Journal of Physical Chemistry A, Vol.108, No.16, 3421-3429, 2004
Magnetic field effects on the photodissociation reaction of triarylphosphine in nonviscous homogeneous solutions
The magnetic field effects (MFEs) on the photodecomposition reactions of triphenylphosphine and its halogen and methyl derivatives are investigated in fluid solutions. The yield of diarylphosphinyl radicals decreased with increasing magnetic field from 0.1 to 5 T but was stationary below 0.1 T and above 5 T. The MFE becomes larger by the substitution of halogen atoms and the 3- or 4-methyl group. In cyclohexane, the yields of the escaped diaryl phosphinyl radicals at 1 T are reduced to 0.69, 0.55, 0.59, and 0.56 of those at 0 T for triphenylphosphine and its tris(4-chloro), tris(3-methyl), and tris(4-methyl) derivatives, respectively. This magnetic field dependence was ascribed to originate from the deactivation process of the excited triplet state, which is a variant of the d-type triplet mechanism originally proposed by Steiner. The interaction between the closely lying npi* and pipi* states makes their solvent dependence complicated.