Exploring the Tl 2H 2 potential energy surface: A comparative analysis with group 13 systems and experiment

Author:

Tang Carson L.1ORCID,Heide Alexander G.1ORCID,Heide Alexandra D.1ORCID,Douberly Gary E.1ORCID,Turney Justin M.1ORCID,Schaefer Henry F.1ORCID

Affiliation:

1. Center for Computational Quantum Chemistry University of Georgia Athens Georgia USA

Abstract

AbstractThallium chemistry is experiencing unprecedented importance. Therefore, it is valuable to characterize some of the simplest thallium compounds. Stationary points along the singlet and triplet TlH potential energy surface have been characterized. Stationary point geometries were optimized with the CCSD(T)/aug‐cc‐pwCVQZ‐PP method. Harmonic vibrational frequencies were computed at the same level of theory while anharmonic vibrational frequencies were computed at the CCSD(T)/aug‐cc‐pwCVTZ‐PP level of theory. Final energetics were obtained with the CCSDT(Q) method. Basis sets up to augmented quintuple‐zeta cardinality (aug‐cc‐pwCV5Z‐PP) were employed to obtain energetics in order to extrapolate to the complete basis set limits using the focal point approach. Zero‐point vibrational energy corrections were appended to the extrapolated energies in order to determine relative energies at 0 K. It was found that the planar dibridged isomer lies lowest in energy while the linear structure lies highest in energy. The results were compared to other group 13 MH (M = B, Al, Ga, In, and Tl) theoretical studies and some interesting variations are found. With respect to experiment, incompatibilities exist.

Publisher

Wiley

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