skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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]
  1. Massachusetts Institute of Technology, Cambridge, MA (United States)
Publication Date:
Research Org.:
Massachusetts Institute of Technology, Cambridge, MA (United States)
Sponsoring Org.:
USDOE
Contributing Org.:
Massachusetts Institute of Technology
OSTI Identifier:
1248460
Alternate Identifier(s):
OSTI ID: 1247610
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.
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. doi:10.1063/1.4945622.
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. doi:10.1063/1.4945622. https://www.osti.gov/servlets/purl/1248460.
@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 = {2016},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Photodissociation of molecular beams of SO2 at 193 nm
journal, December 1982


Spin polarization in SO photochemically generated from SO 2
journal, July 1985

  • Kanamori, Hideto; Butler, James E.; Kawaguchi, Kentarou
  • The Journal of Chemical Physics, Vol. 83, Issue 2
  • DOI: 10.1063/1.449528

Two-photon dissociation of sulfur dioxide at 248 and 308 nm
journal, April 1990


Theoretical Studies on the Potential Energy Surfaces of SO 2 : Electronic States for Photodissociation from the \ ildeC 1 B 2 State
journal, September 1991

  • Kamiya, Kenshu; Matsui, Hiroyuki
  • Bulletin of the Chemical Society of Japan, Vol. 64, Issue 9
  • DOI: 10.1246/bcsj.64.2792

State specific photodissociation of SO2 and state selective detection of the SO fragment
journal, June 1993


Investigation of the predissociation of SO2: state selective detection of the SO and O fragments
journal, June 1995


Degenerate four-wave mixing and photofragment yield spectroscopic study of jet-cooled SO2 in the C̃ 1B2 state: Internal conversion followed by dissociation in the X̃ state
journal, December 1997

  • Okazaki, Akihiro; Ebata, Takayuki; Mikami, Naohiko
  • The Journal of Chemical Physics, Vol. 107, Issue 21
  • DOI: 10.1063/1.475168

Experimental and theoretical exploration of photodissociation of SO2 via the C̃1B2 state: identification of the dissociation pathway
journal, September 1997


Resonance emission spectroscopy of predissociating SO2 C̃(1 1B2): Coupling with a repulsive 1A1 state near 200 nm
journal, October 1998

  • Ray, Paresh C.; Arendt, Michael F.; Butler, Laurie J.
  • The Journal of Chemical Physics, Vol. 109, Issue 13
  • DOI: 10.1063/1.477139

Vibrational propensity in the predissociation rate of SO2(C̃1B2) by two types of nodal patterns in vibrational wavefunctions
journal, September 1998


Quantum calculations of highly excited vibrational spectrum of sulfur dioxide. III. Emission spectra from the C̃ 1B2 state
journal, November 1999

  • Xie, Daiqian; Ma, Guobin; Guo, Hua
  • The Journal of Chemical Physics, Vol. 111, Issue 17
  • DOI: 10.1063/1.480113

A combined experimental and theoretical study of resonance emission spectra of SO2(C̃ )
journal, April 2000


Changes in the Vibrational Population of SO( 3 Σ - ) from the Photodissociation of SO 2 between 202 and 207 nm
journal, November 2000

  • Cosofret, Bogdan R.; Dylewski, Scott M.; Houston, Paul L.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 45
  • DOI: 10.1021/jp001276w

Observation of wavelength-sensitive mass-independent sulfur isotope effects during SO 2 photolysis: Implications for the early atmosphere
journal, December 2001

  • Farquhar, James; Savarino, Joel; Airieau, Sabine
  • Journal of Geophysical Research: Planets, Vol. 106, Issue E12
  • DOI: 10.1029/2000JE001437

Time-resolved Fourier transform infrared study of the 193 nm photolysis of SO2
journal, September 2003


Contribution to the Study of Electronic Spectra of Bent Triatomic Molecules
journal, September 1947

  • Duchesne, Jules; Rosen, B.
  • The Journal of Chemical Physics, Vol. 15, Issue 9
  • DOI: 10.1063/1.1746620

The ultraviolet spectrum of SO2 in matrix isolation and the vibrational structure of the 2348 Å system
journal, July 1973


Sulfur dioxide: Rotational constants and asymmetric structure of the state
journal, March 1976


Asymmetric structure and force field of the 1 B 2 ( 1 A′) state of sulphur dioxide
journal, November 1978


Observation of b2 symmetry vibrational levels of the SO2 C̃ 1B2 state: Vibrational level staggering, Coriolis interactions, and rotation-vibration constants
journal, April 2016

  • Park, G. Barratt; Jiang, Jun; Saladrigas, Catherine A.
  • The Journal of Chemical Physics, Vol. 144, Issue 14
  • DOI: 10.1063/1.4944924

The rotation-vibration structure of the SO2 C̃1B2 state explained by a new internal coordinate force field
journal, April 2016

  • Jiang, Jun; Park, G. Barratt; Field, Robert W.
  • The Journal of Chemical Physics, Vol. 144, Issue 14
  • DOI: 10.1063/1.4945621

The Lower Excited States of some Simple Molecules
journal, January 1958

  • Mulliken, R. S.
  • Canadian Journal of Chemistry, Vol. 36, Issue 1
  • DOI: 10.1139/v58-002

SO2: Origins of unequal bond lengths in the electronic state
journal, November 1986


Investigation of the potential energy surfaces for the ground X̃1A1 and excited C̃1B2 electronic states of SO2
journal, April 1999


The calculation of the vibrational states of SO2 in the C̃1B2 electronic state up to the SO(3Σ−)+O(3P) dissociation limit
journal, March 2000


Fluorescence and predissociation of sulfur dioxide
journal, December 1971

  • Okabe, H.
  • Journal of the American Chemical Society, Vol. 93, Issue 25
  • DOI: 10.1021/ja00754a072

Decay of fluorescence from single vibronic states of SO2
journal, December 1972


The Resonance Fluorescence Spectrum of Sulfur Dioxide
journal, March 1973

  • Brand, J. C. D.; Humphrey, D. R.; Douglas, A. E.
  • Canadian Journal of Physics, Vol. 51, Issue 5
  • DOI: 10.1139/p73-069

Theoretical studies of <mml:math altimg="si7.gif" display="inline" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http://www.elsevier.com/xml/common/dtd" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:cals="http://www.elsevier.com/xml/common/cals/dtd"><mml:mrow><mml:msup><mml:mrow><mml:mover accent="true"><mml:mrow><mml:mi>C</mml:mi></mml:mrow><mml:mrow><mml:mo stretchy="true">∼</mml:mo></mml:mrow></mml:mover></mml:mrow><mml:mrow><mml:mn>1</mml:mn></mml:mrow></mml:msup><mml:msub><mml:mrow><mml:mi>B</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math> absorption spectra of SO2 isotopomers
journal, May 2007


Ground and low-lying excited states of SO2 studied by the SAC/SAC-CI method
journal, June 2008


Theoretical studies of absorption cross sections for the C̃ B12-X̃ A11 system of sulfur dioxide and isotope effects
journal, January 2010

  • Tokue, Ikuo; Nanbu, Shinkoh
  • The Journal of Chemical Physics, Vol. 132, Issue 2
  • DOI: 10.1063/1.3277191

The electronically excited and ionic states of sulphur dioxide: an ab initio molecular orbital CI study and comparison with spectral data
journal, March 2005