Disciplines

Biological and Chemical Physics

Abstract

The angular distribution of products from the ultraviolet photodissociation of nitrous oxide yielding O(1D) and N2(X1Σ+g) was investigated using classical trajectory calculations. The calculations modeled absorption only to the 21A'electronic state but used surface-hopping techniques to model nonadiabatic transitions to the ground electronic state late in the dissociation. Observed values of the anisotrophy parameter β, which decrease as the product N2 rotational quantum number jincreases, could be well reproduced. The relatively low observed βvalues arise principally from nonaxial recoil due to the very strong bending forces present in the excited state. In the main part of the product rotational distribution near 203 nm, an unusual dynamical effect produces the decrease in β with increasing j; nonaxial recoil effects remain approximately constant while higher jproduct molecules arise from parent molecules that had their transition dipole moments aligned more closely along the molecular axis. In both low and high j tails of the rotational distribution, the variations in β with jare caused by changes in the extent of nonaxial recoil. In the high-j tail, additional torque present on the ground state potential energy surface following nonadiabatic transitions causes both the additional rotational excitation and the lower β values.

Comments

Original Citation: George C. McBane and Reinhard Schinke. Product angular distributions in the ultraviolet photodissociation of N2O. J. Chem. Phys., 136(4):044314, 2012.

Share

COinS