A time-resolved photoelectron imaging study on isolated tolane: observation of the biradicalic A state.

Tolane (diphenylacetylene, CH) was studied by picosecond time-resolved photoionisation and photoelectron imaging in a supersonic jet. The low-energy part of the B← S REMPI spectrum is very similar to an earlier LIF spectrum, however additional bands were observed at higher energies above the fluorescence cut-off. For a number of bands the dynamics were investigated via pump-probe photoionisation and photoelectron spectroscopy. Around the B origin the lifetimes are in the ns range, but they drop to some 10 ps at higher excitation energies. For the short-lived bands at higher energies a sequential two-step relaxation to a long-lived electronic state was observed proceeding via an intermediately populated state with a lifetime of 100-200 ps. By comparison with previous quantum chemical calculations we assign this state as the biradicalic trans-bentA state that is ionised in a two-photon process.