Effect of Vibronically Induced Spin-Orbit Coupling of Electronic (pi)(pi)~(*) States on Nonradiative Intersystem Crossing: Naphthalene

摘要

The effect of (I) S_(1)(~(1)B_(2u)) -> T_(1)(~(3)B_(1u)) and (II) S_(1) -> T_(2)(~(3)B_(3g)) -> T_(1) transitions in naphthalene on the rate constant K_(ST)~(s) of the S_(1) -> T_(1) nonradiative transitions to all triplet sublevels s velence z, y, x of the T_(1) state has been investigated in the approximation of vibronically induced spin-orbit couplings, taking into account all out-of-plane vibrational modes. The shapes of the vibrational modes that are most active in these transitions are determined. The calculated values K_(ST) velence (0.33-0.75) X 10~(7) s~(-1), obtained with allowance for the I and I + II transitions, are consistent with the experimental values (K_(ST))_(exp) found by different researchers. It is established in all calculation versions that K_(ST) > K_(ST)~(z) > K_(ST)~(x). This relation is in qualitative agreement with the known magnetooptical data.