PHOTOIONIZATION VIA TRANSIENT STATES - A COHERENT PROBE OF MOLECULAR EIGENSTATES

A new technique is presented to probe the composition of molecular eigenstates underlying transitions to high-lying electronic states. In a first application we measured the photoelectron spectrum of azulene obtained upon ionizing the molecule via the S3 electronic state using transform-limited picosecond laser pulses. It is found that the molecular eigenstates are predominantly of S2 character. Results with the S4 transition are similar, but less conclusive.