A nonperturbative theory for calculating time-resolved photoelectron angular distributions in linear molecules [J. Chem. Phys. 107, 7859 (1997)] is extended to nonlinear systems and reformulated so as to expose and utilize the underlying electronic and rotational symmetries. A sequence of approximations is next introduced, systematically reducing the formally exact expression to cruder forms that are applicable to systems of increasing complexity. As an example of the potential applications of time-resolved photoelectron angular distributions in polyatomic dynamics we examine the information they convey about an ultrafast internal conversion.

• Received 21 February 2001

DOI:https://doi.org/10.1103/PhysRevA.64.042504