The generation of 12C31P and 13C31P by reactive laser vaporization for rare gas matrix electron spin resonance studies: Comparison with a b i n i t i o theoretical calculations

Publisher Website
Google Scholar
Abstract
The 12C31P and 13C31P diatomic radicals have been generated by the laser vaporization reaction between carbon and phosphorus which were pressed into a pellet to form the laser target. This method is applicable to a wide range of nonmetallic systems for generating new reactive intermediates which cannot be done with more conventional approaches. The radicals were isolated in neon and argon matrices at 4 K for detailed ESR investigations. The magnetic parameters (MHz) for neon were: g∥=2.0009(3); g⊥=1.9902(3); A∥(31P)=145.0(3); A⊥(31P)=−269.0(2); A∥(13C)=580.0(3); and A⊥(13C)=422.0(3). The argon A and g tensors were virtually indistinguishable from these neon results. Extensive ab initio theoretical calculations were conducted for CP which yielded nuclear hyperfine A values in close agreement with the experimental results. Valence orbital spin populations extracted from the calculated CI wave functions are compared with those determined directly from the ESR hyperfine parameters for 13C and 31P. The observed g shift for CP agreed with the gas phase spin–rotation constant and indicates the presence of a low lying 2πr state that has not been previously observed.