Spectroscopic and theoretical studies of ThCl and ThCl.
The electronic structures of ThCl and ThCl+have been examined using laser induced fluorescence and two-photon ionization techniques. Rotationally resolved spectra, combined with the predictions from relativistic electronic structure calculations, show that the ground state of the neutral molecule is Th+(7s26d)Cl-, X2Δ3/2. Dispersed fluorescence spectra for ThCl revealed the ground state vibrational levels v = 0-10 and low energy electronic states that also originate from the atomic ion 7s26d configuration. Pulsed field ionization-zero kinetic energy photoelectron spectroscopy established an ionization energy (IE) for ThCl of 51 344(5) cm-1, and the ThCl+vibrational term energies of the v = 1-3 levels. The zero-point level of the first electronically excited state was found at 949(2) cm-1. Comparisons with high-level theoretical results indicate that the ground and excited states are Th2+(7s6d)Cl-X3Δ1and Th2+(7s2)Cl-Σ+1, respectively. Relativistic coupled cluster composite thermochemistry calculations yielded an IE within 1.2 kcal/mol of experiment and a bond dissociation energy (118.3 kcal/mol) in perfect agreement with previous experiments.
Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
Robert A
RA
VanGundy
Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
Joshua H
JH
Bartlett
Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
Michael C
MC
Heaven
Department of Chemistry, Washington State University, Pullman, Washington 99164, USA.
Samuel R
SR
Battey
Department of Chemistry, Washington State University, Pullman, Washington 99164, USA.
Kirk A
0000000349013235
KA
Peterson