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.
Recommended Citation
K. M. Dreux and G. S. Tschumper, "Examination of the Structures, Energetics, and Vibrational Frequencies of Small Sulfur-Containing Prototypical Dimers, (H2S)2 and H2O/h2s," Journal of Computational Chemistry, vol. 40, no. 1, pp. 229 - 236, Wiley, Jan 2019.
The definitive version is available at https://doi.org/10.1002/jcc.25578
Department(s)
Chemistry
Publication Status
Full Access
Keywords and Phrases
anharmonic vibrational frequencies; dissociation energies; hydrogen bonding; second-order vibrational perturbation theory (VPT2); water/hydrogen sulfide homogeneous and heterogeneous dimers
International Standard Serial Number (ISSN)
1096-987X; 0192-8651
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2024 Wiley, All rights reserved.
Publication Date
05 Jan 2019
PubMed ID
30368839
Comments
National Science Foundation, Grant 1664998