Detection of direct NO ligand loss in the ultraviolet photodissociation of Co(CO)3NO

Primary and Secondary Loss of CO and NO Ligands in the Ultraviolet Photodissociation of the Heteroleptic Co(CO)3NO Complex

“…Several β Q K ( k 1 k 2 ) parameters were determined with the use of the angular distributions measured at the R 12 + Q 22 and P 11 transitions on the basis of the analytical formula of photofragment angular distributions derived by Grubb et al The β 0 0 (22) parameter, , which is related to a correlation between a recoil velocity vector v and the total angular momentum vector of the NO fragment j NO , was determined to be −0.58 ± 0.09, suggesting a perpendicular rotational alignment of the NO fragment to its recoil direction. The obtained value exceeds the physical limit [−0.5 < β 0 0 (22) <1.0] without the error presumably because the measurement was limited in a single pump–probe polarization configuration . Nevertheless, the semiquantitative value indicates a fairly high degree of alignment given by the photodissociation.…”

“…To understand the whole photochemistry of the Co­(CO) 3 NO complex, the state distributions of the CO fragment are as important as those of the NO fragment. Although we found a peculiar NO elimination mechanism in the previous ion-imaging study, the lack of CO data prevented us from examining the order of CO/NO losses and the relationship between each pathway, which could be the fundamental questions in the photochemistry of heteroleptic complexes.…”

“…Typically, the higher kinetic-energy components exhibited peculiar angular distributions, which were represented by a linear combination of the zeroth-, second-, and fourth-order Legendre polynomials. The dependence of the contributions of the second and fourth terms on the detection branches indicated rotational alignment of the NO fragment by dynamical constraints . We analyzed the angular distribution of the higher-kinetic-energy components on the basis of a semiclassical bipolar moment formalism , to determine vector–correlation parameters in our previous study; the anisotropy parameter [β = 2β 0 2 (20)] for the NO ( v = 0, J = 39.5) fragment was determined to be 1.6, which is qualitatively explained as the result of rapid dissociation following the photoabsorption with a parallel-type transition.…”

“…The dependence of the contributions of the second and fourth terms on the detection branches indicated rotational alignment of the NO fragment by dynamical constraints . We analyzed the angular distribution of the higher-kinetic-energy components on the basis of a semiclassical bipolar moment formalism , to determine vector–correlation parameters in our previous study; the anisotropy parameter [β = 2β 0 2 (20)] for the NO ( v = 0, J = 39.5) fragment was determined to be 1.6, which is qualitatively explained as the result of rapid dissociation following the photoabsorption with a parallel-type transition. Several β Q K ( k 1 k 2 ) parameters were determined with the use of the angular distributions measured at the R 12 + Q 22 and P 11 transitions on the basis of the analytical formula of photofragment angular distributions derived by Grubb et al The β 0 0 (22) parameter, , which is related to a correlation between a recoil velocity vector v and the total angular momentum vector of the NO fragment j NO , was determined to be −0.58 ± 0.09, suggesting a perpendicular rotational alignment of the NO fragment to its recoil direction.…”

Nonadiabatic dynamics of cobalt tricarbonyl nitrosyl for ligand dissociation induced by electronic excitation

“…Photodissociation also involves the pertinent excitation-driven phenomenon, where excitation is introduced in internal degrees of freedom of the molecule. The photodissociation of ligands on the Co(CO) 3 NO has also been studied in previous experimental works 16 – 20 . While experimental progress based on such excitation-induced dissociation of the Co(CO) 3 NO has been actively reported in terms of relatively long-time processes by taking into account intramolecular vibrational energy redistribution, there have been very few theoretical studies providing microscopic insights on the process.…”