Communication: The influence of vibrational parity in chiral photoionization dynamics.

A pronounced vibrational state dependence of photoelectron angular distributions observed in chiral photoionization experiments is explored using a simple, yet realistic, theoretical model based upon the transiently chiral molecule H2O2. The adiabatic approximation is used to separate vibrational and electronic wavefunctions. The full ionization matrix elements are obtained as an average of the electronic dipole matrix elements over the vibrational coordinate, weighted by the product of neutral and ion state vibrational wavefunctions. It is found that the parity of the vibrational Hermite polynomials influences not just the amplitude, but also the phase of the transition matrix elements, and the latter is sufficient, even in the absence of resonant enhancements, to account for enhanced vibrational dependencies in the chiral photoionization dynamics.