Examination of the structures, energetics, and vibrational frequencies of small sulfur‐containing prototypical dimers, (H₂S)₂ and H₂O/H₂S

Abstract

The optimized geometries, vibrational frequencies, and dissociation energies from MP2 and CCSD(T) computations with large correlation consistent basis sets are reported for (H2S)2 and H2O/H2S. Anharmonic vibrational frequencies have also been computed with second‐order vibrational perturbation theory (VPT2). As such, the fundamental frequencies, overtones, and combination bands reported in this study should also provide a useful road map for future spectroscopic studies of the simple but important heterogeneous H2O/H2S dimer in which the hydrogen bond donor and acceptor can interchange, leading to two unique minima with very similar energies. Near the CCSD(T) complete basis set limit, the HOH⋯SH2 configuration (H2O donor) lies only 0.2 kcal mol−1 below the HSH⋯OH2 structure (H2S donor). When the zero‐point vibrational energy is included, however, the latter configuration becomes slightly lower in energy than the former by <0.1 kcal mol−1. © 2018 Wiley Periodicals, Inc.

Vibrational study in neon matrix of H2S-H2O, H2S-(H2O)2, and (H2S)2-H2O complexes. Identification of the two isomers: HOH-SH2 (H2O proton donor) and HSH-OH2 (H2S proton donor)

“…After a brief description of the experimental conditions, the spectra will be presented. An assignment of the different observed bands to 1:1, 1:2, and 2:1 complexes and isomers will be proposed with the support of theoretical results found in literature 31,32 and of our own calculations for 1:2 and 2:1 complexes.…”

“…The comparison between the theoretical and experimental Δν values can confirm our experimental attributions and helps to deduce, if possible, the structure of the observed 1:1, 1:2, and 2:1 complexes. As mentioned in introduction, calculated vibrational data 32 have been performed for the two 1:1 isomers (H 2 O and H 2 S proton donor), so the harmonic CCSD(T)/ha(Q+d)Z data will be taken as reference to calculate the theoretical shifts. These data are in agreement with those of reference 31 and with our calculations (Table S1 in (Table S3 and S4 in the supplementary material).…”

“…Vibrational theoretical studies were performed on the H 2 S monomer and dimer and on the H 2 S-H 2 O complex at MP2 and CCSD(T) level. 11,[28][29][30][31][32] For this complex, a study 31 gives data on stabilities, geometries and harmonic frequencies only for the H 2 O proton donor complex, HOH-SH 2 . Another recent one 32 gives these data for the two isomers HSH-OH 2 and HOH-SH 2 with in addition anharmonic frequencies and intensities and concludes that the two isomers are isoenergetic.…”

“…11,[28][29][30][31][32] For this complex, a study 31 gives data on stabilities, geometries and harmonic frequencies only for the H 2 O proton donor complex, HOH-SH 2 . Another recent one 32 gives these data for the two isomers HSH-OH 2 and HOH-SH 2 with in addition anharmonic frequencies and intensities and concludes that the two isomers are isoenergetic. With regard to experimental gaps and uncertainties found in literature for these complexes we have undertaken for the first time the infrared study in solid neon of (H 2 S)n-(H 2 O)m complexes, noted n:m, and in particular the 1:1 complex with the observation of the two isomers HOH-SH 2 , noted A, and HSH-OH 2 , noted B, and also (H 2 S) 2 -H 2 O (noted 2:1) and H 2 S-(H 2 O) 2 (noted 1:2) complexes.…”

Nature of the Interaction of Pyridines with OCS. A Theoretical Investigation

“…These complexes involve the interaction of the XB...YZ type where Y possesses one or more electron pairs. They have been classified into halogen bonds where B is a halogen [5][6][7][8][9][10][11][12][13][14][15], chalcogen bonds where B = O, S, Se [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34], and more recently, tetrel bonds where B = C, Si [35][36][37][38][39][40][41][42]. These bonds are unusual in that they involve a close approach of two electronegative atoms such as Cl, O, C on the one hand, and Y atoms such as N on the other hand.…”