Mechanism of efficient firefly bioluminescence via adiabatic transition state and seam of sloped conical intersection.
2008 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 130, no 39, 12880-12881 p.Article in journal (Refereed) Published
Firefly emission is a well-known efficient bioluminescence. However, the mystery of the efficient thermal generation of electronic excited states in firefly still remains unsolved, particularly at the atomic and molecular levels. We performed SA-CASSCF(12,12)/6-31G* and CASPT2(12,12)/6-31G*//SA-CASSCF(12,12)/6-31G* calculations to elucidate the reaction mechanism of bioluminescence from the firefly dioxetanone in the gas phase. Adiabatic transition state (TS) for the O-O bond cleavage and the minimum energy conical intersection (MECI) were located and characterized. The unique topology of MECI featuring a seam of a sloped conical intersection for the firefly dioxetanone, which was uncovered for the first time, emerges along the reaction pathway to provide a widely extended channel to diabatically access the excited-state from the ground state.
Place, publisher, year, edition, pages
2008. Vol. 130, no 39, 12880-12881 p.
Other Basic Medicine
IdentifiersURN: urn:nbn:se:uu:diva-145459DOI: 10.1021/ja8052464ISI: 000259553700022PubMedID: 18767834OAI: oai:DiVA.org:uu-145459DiVA: diva2:396529
Times Cited: 92011-02-102011-02-092016-04-22