Anharmonicity of Vibrational Modes in Hydrogen Chloride-Water Mixtures

Eva Perlt, Sarah Berger, Barbara Kirchner, Anne-Marie Kelterer

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A thorough analysis of molecular vibrations in the binary system hydrogen chloride/water is presented considering a set of small mixed and pure clusters. In addition to the conventional normal-mode analysis based on the diagonalization of the Hessian, anharmonic frequencies were obtained from the perturbative VPT2 and PT2-VSCF method using hybrid density functional theory. For all normal modes, potential energy curves were modeled by displacing the atoms from the minimum geometry along the normal mode vectors. Three model potentials, a harmonic potential, a Morse potential, and a fourth order polynomial, were applied to fit these curves. From these data, it was possible not only to characterize distinct vibrations as mainly harmonic, anharmonic, or involving higher order terms but also to extract force constants, k, and anharmonicity constants, x e . By investigating all different types of intramolecular vibrations including covalent stretching or bending vibrations and intermolecular vibrations such as librations, we could demonstrate that while vibrational frequencies can be obtained applying scaling factors to harmonic results, useful anharmonicity constants cannot be predicted in such a way and the usage of more elaborate vibrational methods is necessary. For each particular type of molecular vibration, we could however determine a relationship between the wavenumber or wavenumber shift and the anharmonicity constant, which allows us to estimate mode dependent anharmonicity constants for larger clusters in the future.

Original languageEnglish
Pages (from-to)2535-2547
Number of pages13
JournalJournal of Chemical Theory and Computation
Issue number4
Publication statusPublished - 2019

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Fields of Expertise

  • Advanced Materials Science

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