The generation of 12C31P and 13C31P by reactive laser vaporization for rare gas matrix electron spin resonance studies: Comparison with ab initio theoretical calculations

ACS Citation

Knight, L. B.; Petty, J. T.; Cobranchi, S. T.; Feller, D.; Davidson, E. R. The generation of 12C31P and 13C31P by reactive laser vaporization for rare gas matrix electron spin resonance studies: Comparison with ab initio theoretical calculations. J. Chem. Phys. 1988, 88, 3441-3441.

Abstract

The 1 2C3 1P and 1 3C3 1P diatomic radicals have been generated by the laser vaporizationreaction 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 ∥(3 1P)=145.0(3); A ⊥(3 1P)=−269.0(2); A ∥(1 3C)=580.0(3); and A ⊥(1 3C)=422.0(3). The argon A and gtensors were virtually indistinguishable from these neon results. Extensive a b i n i t i otheoretical 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 1 3C and 3 1P. The observed g shift for CP agreed with the gas phase spin-“rotation constant and indicates the presence of a low lying 2Ï€ r state that has not been previously observed.

Source Name

Journal of Chemical Physics

Publication Date

1-1-1988

Volume

88

Issue

6

Page(s)

4404-4404

Document Type

Citation

Citation Type

Article

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