Theoretical and numerical study shows that the measurement of time-resolved PADs yields a map of the time evolution of a rovibrational wave packet subject to rotation-vibration interactions. A convenient measure of the rotational composition of a wave packet is the expectation value of cos2 θ, θ being the polar Euler angle between an axis fixed in the molecule and an axis fixed in space. In the absence of rotation-vibration coupling 〈cos2 θ〉 is a smooth function of the pump-probe delay time, reflecting the slow rotational motions.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry