Theoretical study on angular momentum polarization parameters, branching ratios, and anisotropy parameters of chlorine atoms from Photodissociation of Iodine Monochloride

Abstract

AbstractLow‐lying excited state potential energy curves (PECs), nonadiabatic coupling terms, and transition dipole moments of ICl have been obtained by a spin‐orbit configuration interaction method. The angular momentum polarization parameters of photofragments can be calculated from these properties of the molecule. The first‐rank parameter Im[a1(1)(//,⟂)] of the ground state photofragment Cl(2P3/2) in the first absorption band (490–560 nm) is very sensitive to the PECs of the low‐lying excited states, especially the A(1) and B(0+) states. The phase part of the calculated parameter Im[a1(1)(//,⟂)] agrees well with experiment. We further clarify the characteristics of avoided crossing between the X(0+) and B(0+) states. We calculated the product fraction of Cl*(2P1/2) and the anisotropy parameter β to demonstrate the effect of photoabsorption caused by the z(1) state, which supports a recent experimental analysis. © 2012 Wiley Periodicals, Inc.