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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

Abstract

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°.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
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  1. Massachusetts Institute of Technology, Cambridge, MA (United States)
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1248460
Alternate Identifier(s):
OSTI ID: 1247610; OSTI ID: 1733333; OSTI ID: 1831801
Grant/Contract Number:  
FG02-87ER13671; FG0287ER13671
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 14; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; SO2; sulfur dioxide; pseudo Jahn-Teller; vibronic interaction; potential energy surfaces; dissociation; oscillators; electroluminescence

Citation Formats

Park, G. Barratt, Jiang, Jun, and Field, Robert W. 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. United States: N. p., 2016. Web. doi:10.1063/1.4945622.
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Park, G. Barratt, Jiang, Jun, & Field, Robert W. 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. United States. https://doi.org/10.1063/1.4945622
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Park, G. Barratt, Jiang, Jun, and Field, Robert W. Thu . "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". United States. https://doi.org/10.1063/1.4945622. https://www.osti.gov/servlets/purl/1248460.
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@article{osti_1248460,
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},
author = {Park, G. Barratt and Jiang, Jun and Field, Robert W.},
abstractNote = {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°.},
doi = {10.1063/1.4945622},
journal = {Journal of Chemical Physics},
number = 14,
volume = 144,
place = {United States},
year = {Thu Apr 14 00:00:00 EDT 2016},
month = {Thu Apr 14 00:00:00 EDT 2016}
}
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https://doi.org/10.1063/1.4945622
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The ultraviolet spectrum of SO2 in matrix isolation and the vibrational structure of the 2348 Å system
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