Photodissociation of water in the first absorption band

A prototype for dissociation on a repulsive potential energy surface

V. Engel, V. Staemmler, Randy Lee Vander Wal, F. F. Crim, R. J. Sension, B. Hudson, P. Andresen, S. Hennig, K. Weide, R. Schinke

Research output: Contribution to journalReview article

158 Citations (Scopus)

Abstract

The photodissociation of water in the first absorption band, H2O(X̃) + (Latin small letter h with stroke)ω → H2O(Ã1B1) → H(2S) + OH(2Π), is a prototype of fast and direct bond rupture in an excited electronic state. It has been investigated from several perspectives - absorption spectrum, final state distributions of the products, dissociation of vibrationally excited states, isotope effects, and emission spectroscopy. The availability of a calculated potential energy surface for the à state, including all three internal degrees of freedom, allows comparison of all experimental data with the results of rigorous quantum mechanical calculations without any fitting parameters or simplifying model assumptions. As the result of the confluence of ab initio electronic structure theory, dynamical theory, and experiment, water is probably the best studied and best understood polyatomic photodissociation system. In this article we review the joint experimental and theoretical advances which make water a unique system for studying molecular dynamics in excited electronic states. We focus our attention especially on the interrelation between the various perspectives and the correlation with the characteristic features of the upper-state potential energy surface.

Original languageEnglish (US)
Pages (from-to)3201-3213
Number of pages13
JournalJournal of Physical Chemistry
Volume96
Issue number8
DOIs
StatePublished - Jan 1 1992

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Photodissociation
Potential energy surfaces
photodissociation
Absorption spectra
potential energy
prototypes
Electronic states
dissociation
absorption spectra
Water
water
Emission spectroscopy
strokes
electronics
Excited states
Isotopes
isotope effect
Electronic structure
availability
Molecular dynamics

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

Engel, V. ; Staemmler, V. ; Vander Wal, Randy Lee ; Crim, F. F. ; Sension, R. J. ; Hudson, B. ; Andresen, P. ; Hennig, S. ; Weide, K. ; Schinke, R. / Photodissociation of water in the first absorption band : A prototype for dissociation on a repulsive potential energy surface. In: Journal of Physical Chemistry. 1992 ; Vol. 96, No. 8. pp. 3201-3213.
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title = "Photodissociation of water in the first absorption band: A prototype for dissociation on a repulsive potential energy surface",
abstract = "The photodissociation of water in the first absorption band, H2O(X̃) + (Latin small letter h with stroke)ω → H2O({\~A}1B1) → H(2S) + OH(2Π), is a prototype of fast and direct bond rupture in an excited electronic state. It has been investigated from several perspectives - absorption spectrum, final state distributions of the products, dissociation of vibrationally excited states, isotope effects, and emission spectroscopy. The availability of a calculated potential energy surface for the {\~A} state, including all three internal degrees of freedom, allows comparison of all experimental data with the results of rigorous quantum mechanical calculations without any fitting parameters or simplifying model assumptions. As the result of the confluence of ab initio electronic structure theory, dynamical theory, and experiment, water is probably the best studied and best understood polyatomic photodissociation system. In this article we review the joint experimental and theoretical advances which make water a unique system for studying molecular dynamics in excited electronic states. We focus our attention especially on the interrelation between the various perspectives and the correlation with the characteristic features of the upper-state potential energy surface.",
author = "V. Engel and V. Staemmler and {Vander Wal}, {Randy Lee} and Crim, {F. F.} and Sension, {R. J.} and B. Hudson and P. Andresen and S. Hennig and K. Weide and R. Schinke",
year = "1992",
month = "1",
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doi = "10.1021/j100187a007",
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Engel, V, Staemmler, V, Vander Wal, RL, Crim, FF, Sension, RJ, Hudson, B, Andresen, P, Hennig, S, Weide, K & Schinke, R 1992, 'Photodissociation of water in the first absorption band: A prototype for dissociation on a repulsive potential energy surface', Journal of Physical Chemistry, vol. 96, no. 8, pp. 3201-3213. https://doi.org/10.1021/j100187a007

Photodissociation of water in the first absorption band : A prototype for dissociation on a repulsive potential energy surface. / Engel, V.; Staemmler, V.; Vander Wal, Randy Lee; Crim, F. F.; Sension, R. J.; Hudson, B.; Andresen, P.; Hennig, S.; Weide, K.; Schinke, R.

In: Journal of Physical Chemistry, Vol. 96, No. 8, 01.01.1992, p. 3201-3213.

Research output: Contribution to journalReview article

TY - JOUR

T1 - Photodissociation of water in the first absorption band

T2 - A prototype for dissociation on a repulsive potential energy surface

AU - Engel, V.

AU - Staemmler, V.

AU - Vander Wal, Randy Lee

AU - Crim, F. F.

AU - Sension, R. J.

AU - Hudson, B.

AU - Andresen, P.

AU - Hennig, S.

AU - Weide, K.

AU - Schinke, R.

PY - 1992/1/1

Y1 - 1992/1/1

N2 - The photodissociation of water in the first absorption band, H2O(X̃) + (Latin small letter h with stroke)ω → H2O(Ã1B1) → H(2S) + OH(2Π), is a prototype of fast and direct bond rupture in an excited electronic state. It has been investigated from several perspectives - absorption spectrum, final state distributions of the products, dissociation of vibrationally excited states, isotope effects, and emission spectroscopy. The availability of a calculated potential energy surface for the à state, including all three internal degrees of freedom, allows comparison of all experimental data with the results of rigorous quantum mechanical calculations without any fitting parameters or simplifying model assumptions. As the result of the confluence of ab initio electronic structure theory, dynamical theory, and experiment, water is probably the best studied and best understood polyatomic photodissociation system. In this article we review the joint experimental and theoretical advances which make water a unique system for studying molecular dynamics in excited electronic states. We focus our attention especially on the interrelation between the various perspectives and the correlation with the characteristic features of the upper-state potential energy surface.

AB - The photodissociation of water in the first absorption band, H2O(X̃) + (Latin small letter h with stroke)ω → H2O(Ã1B1) → H(2S) + OH(2Π), is a prototype of fast and direct bond rupture in an excited electronic state. It has been investigated from several perspectives - absorption spectrum, final state distributions of the products, dissociation of vibrationally excited states, isotope effects, and emission spectroscopy. The availability of a calculated potential energy surface for the à state, including all three internal degrees of freedom, allows comparison of all experimental data with the results of rigorous quantum mechanical calculations without any fitting parameters or simplifying model assumptions. As the result of the confluence of ab initio electronic structure theory, dynamical theory, and experiment, water is probably the best studied and best understood polyatomic photodissociation system. In this article we review the joint experimental and theoretical advances which make water a unique system for studying molecular dynamics in excited electronic states. We focus our attention especially on the interrelation between the various perspectives and the correlation with the characteristic features of the upper-state potential energy surface.

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U2 - 10.1021/j100187a007

DO - 10.1021/j100187a007

M3 - Review article

VL - 96

SP - 3201

EP - 3213

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 8

ER -