Magnetic circular dichroism and absorption spectra of phosphinidene in noble-gas matrices

Electronic magnetic circular dichroism and absorption spectra are reported for the A 3pi(i) <-- X 3sigma- transitions of phosphinidene (PH) isolated in Ar, Kr, and Xe matrices at cryogenic temperatures (approximately 1.4-20 K) and over a range of magnetic field strengths (0-5 T). The results are analyzed by the method of moments, and parameters are extracted by fitting the experimental data to a model in which the A 3pi(i) term is split by spin-orbit (SO) coupling interactions, while the X 3sigma- term is split by spin-spin and higher-order SO coupling. The analysis indicates that, unlike the equivalent imidogen (NH) systems, ground-state PH radicals isolated in noble-gas matrices do not behave as free rotors. Trends in excited-state SO coupling constants are attributed to the external heavy-atom effect and guest-host orbital mixing. It is tentatively concluded that librational amplitudes of the guest radical decrease in the order Ar > Xe > Kr, probably as a consequence of competition between stronger guest-host interactions and larger matrix sites in heavier hosts.