DCl-H2O, HCl-D2O, and DCl-D2O Dimers: Inter- and Intramolecular Vibrational States and Frequency Shifts from Fully Coupled Quantum Calculations on a Full-Dimensional Neural Network Potential Energy Surface

Peter M Felker; Yang Liu; Jun Li; Zlatko Bačić

doi:10.1021/acs.jpca.1c04662

DCl-H₂O, HCl-D₂O, and DCl-D₂O Dimers: Inter- and Intramolecular Vibrational States and Frequency Shifts from Fully Coupled Quantum Calculations on a Full-Dimensional Neural Network Potential Energy Surface

J Phys Chem A. 2021 Jul 29;125(29):6437-6449. doi: 10.1021/acs.jpca.1c04662. Epub 2021 Jul 15.

Authors

Peter M Felker¹, Yang Liu², Jun Li², Zlatko Bačić^{3

4}

Affiliations

¹ Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United States.
² School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 401331, China.
³ Department of Chemistry, New York University, New York, New York 10003, United States.
⁴ NYU-ECNU Center for Computational Chemistry at NYU Shanghai, 3663 Zhongshan Road North, Shanghai 200062, China.

PMID: 34261318
DOI: 10.1021/acs.jpca.1c04662

Abstract

We report full-dimensional and fully coupled quantum calculations of the inter- and intramolecular vibrational states of three isotopologues of the hydrogen chloride-water dimer: DCl-H₂O (DH), HCl-D₂O (HD), and DCl-D₂O (DD). The present study extends our recent theoretical investigation of the nine-dimensional (9D) vibrational level structure of the HCl-H₂O (HH) dimer [Liu, Y.; Li, J.; Felker, P. M.; Bačić, Z. Phys. Chem. Chem. Phys. 2021, 23, 7101-7114]. It employs the same accurate 9D permutation invariant polynomial-neural network potential energy surface and the highly efficient bound-state methodology. The objective of this work is to elucidate the isotopologue variations of a range of bound-state properties of the hydrogen chloride-water dimer and compare them to those of the HH dimer. In order to achieve this, for the isotopologues considered, the rigorous 9D quantum calculations performed encompass all intramolecular vibrational fundamentals, and their frequency shifts relative to the isolated monomer values, together with the low-lying intermolecular vibrational states in each of the intramolecular vibrational manifolds of interest. Moreover, for the ground state of each isotopologue, several informative vibrationally averaged intermolecular geometric properties of the dimer are computed, as well as the three rotational constants. The energies of the intermolecular inversion and rock modes, which mainly involve the motions of the water moiety, differ greatly for H₂O and D₂O, but are much less sensitive to whether the hydrogen chloride isotopologue is HCl or DCl. On the other hand, the excitation of the HCl/DCl stretch changes significantly the energies of the water inversion and rock modes. The DCl stretch frequency shift computed in 9D for the DD dimer, -114.91 cm^-1, agrees extremely well with the corresponding experimental value of -115.20 cm^-1 measured by Saykally and co-workers.