Sub-5-fs resolved nonlinear optical processes in polydiacetylene

Molecular vibration of several modes in blue-phase polydiacetylene-3- butoxycarbonylmethylurethane (PDA-3BCMU) was real-time observed by 5-fs pump-probe measurement. The contribution of the vibrational wavepackets in the ground state and in the ground state and in the excited state in the signal were separated by multi-channel measurement. The C=C stretching mode in the ground state starts to oscillate π-out-of-phase with the C≡C stretching mode. The structure of PDA-3BCMU in the geometrically relaxed state is not pure butatriene-type but more like acetylene-type. The frequencies of C=C and C≡C stretching modes there were determined by singular value decomposition method to be 1472 ± 6 cm-1 and 2092 ± 6 cm-1, respectively. The double and triple bond stretching frequencies in the ground state which are 1463 ± 6 cm-1 2083 ± 6 cm-1, respectively.