Theoretical and experimental investigations of the electronic Rydberg states of diazomethane: assignments and state interactions

Igor Fedorov, Lucas Koziol, Guosheng Li, Jessica A Parr, Anna I Krylov, Hanna Reisler
Journal of Physical Chemistry. A 2007 May 31, 111 (21): 4557-66
The electronic states of diazomethane in the region 3.00-8.00 eV have been characterized by ab initio calculations, and electronic transitions in the region 6.32-7.30 eV have been examined experimentally using a combination of 2 + 1 REMPI spectroscopy and photoelectron imaging in a molecular beam. In the examined region, three Rydberg states of 3p character contribute to the transitions, 2(1)A2(3p(y) <-- pi), 2(1)B1(3p(z) <-- pi), and 3(1)A1(3p(x) <-- pi). The former two states are of mostly pure Rydberg character and exhibit a resolved K structure, whereas the 3(1)A1(3p(x) <-- pi) state is mixed with the valence 2(1)A1(pi* <-- pi) state, which is unbound and is strongly predissociative. Analyses of photoelectron kinetic energy distributions indicate that the ground vibrational level of the 2(1)B1(3p(z)) state is mixed with the 2(1)A2(3p(y)) nu(9) level, which is of B1 vibronic symmetry. The other 2(1)A2(3p(y)) vibronic states exhibit pure Rydberg character, generating ions in single vibrational levels. The photoelectron spectra of the 3(1)A1(3p(x) <-- pi) state, on the other hand, give rise to many states of the ion as a result of strong mixing with the valence state, as evidenced also in the ab initio calculations. The equilibrium geometries of the electronic states of neutral diazomethane were calculated by CCSD(T), using the cc-pVTZ basis, and by B3LYP, using the 6-311G(2df,p) basis. Geometry and frequencies of the ground state of the cation were calculated by CCSD(T)/cc-pVTZ, using the unrestricted (UHF) reference. Vertical excitation energies were calculated using EOM-CCSD/6-311(3+,+)G* at the B3LYP optimized geometry. The theoretical results show that the 2(1)A2(3p(y) <-- pi) and 2(1)B1(3p(z) <-- pi) states have geometries similar to the ion, which has C(2v) symmetry, with slight differences due to the interactions of the electron in the 3p orbital with the nuclei charge distributions. The geometry of the 3(1)A1(3p(x) <-- pi) state is quite different and has Cs symmetry. The experimental and theoretical results agree very well, both in regard to excitation energies and to vibrational modes of the ion.

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