Journal of Physical Chemistry A, Vol.121, No.5, 1012-1021, 2017
Photoabsorption Assignments for the (C)over-tilde(1)B(2) <-(X)over-tilde(1)A(1)bronic Transitions of SO2, Using New Ab lnitio Potential Energy and Transition Dipole Surfaces
The high resolution spectroscopy of the SO2 molecule is of great topical interest, in a wide variety of contexts ranging from origins of higher life, to astrophysics of the interstellar medium, to environmental chemistry. In particular, the (CB2)-B-1 <- X(1)A(1) UV photoabsorption spectrum has received considerable attention. This spectrum exhibits a highly regular progression of similar to 20 or so strong peaks, spaced roughly 350 cm(-1) apart, which is comparable to the C1B2 bending vibrational frequency. Accordingly, they have for decades been largely attributed to the (1, v gamma 2) <- (0, 0, 0) bend progression. Using a highly accurate new ab initio potential energy surface (PES) for the C1B2 state, we compute vibrational energy levels and wave functions, and compare with a photoabsorption calculation obtained using the same PES and corresponding (CB2)-B-1 <- X(1)A(1), transition dipole surface (TDS). We find that the above putative assignment is incorrect, contradicting even general qualitative trends thus necessitating a very different dynamical picture for this highly unusual molecule.