TY - JOUR
T1 - Computational prediction of the ISC rate for triplet norbornene
AU - Harvey, Jeremy N.
AU - Grimme, Stefan
AU - Woeller, Markus
AU - Peyerimhoff, Sigrid D.
AU - Danovich, David
AU - Shaik, Sason
PY - 2000/5/26
Y1 - 2000/5/26
N2 - The radiationless decay of T1 norbornene to the singlet ground state is studied using density-functional and ab initio CASSCF calculations of the potential energy surface crossing and of the spin-orbit coupling. The rate of decay is predicted using two approximate multi-dimensional non-adiabatic methods, one of which is based on Fermi's Golden Rule, and the other is a version of RRKM theory adapted for non-adiabatic processes. Unlike a previous Landau-Zener treatment of this process by some of us [Chem. Phys. Lett. 287 (1998) 601-607], both methods correctly predict a short lifetime for the triplet excited state, in reasonable agreement with experimental data. This underlines the importance of tunnelling in non-radiative relaxation processes.
AB - The radiationless decay of T1 norbornene to the singlet ground state is studied using density-functional and ab initio CASSCF calculations of the potential energy surface crossing and of the spin-orbit coupling. The rate of decay is predicted using two approximate multi-dimensional non-adiabatic methods, one of which is based on Fermi's Golden Rule, and the other is a version of RRKM theory adapted for non-adiabatic processes. Unlike a previous Landau-Zener treatment of this process by some of us [Chem. Phys. Lett. 287 (1998) 601-607], both methods correctly predict a short lifetime for the triplet excited state, in reasonable agreement with experimental data. This underlines the importance of tunnelling in non-radiative relaxation processes.
UR - http://www.scopus.com/inward/record.url?scp=0005408460&partnerID=8YFLogxK
U2 - 10.1016/S0009-2614(00)00442-5
DO - 10.1016/S0009-2614(00)00442-5
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
AN - SCOPUS:0005408460
SN - 0009-2614
VL - 322
SP - 358
EP - 362
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 5
ER -