Electronic spectroscopy and excited state mixing of OThF

Arianna Rodriguez; Jiande Han; Jiarui Yan; Michael C Heaven; Lan Cheng

doi:10.1063/5.0245862

Electronic spectroscopy and excited state mixing of OThF

J Chem Phys. 2025 Jan 14;162(2):024305. doi: 10.1063/5.0245862.

Authors

Arianna Rodriguez¹, Jiande Han¹, Jiarui Yan¹, Michael C Heaven¹, Lan Cheng²

Affiliations

¹ Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
² Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.

PMID: 39791495
DOI: 10.1063/5.0245862

Abstract

Electronic spectra for OThF have been recorded using fluorescence excitation and two-photon resonantly enhanced ionization techniques. Multiple vibronic bands were observed in the 340-460 nm range. Dispersed fluorescence spectra provided ground state vibrational constants and evidence of extensive vibronic state mixing at higher excitation energies. Two-photon ionization measurements established the ionization energy for OThF of 6.283(5) eV. To guide the assignment of the OThF spectra, electronic structure calculations were carried out using relativistic equation-of-motion coupled-cluster singles and doubles methods. These calculations indicated that spin-orbit induced mixing of the 32A″ and 42A' states was mediated by a seam of potential energy surface intersections.