Energy Disposal in the Photodissociation of Co(CO)₃NO near 225 nm (original) (raw)

Journal of Physical Chemistry A, 1998

Abstract

ABSTRACT The photodissociation of Co(CO)3NO was studied near 225 nm. Apparent two-photon dissociation of the parent compound produces Co* in a number of excited states that emit in the range of 340−360 nm. Both quartet and doublet states of Co* are observed, implying the existence of spin-conserving and nonspin-conserving dissociation channels. Assignment of the Co* emission is used to calculate an upper limit for the average metal−ligand bond dissociation energy of 36.2−38.6 kcal/mol with no spin-conservation restrictions and 41.2−43.9 kcal/mol with spin-conservation restrictions. The Co* emission intensities are used to determine the relative populations of particular J and spin states and to demonstrate that J states within a particular LS configuration are statistically populated. The NO photoproduct was detected by fluorescence excitation spectroscopy. The NO appears to follow dual Boltzmann statistics with rotational temperatures of 580 ± 70 K for Erot < 500 cm-1 and 2800 ± 300 K for Erot > 500 cm-1.

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