Title

Electron spin resonance studies of P2H+6and PH+3 radical cations in rare gas matrices at 4 K. Comparison with theoretical calculations

ACS Citation

Knight, L. B.; Tyler, D. J.; Kudelko, P.; Lyon, J. B.; McKinley, A. J. Electron spin resonance studies of P2H+6 and PH+3 radical cations in rare gas matrices at 4 K. Comparison with theoretical calculations. J. Chem. Phys. 1993, 99, 7384-7384.

Abstract

Detailed experimental and theoreticalelectron spin resonance(ESR) studies of the cation radicals, PH+ 3 and P2H+ 6, isolated in neon and argon matrices are reported. These cations were generated by photoionization (17 eV) and x‐irradiation (80 keV) methods. The observed nuclear hyperfine interactions (Atensors) showed reasonable agreement with A iso and A dipolar values calculated at the ab initioconfiguration interaction (CI) level. These ESR results for PH+ 3 clearly indicate its nonplanarity; for P2H+ 6, an earlier theoretical prediction of a C 2h distortion from C 3v was confirmed by these new experimental results which reveal two different H atom environments. The neon magnetic parameters for PH+ 3 are g ∥=2.002(1), g ⊥=2.007(1), A ⊥=920(3), and A ∥=1638(15) MHz for 31P and A(H)≤6 MHz. The neon parameters for P2H+ 6 are g ∥=2.001(1), g ⊥=2.003(1), A ⊥=1527(2), and A ∥=1909(4) MHz for 31P and A(2H)=182(2) and A(4H)=±22(2) MHz.

Source Name

Journal of Chemical Physics

Publication Date

1-1-1993

Volume

99

Issue

10

Page(s)

3289-3293

Document Type

Citation

Citation Type

Article