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Title: The origin of unequal bond lengths in the C1B2 state of SO2: Signatures of high-lying potential energy surface crossings in the low-lying vibrational structure

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4945622· OSTI ID:1248460
ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Massachusetts Institute of Technology, Cambridge, MA (United States)
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Here the C1B2 state of SO2 has a double-minimum potential in the antisymmetric stretch coordinate, such that the minimum energy geometry has nonequivalent SO bond lengths. The asymmetry in the potential energy surface is expressed as a staggering in the energy levels of the v'3 progression. We have recently made the first observation of low-lying levels with odd quanta of v'3, which allows us--in the current work--to characterize the origins of the level staggering. Our work demonstrates the usefulness of low-lying vibrational level structure, where the character of the wavefunctions can be relatively easily understood, to extract information about dynamically important potential energy surface crossings that occur at much higher energy. The measured staggering pattern is consistent with a vibronic coupling model for the double-minimum, which involves direct coupling to the bound 2 1A1 state and indirect coupling with the repulsive 3 1A1 state. The degree of staggering in the v'3 levels increases with quanta of bending excitation, which is consistent with the approach along the C state potential energy surface to a conical intersection with the 2 1A1 surface at a bond angle of ~145°.

Research Organization:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
FG02-87ER13671; FG0287ER13671
OSTI ID:
1248460
Alternate ID(s):
OSTI ID: 1247610; OSTI ID: 1733333; OSTI ID: 1831801
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 14; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

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Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
SO2
sulfur dioxide
pseudo Jahn-Teller
vibronic interaction
potential energy surfaces
dissociation
oscillators
electroluminescence