摘要：

Tentative assignment of the low-lying vibrational features of the first electronic excited singlet-state S1 of diphenyl ether (Ph2O), obtained from resonance-enhanced multiphoton ionisation (REMPI) spectroscopy, is performed using CIS and time-dependent density functional theory (TD-DFT) methods. The potential energy surfaces, regarding the rotation of the phenyl rings relatively to the C–O–C plane, are obtained at the B3LYP/6-31G(d) level of theory, for the ground-state of neutral and cationic Ph2O and for its first excited singlet state. The torsional barriers of the ground state of diphenyl ether were studied by means of quantum-chemical perturbations of increasing accuracy and an extrapolation to the complete basis set limit and full configuration interaction (FCI) was performed through the use of correlation consistent basis sets and the continued fraction method. The first adiabatic ionisation energy (AIE) of the twist conformer is computed at 8.60 eV in the FCI limit, much higher than the experimental results of Terlouw et al. (8.09±0.03 eV) and Paiva et al. (7.8±0.1 eV). The B3LYP result of 7.82 eV is, however, in reasonable agreement with the result of Paiva et al. The first singlet excitation energy for the twist conformation is found to be 5.5 eV at the CIS/6-311++G(d,p) level of theory. Some features of the experimental REMPI spectrum, previously obtained by one of the authors, are explained and a new insight on the ionisation energy of diphenyl ether is presented.

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