Chemistry (all); Biochemistry, Genetics and Molecular Biology (all); Physics and Astronomy (all)
Abstract :
[en] 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 H2S dimer, in comparison with the well-studied water dimer, in unprecedented detail. We record a mass-selected IR spectrum of the H2S 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 H2S 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.
Disciplines :
Chemistry
Author, co-author :
Jäger, Svenja ; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany
Khatri, Jai ; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany
Meyer, Philipp ; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany
Henkel, Stefan; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany
Schwaab, Gerhard ; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany
NANDI, Apurba ; University of Luxembourg ; Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, GA, 30322, USA
Pandey, Priyanka ; Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, GA, 30322, USA
Barlow, Kayleigh R; Department of Chemistry and Biochemistry, University of Mississippi, University, MS, 38677-1848, USA
Perkins, Morgan A; Department of Chemistry and Biochemistry, University of Mississippi, University, MS, 38677-1848, USA
Tschumper, Gregory S ; Department of Chemistry and Biochemistry, University of Mississippi, University, MS, 38677-1848, USA
Bowman, Joel M ; Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, GA, 30322, USA. jmbowma@emory.edu
van der Avoird, Ad ; Theoretical Chemistry, Institute for Molecules and Materials, Radboud University, Heyendaalseweg 135, 6525 AJ, Nijmegen, Netherlands. A.vanderAvoird@theochem.ru.nl
Havenith, Martina ; Department of Physical Chemistry II, Ruhr University Bochum, 44801, Bochum, Germany. martina.havenith@rub.de
The authors thank Claude Leforestier for making available his computer programs based on the split Wigner pseudospectral method and for valuable discussions. This study has been funded by the Deutsche Forschungsgemeinschaft (DFG; German Research Foundation) under Germany\u2019s Excellence Strategy\u2014EXC 2033\u2014Projektnummer 390677874, NASA (80NSSC22K1167) and by the National Science Foundation (CHE-2154403). This publication is also based upon work of COST Action CA21101 on Confined molecular systems: from a new generation of materials to the stars (COSY) supported by COST (European Cooperation in Science and Technology).
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