FRAGMENT PAIR CORRELATIONS IN THE VIBRATIONALLY MEDIATED PHOTODISSOCIATION OF H2O2 - ROTATION VIBRATION COUPLING IN THE 3RD OH STRETCHING OVERTONE STATE

Photofragment scalar pair correlations are determined following photodissociation of selected rovibrational levels of the third OH stretching overtone state of H2O2 at lambda almost-equal-to 748 nm. An anticorrelation between the rotational populations of the two sibling OH fragments is observed that is insensitive to the selected K(a) level in the range 1-5 with [J] almost-equal-to 7-14. Simulations of the OH pair correlations, and previously measured v-j correlations and rotational distributions, indicate the breakdown of K(a) as a good quantum number in the interrogated third OH stretching overtone state of H2O2 and highlight the role of a-axis rotation in promoting rotation-vibration coupling.