Spin-orbit coupling in highly vibrationally excited O-2(upsilon) and O-2(upsilon=0)-O-2(upsilon)

Citation
R. Hernandez-lamoneda et A. Ramirez-solis, Spin-orbit coupling in highly vibrationally excited O-2(upsilon) and O-2(upsilon=0)-O-2(upsilon), CHEM P LETT, 321(3-4), 2000, pp. 191-196
Citations number
23
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
CHEMICAL PHYSICS LETTERS
ISSN journal
00092614 → ACNP
Volume
321
Issue
3-4
Year of publication
2000
Pages
191 - 196
Database
ISI
SICI code
0009-2614(20000428)321:3-4<191:SCIHVE>2.0.ZU;2-B
Abstract
Highly correlated ab initio calculations of the ground and low-lying electr onic states of O-2 and O-4 together with a semi-empirical estimate of the s pin-orbit coupling among them have been performed. For the diatomic, our ca lculations agree well with recent spectroscopic measurements. For the O-2(v = 0)-O-2(v) collision system, avoided crossings allow mixing of the electr onic configurations with appreciable spin-orbit coupling into the lowest-ly ing excited states. As a consequence, spin-orbit transitions can occur at s ignificantly lower vibrational energies of the O-2(v) moiety induced by col lisions with O-2(v = 0). This mechanism must be partially responsible for t he observed jump in depletion rates of O-2(v) determined experimentally, (C ) 2000 Elsevier Science B.V. All rights reserved.