 ], HXeCl/Br⋯HCl/Br [ 20 , 34 ], HXeI⋯HBr/I [ 35 ], HXeI⋯HCl and HXeI⋯HCCH [ 36 ], (HXeF) and (HXeF) [ 37 ], HXeF⋯HF [ 13 , 34 , 38 ], HXeBr/Cl⋯HCl/Br and HXeCCH⋯CO [ 14 ], HXeBr⋯CO [ 39 ], HXeSH⋯H O/H S [ 40 ], and HXeOH⋯H S. Recently, Zhang et al [ 15 ] investigated a large set of systems, i.e., HXeY⋯HX (Y = Cl/Br/I and X = OH/Cl/Br/I/CCH/CN), and established the charge-shift nature of the H-Xe bonding in the noble-gas molecule.…”

The Quantum Electronic Partitioning as Modernization in the Studies of the Intermolecular Interactions

“…Traditionally, it can be seen that the interaction energies scan a large spectrum with results from -0.60 up to -65.47 Kcal/mol, there is no any detailed explanation with respect to origins of these interaction energies. In complexes whose structure bring the presence of inert gases, e.g., xenon, in a study signed by Cukras and co-authors [37], it is not the dispersion that stands out, but truly the spin exchange bringing its destabilization in many cases, e.g., HXeOH•••H2S and HXeSH•••H2S (see Fig. 2), wherein it outweighs or equivalents with the electrostatic character due to the values of 73.22 (E exch (10) ) and -59.17 KJ/mol (E elec (10) ) as well as 46.11 (E exch (10) ) and -35.46 KJ/mol (E elec (10) ).…”