High-resolution photoelectron spectroscopy of linear ← bent polyatomic photodetachment transitions: The electron affinity of CS 2

S. J. Cavanagh; S. T. Gibson; B. R. Lewis

doi:10.1063/1.4757726

High-resolution photoelectron spectroscopy of linear ← bent polyatomic photodetachment transitions: The electron affinity of CS ₂

S. J. Cavanagh^*, S. T. Gibson, B. R. Lewis

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

A combination of high-resolution velocity-map-imaging photoelectron spectroscopy and isotopic substitution is used to show that precise electron affinities can be obtained from polyatomic photodetachment spectra, even for cases involving significant changes in equilibrium geometry between the molecular neutral and anion. The chosen example CS ₂ (X ¹Σ _g ⁺) (linear) ← CS ₂ ^- (X ²A ₁) (bent) photodetachment transition is found to preferentially access highly-excited v ₂ (bending) levels of the neutral, with no observation possible of the lowest-v ₂ bands. Nevertheless, through ¹³C isotopic substitution, the v ₂ numbering is established unambiguously and the adiabatic electron affinity of CS ₂ is found to be 4456(10) cm ^-1 [0.5525(13) eV], by far the most precise value reported to date.

Original language	English
Article number	144304
Journal	Journal of Chemical Physics
Volume	137
Issue number	14
DOIs	https://doi.org/10.1063/1.4757726
Publication status	Published - 14 Oct 2012

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title = "High-resolution photoelectron spectroscopy of linear ← bent polyatomic photodetachment transitions: The electron affinity of CS 2",

abstract = "A combination of high-resolution velocity-map-imaging photoelectron spectroscopy and isotopic substitution is used to show that precise electron affinities can be obtained from polyatomic photodetachment spectra, even for cases involving significant changes in equilibrium geometry between the molecular neutral and anion. The chosen example CS 2 (X 1Σ g +) (linear) ← CS 2 - (X 2A 1) (bent) photodetachment transition is found to preferentially access highly-excited v 2 (bending) levels of the neutral, with no observation possible of the lowest-v 2 bands. Nevertheless, through 13C isotopic substitution, the v 2 numbering is established unambiguously and the adiabatic electron affinity of CS 2 is found to be 4456(10) cm -1 [0.5525(13) eV], by far the most precise value reported to date.",

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T1 - High-resolution photoelectron spectroscopy of linear ← bent polyatomic photodetachment transitions

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AU - Cavanagh, S. J.

AU - Gibson, S. T.

AU - Lewis, B. R.

PY - 2012/10/14

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N2 - A combination of high-resolution velocity-map-imaging photoelectron spectroscopy and isotopic substitution is used to show that precise electron affinities can be obtained from polyatomic photodetachment spectra, even for cases involving significant changes in equilibrium geometry between the molecular neutral and anion. The chosen example CS 2 (X 1Σ g +) (linear) ← CS 2 - (X 2A 1) (bent) photodetachment transition is found to preferentially access highly-excited v 2 (bending) levels of the neutral, with no observation possible of the lowest-v 2 bands. Nevertheless, through 13C isotopic substitution, the v 2 numbering is established unambiguously and the adiabatic electron affinity of CS 2 is found to be 4456(10) cm -1 [0.5525(13) eV], by far the most precise value reported to date.

AB - A combination of high-resolution velocity-map-imaging photoelectron spectroscopy and isotopic substitution is used to show that precise electron affinities can be obtained from polyatomic photodetachment spectra, even for cases involving significant changes in equilibrium geometry between the molecular neutral and anion. The chosen example CS 2 (X 1Σ g +) (linear) ← CS 2 - (X 2A 1) (bent) photodetachment transition is found to preferentially access highly-excited v 2 (bending) levels of the neutral, with no observation possible of the lowest-v 2 bands. Nevertheless, through 13C isotopic substitution, the v 2 numbering is established unambiguously and the adiabatic electron affinity of CS 2 is found to be 4456(10) cm -1 [0.5525(13) eV], by far the most precise value reported to date.

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JF - Journal of Chemical Physics

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High-resolution photoelectron spectroscopy of linear ← bent polyatomic photodetachment transitions: The electron affinity of CS ₂

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