We present quantitative results on photodissociation of CH2 (X̃ 3B1) and its isotopomers CHD and CD2 through the first excited triplet state (1 3A1). A two‐dimensional wave packet method employing... Show moreWe present quantitative results on photodissociation of CH2 (X̃ 3B1) and its isotopomers CHD and CD2 through the first excited triplet state (1 3A1). A two‐dimensional wave packet method employing the light–heavy–light approximation was used to perform the dynamics. The potential energy surfaces and the transition dipole moment function used were all taken from abinitio calculations. The peak positions in the calculated CH2 and CD2 spectra nearly coincide with the positions of unassigned peaks in experimental CH2 and CD2 3+1 resonance enhanced multiphoton ionization spectra, provided that the experimental peaks are interpreted as two‐photon transitions. Comparing the photodissociation of CH2 and its isotopomers to photodissociation of water in the first absorption band, we find these processes to be very similar in all aspects discussed in this work. These aspects include the origin of the diffuse structure and the overall shape of the total absorption spectra of vibrationless and vibrationally excited CH2 , trends seen in the fragment vibrational level distribution of the different isotopomers, and selectivity of photodissociation of both vibrationless and vibrationally excited CHD. In particular, we find that the CD/CH branching ratio exceeds two for all wavelengths in photodissociation of vibrationless CHD. Show less
The lower excited states of the planar all-trans isomers of crotonaldehyde, hexadienal, and octatrienal have been investigated by multi-reference single and double excitation configuration... Show moreThe lower excited states of the planar all-trans isomers of crotonaldehyde, hexadienal, and octatrienal have been investigated by multi-reference single and double excitation configuration interaction (MRD-CI) calculations. For crotonaldehyde we find both the lowest excited singlet state S1 and the lowest triplet state T0 to be n-pi* in nature; for hexadienal and octatrienal S1 is n-pi* and T0 is pi-pi* in nature. Bond-order reversal stabilizes the lower excited states and destabilizes the ground state. The pi-pi* states decrease more in energy than the n-pi* states upon lengthening the polyenal. We calculate the radiative lifetime of the 3-pi-pi* state in the ground-state geometry to vary from 35 ms for crotonaldehyde to 75 s for octatrienal and explain the absence of phosphorescence for polyenals. Show less
Buma, W.J.; Groenen, E.J.J.; Hemert, M.C. van 1990
