TY - JOUR
T1 - Photoabsorption Assignments for the C1B2 ← X1A1 Vibronic Transitions of SO2, Using New Ab Initio Potential Energy and Transition Dipole Surfaces
AU - Kumar, Praveen
AU - Jiang, Bin
AU - Guo, Hua
AU - Kłos, Jacek
AU - Alexander, Millard H.
AU - Poirier, Bill
N1 - Funding Information:
This work was largely supported by a research grant (NNX13AJ49G-EXO) from NASA Astrobiology, together with both a research grant (CHE-1012662) and a CRIF MU instrumentation grant (CHE-0840493) from the National Science Foundation. The authors gratefully acknowledge the following entities for providing access and technical support of their respective computing clusters: Texas Tech University for use of the Hrothgar and Robinson clusters; the Texas Advanced Computing Center, for use of the Lonestar facility.
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/2/9
Y1 - 2017/2/9
N2 - 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 C1B2 ← X1A1 UV photoabsorption spectrum has received considerable attention. This spectrum exhibits a highly regular progression of ∼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, v2′, 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 C1B2 ← X1A1 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.
AB - 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 C1B2 ← X1A1 UV photoabsorption spectrum has received considerable attention. This spectrum exhibits a highly regular progression of ∼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, v2′, 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 C1B2 ← X1A1 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.
UR - http://www.scopus.com/inward/record.url?scp=85018638128&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.6b12958
DO - 10.1021/acs.jpca.6b12958
M3 - Article
C2 - 28068096
AN - SCOPUS:85018638128
VL - 121
SP - 1012
EP - 1021
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 5
ER -