Observation of NH X(3)Σ(-) as a Primary Product of Methylamine Photodissociation: Evidence of Roaming-Mediated Intersystem Crossing?
3+1 Resonance-enhanced multiphoton ionization and photofragment excitation spectroscopy have been used to identify NH X(3)Σ(-) as a primary product of methylamine photodissociation after state-specific excitation to the S1 state. On the basis of standard thermochemical data, NH X(3)Σ(-) can be formed only in conjunction with closed-shell CH4 coproducts, indicating that dissociation must occur on the T1 surface. It is proposed that the mechanism for the formation of triplet NH and CH4 involves intramolecular abstraction between frustrated radical products and is an example of roaming-mediated intersystem crossing.
‡School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, U.K.
James O
JO
Thomas
‡School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, U.K.
Katherine E
KE
Lower
†School of Chemistry, University of Glasgow, University Avenue, Glasgow G12 8QQ, U.K.
Craig
C
Murray
intersystem crossing; methylamine; photochemistry; photodissociation dynamics; roaming