On the nature of hydrogen bonding in the H 2 S dimer.

Autor: Jäger S; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany., Khatri J; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany., Meyer P; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany., Henkel S; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany., Schwaab G; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany., Nandi A; Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, GA, 30322, USA., Pandey P; Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, GA, 30322, USA., Barlow KR; Department of Chemistry and Biochemistry, University of Mississippi, University, MS, 38677-1848, USA., Perkins MA; Department of Chemistry and Biochemistry, University of Mississippi, University, MS, 38677-1848, USA., Tschumper GS; Department of Chemistry and Biochemistry, University of Mississippi, University, MS, 38677-1848, USA., Bowman JM; Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, GA, 30322, USA. jmbowma@emory.edu., van der Avoird A; Theoretical Chemistry, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ, Nijmegen, Netherlands. A.vanderAvoird@theochem.ru.nl., Havenith M; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany. martina.havenith@rub.de.
Jazyk: angličtina
Zdroj: Nature communications [Nat Commun] 2024 Nov 05; Vol. 15 (1), pp. 9540. Date of Electronic Publication: 2024 Nov 05.
DOI: 10.1038/s41467-024-53444-6
Abstrakt: Hydrogen bonding is a central concept in chemistry and biochemistry, and so it continues to attract intense study. Here, we examine hydrogen bonding in the H 2 S dimer, in comparison with the well-studied water dimer, in unprecedented detail. We record a mass-selected IR spectrum of the H 2 S dimer in superfluid helium nanodroplets. We are able to resolve a rotational substructure in each of the three distinct bands and, based on it, assign these to vibration-rotation-tunneling transitions of a single intramolecular vibration. With the use of high-level potential and dipole-moment surfaces we compute the vibration-rotation-tunneling dynamics and far-infrared spectrum with rigorous quantum methods. Intramolecular mode Vibrational Self-Consistent-Field and Configuration-Interaction calculations provide the frequencies and intensities of the four SH-stretch modes, with a focus on the most intense, the donor bound SH mode which yields the experimentally observed bands. We show that the intermolecular modes in the H 2 S dimer are substantially more delocalized and more strongly mixed than in the water dimer. The less directional nature of the hydrogen bonding can be quantified in terms of weaker electrostatic and more important dispersion interactions. The present study reconciles all previous spectroscopic data, and serves as a sensitive test for the potential and dipole-moment surfaces.
(© 2024. The Author(s).)
Databáze: MEDLINE
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