The decay of triplet pyrazine and methylpyrazine in supersonic jets. Substitution effects

We have measured the decay rates of optically excited triplet states of pyrazine and methylpyrazine in a supersonic jet. The excess vibrational energy dependence of the radiationless rate constants in the energy range between the T1 and the S1 electronic origins of the isolated molecules was explored. Decay rates between 5×102 and 105 s−1 were found in the 1800 cm−1 range of excess vibrational energy above the origin of the T1 state in pyrazine. In methylpyrazine the decay rates increase from 8×102 to 3.3×104 in the first 600 cm−1 excess energy range above the T1 origin. The decay rates are free of mode specificity and rotational effects. The wide dynamic range of the T1→S0 radiationless rates of pyrazine is substantially enhanced by methyl substitution. The results support a model which suggests that certain vibrational modes, those which undergo large frequency decreases in the excited state, control the strong vibrational energy dependence of the T1→S0 intersystem crossing of pyrazine. These large frequency changes result from the interaction of the near lying 3nπ* and 3ππ* states (the ‘‘proximity effect’’). The enhancement of the excess energy dependence of the decay rates by methyl substitution indicates a further decrease in the frequency of these modes. This effect of the methyl group is consistent with the ‘‘proximity effect.’’ The frequency reduction of these modes in the S1 manifold of methylpyrazine also support this mechanism.