Rydberg and valence excited states of dibromomethane in 35,000–95,000cm−1 region studied using synchrotron radiation.

Abstract: The UV–VUV photoabsorption spectrum of dibromomethane (CH2Br2) in the energy region 4.3–11.8eV (35,000–95,000cm−1) is investigated using synchrotron radiation. Rydberg series converging to the first four ionization limits at 10.52, 10.74, 11.21 and 11.30eV corresponding to excitations from the 3b1, 2b2, 1a2, and 4a1 orbitals of CH2Br2 are identified and analyzed. Quantum defect values are observed to be consistent with excitation from the bromine lone pair orbitals. Assignments of the ns Rydberg series are revised and the np and nd Rydberg series are assigned for the first time. Observed vibrational features accompanying the 5p and 4d Rydberg states are assigned exclusively to the totally symmetric (a1) –CBr symmetric stretching mode (ν3) in contrast to the earlier assignment to ν3 and –CH2 bending (ν2) modes. The Rydberg and valence transitions observed in the present experiment are found to be in good agreement with the vertical excited states calculated using the TDDFT method. The calculations are further used to infer the valence transitions responsible for the broad intensity pedestals underlying the Rydberg transitions. The assignments are confirmed using isotopic substitution studies on CD2Br2 whose UV–VUV photoabsorption spectrum is reported here for the first time. This work presents a consolidated analysis of the UV–VUV photoabsorption spectrum of dibromomethane. [Copyright &y& Elsevier]