HCl trimer: HCl-stretch excited intramolecular and intermolecular vibrational states from 12D fully coupled quantum calculations employing contracted intra- and inter-molecular bases

Irén Simkó; Peter M Felker; Zlatko Bačić

doi:10.1063/5.0207366

HCl trimer: HCl-stretch excited intramolecular and intermolecular vibrational states from 12D fully coupled quantum calculations employing contracted intra- and inter-molecular bases

J Chem Phys. 2024 Apr 28;160(16):164304. doi: 10.1063/5.0207366.

Authors

Irén Simkó^{1

2}, Peter M Felker³, Zlatko Bačić^{1

2

4}

Affiliations

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.
³ Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
⁴ NYU-ECNU Center for Computational Chemistry at NYU Shanghai, 3663 Zhongshan Road North, Shanghai 200062, China.

PMID: 38647302
DOI: 10.1063/5.0207366

Abstract

We present fully coupled, full-dimensional quantum calculations of the inter- and intra-molecular vibrational states of HCl trimer, a paradigmatic hydrogen-bonded molecular trimer. They are performed utilizing the recently developed methodology for the rigorous 12D quantum treatment of the vibrations of the noncovalently bound trimers of flexible diatomic molecules [Felker and Bačić, J. Chem. Phys. 158, 234109 (2023)], which was previously applied to the HF trimer by us. In this work, the many-body 12D potential energy surface (PES) of (HCl)3 [Mancini and Bowman, J. Phys. Chem. A 118, 7367 (2014)] is employed. The calculations extend to the intramolecular HCl-stretch excited vibrational states of the trimer with one- and two-quanta, together with the low-energy intermolecular vibrational states in the two excited v = 1 intramolecular vibrational manifolds. They reveal significant coupling between the intra- and inter-molecular vibrational modes. The 12D calculations also show that the frequencies of the v = 1 HCl stretching states of the HCl trimer are significantly redshifted relative to those of the isolated HCl monomer. Detailed comparison is made between the results of the 12D calculations on the two-body PES, obtained by removing the three-body term from the original 2 + 3-body PES, and those computed on the 2 + 3-body PES. It demonstrates that the three-body interactions have a strong effect on the trimer binding energy as well as on its intra- and inter-molecular vibrational energy levels. Comparison with the available spectroscopic data shows that good agreement with the experiment is achieved only if the three-body interactions are included. Some low-energy vibrational states localized in a secondary minimum of the PES are characterized as well.