A dispersed fluorescence and ab initio investigation of the X2B1 and A2A1 electronic states of the PH2 molecule.
In this work, the X2B1 and A2A1 electronic states of the phosphino (PH2) free radical have been studied by dispersed fluorescence and ab initio methods. PH2 molecules were produced in a molecular free-jet apparatus by laser vaporizing a silicon rod in the presence of phosphine (PH3) gas diluted in helium. The laser-induced fluorescence, from the excited A2A1 electronic state down to the ground electronic state, was dispersed and analyzed. Ten (upsilon1upsilon2upsilon3) vibrationally excited levels of the ground electronic state, with upsilon1 < or = 2, upsilon2 < or = 6, and upsilon3 = 0, have been observed. Ab initio potential-energy surfaces for the X2B1 and A2A1 electronic states have been calculated at 210 points. These two states correlate with a 2Pi(u) state at linearity and they interact by the Renner-Teller coupling and spin-orbit coupling. Using the ab initio potential-energy surfaces with our RENNER computer program system, the vibronic structure and relative intensities of the A2A1 --> X2B1 emission band system have been calculated in order to corroborate the experimental assignments.
Jakubek
Z J
ZJ
Steacie Institute for Molecular Sciences, National Research Council of Canada, Ottawa, Ontario K1A 0R6, Canada. zygmunt.jakubek@nrc.ca
Bunker
P R
PR
Zachwieja
M
M
Nakhate
S G
SG
Simard
B
B
Yurchenko
S N
SN
Thiel
W
W
Jensen
Per
P