HCl-H2O dimer: an accurate full-dimensional potential energy surface and fully coupled quantum calculations of intra- And intermolecular vibrational states and frequency shifts

Yang Liu, Jun Li, Peter M. Felker, Zlatko Bačić

Research output: Contribution to journalArticlepeer-review

Abstract

The interaction between HCl and H2O is of considerable theoretical and experimental interest due to its important role in atmospheric chemistry and understanding the onset of the dissociation of HCl in water. In this work, the HCl-H2O complex is quantitatively characterized in two ways. First, we report a new full-dimensional potential energy surface (PES) for the HCl + H2O system. The nine-dimensional (9D) PES is based oncirca43 000ab initiopoints calculated at the level of CCSD(T)-F12a/AVTZ with the basis set superposition error correction using the permutation invariant polynomial-neural network method, which can accurately and efficiently reproduce the geometries, energies, frequencies of the complex of HCl with H2O, as well as the relevant minimum energy path. Next, we present the results of the first fully coupled 9D quantum calculations of the intra- and intermolecular vibrational states of the HCl-H2O dimer, performed on the new PES. They employ the highly efficient bound-state methodology previously used to compute accurately the rovibrational level structure of the H2O/D2O-CO and HDO-CO complexes [P. M. Felker and Z. Bačić,J. Chem. Phys., 2020,153, 074107;J. Phys. Chem. A, 2021,125, 980]. The 9D calculations characterize the vibrationally averaged nonplanar ground-state geometry of the HCl-H2O complex, the intramolecular vibrational fundamentals of both H2O and HCl moieties, and their frequency shifts, as well as the low-energy intermolecular vibrational states in each of the intramolecular vibrational manifolds and the effects of the coupling between the two sets of modes. The calculated properties of the HCl-H2O dimer are in excellent agreement with the available spectroscopic data. The 9D computed dimer binding energyD0of 1334.63 cm−1agrees extremely well with the experimentalD0equal to 1334 ± 10 cm−1[B. E. Casterline and A. K. Mollner and L. C. Ch'ng and H. Reisler,J. Chem. Phys., 2010,114, 9774]. Moreover, the ground-state expectation value of the out-of-plane bend angle of H2O, 33.80°, and the computed HCl stretch frequency shift, −157.9 cm−1, both from the 9D calculations, are in very good accord with the corresponding experimental values.

Original languageEnglish (US)
Pages (from-to)7101-7114
Number of pages14
JournalPhysical Chemistry Chemical Physics
Volume23
Issue number12
DOIs
StatePublished - Mar 28 2021

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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