State-diagnosed electron capture collisions of CS<sub>2</sub><sup>q+</sup>(q=2, 3) with atomic and molecular gases

Mathur, D.; Kingston, R. G.; Harris, F.M.; Beynon, J. H.

doi:10.1088/0022-3700/19/17/006

Cited by 27 publications

(4 citation statements)

References 8 publications

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“…However, in recent years more interest has been paid to the fate of these energy rich species following laser excitation 20,21 or collisions with atoms and molecules. [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] These studies show that for a polyatomic di-cation XF 3 2ϩ , where X can be C, Si, or S, a variety of reaction channels are available following a collision with a raregas ͑Rg͒ atom: Polyatomic dications exhibit a far more varied range of reactivity in collisions with rare-gas atoms than do diatomic dications. For example, neutral-loss reactions are more likely to be observed for polyatomic dications, and several bond forming reactions have now been detected for polyatomic dications.…”

Section: Introductionmentioning

confidence: 99%

Laser photofragmentation and collision-induced reactions of SiF22+ and SiF32+

Lee

Leone

Champkin

et al. 1997

The Journal of Chemical Physics

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Laser photofragmentation processes of the doubly charged ions SiF 2 2ϩ and SiF 3 2ϩ are studied at 1064, 532, and 355 nm. The observed photoproducts are compared with those of the reaction pathways induced by the collisions of these dications with the rare gases. Photodissociation, via absorption of a single photon occurs readily for both dications, and the photoion yields are dominated by the products of neutral-loss pathways: SiF 2ϩ from SiF 2 2ϩ and SiF 2 2ϩ from SiF 3 2ϩ . A minor contribution from photoinduced charge separation is also observed. For SiF 2 2ϩ , a neutral-loss pathway forming the atomic dication Si 2ϩ is also detected at higher photon energies. The excitation energy required for this fragmentation process is determined to be 2.2Ϯ0.2 eV. Collisions of SiF 2 2ϩ and SiF 3 2ϩ with He and Ne are also dominated by neutral-loss reactions. With the heavier rare gases, charge transfer is exothermic and dominates the product ion yield, although neutral-loss reactions still occur. Interpretation of the charge transfer results using Landau-Zener theory suggests that two electronic states of SiF 2 2ϩ , lying at 31.0Ϯ0.5 eV and 35.5Ϯ0.5 eV above the ground state of the neutral molecule, are present in the dication beam. Ab initio calculations reveal that SiF 3 2ϩ adopts an equilibrium geometry of C 2v symmetry with one elongated bond. Hence, electron capture by SiF 3 2ϩ results in the formation of SiF 3 ϩ in an energetically unfavorable conformation. By taking account of these geometry differences in the Landau-Zener algorithm, a satisfactory rationalization of the ion yields from the charge transfer reactions of SiF 3 2ϩ is achieved.

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Section: Introductionmentioning

confidence: 99%

Laser photofragmentation and collision-induced reactions of SiF22+ and SiF32+

Lee

Leone

Champkin

et al. 1997

The Journal of Chemical Physics

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“…He 2+ ), although data for partially-stripped dications, such as C 2+ and N 2+ was also reported. [99] The centre-of-mass (CM) collision energies T were frequently large, often in the keV range, [100][101][102][103] a regime where bond-forming reactivity would not be expected and electron transfer (ET) processes were unsurprisingly the dominant reactive pathway:…”

Section: Bimolecular Reactions Of Dications 41 Electron Transfer Reactions Of Atomic Dicationsmentioning

confidence: 99%

“…Initial investigations of the collisional behaviour of bimolecular dications were made at high (>1 keV) collision energies in conventional mass spectrometers. [100][101][102][103][116][117][118][119][120][121][122][123][124] However, experiments were soon extended to lower collision energies, below 100 eV. At first, the focus of these experiments involved collisions with the rare gases where the major product channels involved electron transfer.…”

Section: Electron Transfer Reactions Of Molecular Dicationsmentioning

confidence: 99%

Bimolecular reactions of the dications and trications of atoms and small molecules in the gas-phase

Price

Fletcher

Gossan

et al. 2017

International Reviews in Physical Chemistry

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This review discusses the recent developments in our understanding of the electron transfer and bond-forming reactions of small atomic and molecular dications in the gas-phase. A summary of the properties of isolated dications is presented, followed by a review of the major experimental techniques used to probe dicationic reactivity. Electron transfer reactions of dications with neutral species are then discussed, including recent rationalizations of this class of reactivity using simple electrostatic models. Our current understanding of the reactions of dications with neutral atoms and molecules which result in the formation of new chemical bonds is then presented. This part of the account is built around three case studies, including some new results on the bond-forming reactions of O2 2+ with CH4. Moving beyond dicationic species, the account then discusses recent results concerning the bond-forming reactivity of tricationic atoms and small molecules. This section includes the mechanistic conclusions drawn from the first results involving the coincident detection of all three positively charged species generated from the reaction of a molecular trication: CS2 3+ + O2  SO + + CS + + O + . The review concludes with some thoughts concerning the future development of the field.

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“…7,[19][20][21][22][23][24][25][26] Collisions of dications with neutrals had been studied before this date, but almost invariably at high collision energies in adapted conventional MSs, conditions where bond-forming chemistry is unlikely. [27][28][29][30] Although there were a few pioneering studies of dicationic reactivity at low collision energies, 31,32 it was not until the 1990s that the low-energy collisions of dications, collisions where conventional chemistry might be expected to occur, were investigated systematically. It is the aim of this article to discuss representative examples of the extensive and varied chemistries that have been revealed by these studies.…”

Section: +mentioning

confidence: 99%

Bond-Forming Chemistry in the Gas-Phase Reactions of Atomic and Molecular Dications and Trications

Price¹

2015

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

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State-diagnosed electron capture collisions of CS₂^q+(q=2, 3) with atomic and molecular gases

Cited by 27 publications

References 8 publications

Laser photofragmentation and collision-induced reactions of SiF22+ and SiF32+

Laser photofragmentation and collision-induced reactions of SiF22+ and SiF32+

Bimolecular reactions of the dications and trications of atoms and small molecules in the gas-phase

Bond-Forming Chemistry in the Gas-Phase Reactions of Atomic and Molecular Dications and Trications

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State-diagnosed electron capture collisions of CS2q+(q=2, 3) with atomic and molecular gases

Cited by 27 publications

References 8 publications

Laser photofragmentation and collision-induced reactions of SiF22+ and SiF32+

Laser photofragmentation and collision-induced reactions of SiF22+ and SiF32+

Bimolecular reactions of the dications and trications of atoms and small molecules in the gas-phase

Bond-Forming Chemistry in the Gas-Phase Reactions of Atomic and Molecular Dications and Trications

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Product

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State-diagnosed electron capture collisions of CS₂^q+(q=2, 3) with atomic and molecular gases