Response calculations of electronic and vibrational transitions in molecular oxygen induced by interaction with noble gases.
The Einstein coefficient for the singlet oxygen emission a1Deltag-->X3Sigmag- at lambda=1270 nm and b1Sigmag+-->X3Sigmag- emission at lambda=750 nm were calculated by quadratic response (QR) multiconfiguration self-consisted field (MCSCF) method for a number of collision complexes O2+M, where M=He, Ne, Ar. Interaction with He clusters was studied in order to simulate cooperative effect of the environment on the oxygen emission. Calculations of the dipole transition moment for the Noxon band, b1Sigmag+-a1Deltag, by linear response (LR) MCSCF method were also performed for a number of collision complexes. Spin-orbit coupling (SOC) between the b1Sigmag+ and X3Sigmag- (MS=0) states does not change much upon collisions, thus the a-X transition borrows intensity mostly from the collision-induced Noxon band b-a. The a-X intensity borrowing from the Schumann-Runge transition is negligible. The calculations show that the b-a and a-X transition probabilities are enhanced approximately by 10(5) and 10(3) times by O2+M collisions. An order of magnitude differences occur for both transitions for noble gases with large difference in polarizability. A strong cooperative effect is obtained when few He atoms perturb the oxygen molecule. Depending on mutual orientation of the partners it can be a complete quenching of the a-->X emission or strong non-additive enhancement. Collision-induced infrared vibrational transitions in a number of molecular oxygen excited states were studied and shown to be state selective.
Minaev
Boris F
BF
Cherkassy Engineering and Technological Institute, 257006 Cherkassy, Ukraine. boris@theochem.kth.se
Kobzev
G I
GI
D008958:Models, Molecular; D005741:Noble Gases / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
D005741:Noble Gases; D010100:Oxygen