Dioxygen spectra and bioactivation
2013 (English)In: International Journal of Quantum Chemistry, ISSN 0020-7608, E-ISSN 1097-461X, Vol. 113, no 14, 1847-1867 p.Article in journal (Refereed) Published
Intensities of spin-forbidden transitions in electronic absorption and emission spectra of molecular oxygen are analyzed in order to understand the key mechanisms of spin-states mixing induced by spin-orbit coupling (SOC) and the ways to overcome spin prohibition for various photophysical and biochemical processes. Multireference configuration interaction calculations with SOC account are used to generalize spin-selection rules for the oxygen atmospheric and Herzberg bands in free O2 molecule and in collision complexes. Intensity enhancement of the atmospheric a1g X3 sigma g-, b1 sigma g+ X3 sigma g-, and Noxon b1 sigma g+ a1g transitions upon bimolecular collisions are compared with those for Herzberg III transitions A3u X3 sigma g-. Electric quadrupole, dipole, and magnetic approximations are used for transition probability calculations. Intensity distribution in rotational lines is also considered. With this background, we propose some simple spin-selection rules for dioxygen activation in enzymatic reactions. (c) 2013 Wiley Periodicals, Inc.
Place, publisher, year, edition, pages
2013. Vol. 113, no 14, 1847-1867 p.
IdentifiersURN: urn:nbn:se:kth:diva-124564DOI: 10.1002/qua.24390ISI: 000319996300006ScopusID: 2-s2.0-84878736410OAI: oai:DiVA.org:kth-124564DiVA: diva2:636850
QC 201307122013-07-122013-07-122013-07-19Bibliographically approved