Effects of isomer coexistence and solvent-induced core switching in the photodissociation of bare and solvated (CS2)2- anions

Terefe Habteyes, Luis Velarde, Andrei M Sanov

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The photodissociation of the (CS2)2- dimer anion, known to exist in the form of several electronic and structural isomers, has been investigated at 532, 355, and 266 nm. The observed anionic fragments are CS 2- and C2 S2- at 532 nm, and C 2 S2-, CS 2-, CS 3-, S2-, and S- at 355 and 266 nm. In addition to the photon energy, the fractional yields of the photofragments depend on the ion source conditions and solvation of the dimer anion. Specifically, the (C2 S2- + S2-) / CS 2- product ratio is significantly higher when (CS2)2- is formed in the presence of water in the precursor gas mixture, even though the parent anion itself does not include H2 O. On the other hand, an abrupt decrease in the above product ratio is observed upon the addition of solvent molecules (CS2 or H2 O) to the (CS2)2- anion. Since the variation of this product ratio exhibits positive correlation with the relative intensity of the photoelectron band assigned to the C2v (B2 1) covalent structure of C2 S4- by Habteyes [J. Phys. Chem. A 112, 10134 (2008)], this structure is suggested as the primary origin of the C2 S 2- and S2- photoproducts. The switching of the fragmentation yield from C2 S2 - and S2- to other products upon solvation is ascribed to the diminished presence of the C2v (B2 1) dimer-anion structure relative to the CS 2- based clusters. This population shift is attributed to the more effective solvation of the latter. The CS 2- based clusters are suggested as the origin of the S- photoproduct, while CS 3- is formed through the secondary S- + CS2 intracluster association reaction.

Original languageEnglish (US)
Article number124301
JournalThe Journal of Chemical Physics
Volume130
Issue number12
DOIs
StatePublished - 2009

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Photodissociation
Isomers
photodissociation
Anions
isomers
anions
Solvation
Dimers
solvation
dimers
products
association reactions
Ion sources
Photoelectrons
Gas mixtures
ion sources
gas mixtures
fragmentation
photoelectrons
Photons

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Effects of isomer coexistence and solvent-induced core switching in the photodissociation of bare and solvated (CS2)2- anions. / Habteyes, Terefe; Velarde, Luis; Sanov, Andrei M.

In: The Journal of Chemical Physics, Vol. 130, No. 12, 124301, 2009.

Research output: Contribution to journalArticle

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abstract = "The photodissociation of the (CS2)2- dimer anion, known to exist in the form of several electronic and structural isomers, has been investigated at 532, 355, and 266 nm. The observed anionic fragments are CS 2- and C2 S2- at 532 nm, and C 2 S2-, CS 2-, CS 3-, S2-, and S- at 355 and 266 nm. In addition to the photon energy, the fractional yields of the photofragments depend on the ion source conditions and solvation of the dimer anion. Specifically, the (C2 S2- + S2-) / CS 2- product ratio is significantly higher when (CS2)2- is formed in the presence of water in the precursor gas mixture, even though the parent anion itself does not include H2 O. On the other hand, an abrupt decrease in the above product ratio is observed upon the addition of solvent molecules (CS2 or H2 O) to the (CS2)2- anion. Since the variation of this product ratio exhibits positive correlation with the relative intensity of the photoelectron band assigned to the C2v (B2 1) covalent structure of C2 S4- by Habteyes [J. Phys. Chem. A 112, 10134 (2008)], this structure is suggested as the primary origin of the C2 S 2- and S2- photoproducts. The switching of the fragmentation yield from C2 S2 - and S2- to other products upon solvation is ascribed to the diminished presence of the C2v (B2 1) dimer-anion structure relative to the CS 2- based clusters. This population shift is attributed to the more effective solvation of the latter. The CS 2- based clusters are suggested as the origin of the S- photoproduct, while CS 3- is formed through the secondary S- + CS2 intracluster association reaction.",
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AB - The photodissociation of the (CS2)2- dimer anion, known to exist in the form of several electronic and structural isomers, has been investigated at 532, 355, and 266 nm. The observed anionic fragments are CS 2- and C2 S2- at 532 nm, and C 2 S2-, CS 2-, CS 3-, S2-, and S- at 355 and 266 nm. In addition to the photon energy, the fractional yields of the photofragments depend on the ion source conditions and solvation of the dimer anion. Specifically, the (C2 S2- + S2-) / CS 2- product ratio is significantly higher when (CS2)2- is formed in the presence of water in the precursor gas mixture, even though the parent anion itself does not include H2 O. On the other hand, an abrupt decrease in the above product ratio is observed upon the addition of solvent molecules (CS2 or H2 O) to the (CS2)2- anion. Since the variation of this product ratio exhibits positive correlation with the relative intensity of the photoelectron band assigned to the C2v (B2 1) covalent structure of C2 S4- by Habteyes [J. Phys. Chem. A 112, 10134 (2008)], this structure is suggested as the primary origin of the C2 S 2- and S2- photoproducts. The switching of the fragmentation yield from C2 S2 - and S2- to other products upon solvation is ascribed to the diminished presence of the C2v (B2 1) dimer-anion structure relative to the CS 2- based clusters. This population shift is attributed to the more effective solvation of the latter. The CS 2- based clusters are suggested as the origin of the S- photoproduct, while CS 3- is formed through the secondary S- + CS2 intracluster association reaction.

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