A convenient set of vibrational coordinates for 2D calculation of the tunneling splittings of the ground state and some excited vibrational states for the inversion motion in H3O+, H3O−, and H3O

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Vol. 296; p. 122660
• Main Authors: Pitsevich, George A., Malevich, Alex E., Kamnev, Alexander A.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 05.08.2023
• Subjects: DVR; Explicitly correlated methods; H3O• radical; H3O− anion; Hydronium cation, H3O; PES; Tunneling, potential barriers; DVR; H3O− anion; H3O• radical; Tunneling, potential barriers; Hydronium cation, H3O; PES; Explicitly correlated methods
• ISSN: 1386-1425
• DOI: 10.1016/j.saa.2023.122660

[Display omitted] •Inversion tunneling in the H3O+ ion was analyzed by calculating the 2D PES.•The CCSD(T)/Aug-cc-pVTZ and CCSD(T)-F12/cc-pVTZ-F12 levels of theory were used.•An original set of two vibrational coordinates was used to simplify calculations.•Calculated splittings for the mode ν2 are in good agreement with experimental data. Splitting of the ground state and some excited symmetric bending vibrational states due to inversion tunneling of the oxygen atom in the H3O+, H3O− ions and in the H3O radical are analyzed by numerically solving the vibrational Schrödinger equation of restricted (2D) dimensionality. As two vibrational coordinates, we used 1) the distance of the oxygen atom from the plane of a regular triangle formed by three hydrogen atoms and 2) a symmetry coordinate composed of three distances between chemically non-bonded hydrogen atoms. The kinetic energy operator in this case takes the simplest form. The 2D potential energy surface (PES) in the given coordinates was calculated for H3O+ at the CCSD(T)/aug-cc-pVTZ and CCSD(T)-F12/cc-pVTZ-F12 levels of theory. The same 2D PES for the H3O− anion and H3O radical were calculated at the CCSD(T)/aug-cc-pVQZ, CCSD(T)/d-aug-cc-pVQZ and UCCSD(T)/aug-cc-pVQZ, UCCSD(T)/d-aug-cc-pVQZ levels of theory, respectively. The tunneling splittings were calculated for the cations H316O+, D316O+, T316O+, H318O+, D318O+, T318O+. The tunneling splittings for the H3O−, D3O−, T3O− anions and H3O, D3O, T3O radicals were calculated for the first time. The results of calculations demonstrate good agreement with experimental values of the tunneling splittings in the ground state and in some excited vibrational states of the H316O+ and D316O+ cations.