The water trimer, as the smallest water cluster in which the three-body interactions can manifest, is arguably the most important hydrogen-bonded trimer. Accurate, fully coupled quantum treatment of its excited intermolecular vibrations has long been an elusive goal. Here, we present the methodology that for the first time allows rigorous twelve-dimensional (12D) quantum calculation of the intermolecular vibration-tunneling eigenstates of the water trimer, with the monomers treated as rigid. These 12D eigenstates are used to simulate the low-frequency absorption spectrum of the trimer for direct comparison with the measured far-infrared (FIR) spectrum of the water trimer in helium nanodroplets. The 12D calculations reveal weak coupling between the large-amplitude torsional and intermolecular stretching vibrations. The calculated torsional tunneling splittings are in excellent agreement with spectroscopic results. There are visible differences between the spectrum simulated using the 12D eigenstates and that based on our earlier 9D calculations where the stretching vibrations are not included. The peaks in the 12D spectrum are generally shifted to slightly lower energies relative to those in the 9D spectrum, as well as the measured FIR spectrum, and are often split by intermolecular stretch–bend Fermi resonances that the 9D treatment cannot capture.
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H2O trimer: Rigorous 12D quantum calculations of intermolecular vibrational states, tunneling splittings, and low-frequency spectrum
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21 January 2025
Research Article|
January 15 2025
H2O trimer: Rigorous 12D quantum calculations of intermolecular vibrational states, tunneling splittings, and low-frequency spectrum
Irén Simkó
;
Irén Simkó
a)
(Conceptualization, Formal analysis, Funding acquisition, Methodology, Writing – original draft, Writing – review & editing)
1
Department of Chemistry, New York University
, New York, New York 10003, USA
2
Simons Center for Computational Physical Chemistry at New York University
, New York, New York 10003, USA
a)Authors to whom correspondence should be addressed: [email protected]; [email protected]; and [email protected]
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Peter M. Felker
;
Peter M. Felker
a)
(Conceptualization, Formal analysis, Funding acquisition, Methodology, Writing – original draft, Writing – review & editing)
3
Department of Chemistry and Biochemistry, University of California
, Los Angeles, California 90095-1569, USA
a)Authors to whom correspondence should be addressed: [email protected]; [email protected]; and [email protected]
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Zlatko Bačić
Zlatko Bačić
a)
(Conceptualization, Formal analysis, Funding acquisition, Methodology, Writing – original draft, Writing – review & editing)
1
Department of Chemistry, New York University
, New York, New York 10003, USA
2
Simons Center for Computational Physical Chemistry at New York University
, New York, New York 10003, USA
4
NYU-ECNU Center for Computational Chemistry at NYU Shanghai
, 3663 Zhongshan Road North, Shanghai 200062, China
a)Authors to whom correspondence should be addressed: [email protected]; [email protected]; and [email protected]
Search for other works by this author on:
a)Authors to whom correspondence should be addressed: [email protected]; [email protected]; and [email protected]
J. Chem. Phys. 162, 034301 (2025)
Article history
Received:
November 21 2024
Accepted:
December 13 2024
Citation
Irén Simkó, Peter M. Felker, Zlatko Bačić; H2O trimer: Rigorous 12D quantum calculations of intermolecular vibrational states, tunneling splittings, and low-frequency spectrum. J. Chem. Phys. 21 January 2025; 162 (3): 034301. https://doi.org/10.1063/5.0250018
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