The reactions of Cl+(3P) and Cl+(1D) with hydrogen sulphide. A G2 molecular orbital study

Manuel, M.

doi:10.1080/00268979909482955

Cited by 4 publications

(5 citation statements)

References 48 publications

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“…As shown in Figure , the changes in the optimized geometrical parameters are negligible. This confirms previous findings,8h at least in the sense that a QCISD procedure is required to adequately describe the geometries of these weakly bound complexes.…”

Section: Resultssupporting

confidence: 91%

“…In the past few years our research group has focused its attention on the subset of reactive processes which involve open-shell monocations . Along this line, a particular interest was concentrated on reactions involving the halogen cations, 8e-g because these are characterized by quite-large recombination energies which strongly favor charge-transfer processes, 8e-g and because they usually yield weakly bound species when reacting in the ground state. In contrast, when the reaction takes place in the first singlet excited state, covalently bound species are formed.…”

Section: Introductionmentioning

confidence: 99%

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Thermochemistry of the Reactions F⁺(³P, ¹D) + PH₃ in the Gas Phase

et al. 2000

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High-level ab initio calculations in the framework of the G2 theory have been performed for the [H3, P, F]+ singlet- and triplet-state cations. The bonding characteristics of singlet- and triplet-state cations are rather different. The latter are weakly bound species involving electrostatic and/or polarization interactions, while the former present covalent bonds. As a consequence, while in the F+(3P) + PH3(1A1) reactions in the gas phase the charge-transfer process competes with the formation of HF(1Σ+) + PH2 +(3B1), the main products when the reaction involves the F+ cation in its 1D first excited state are HF(1Σ+) + PH2 +(1A1). In both cases, the reactions are extremely exothermic, and therefore, the products are anticipated to be vibrationally excited. The [H3, P, F]+ triplet-state cations are good examples of molecular planetary systems, in which a neutral fluorine atom or a neutral HF molecule orbits around a PH3 + or a PH2 + moiety, respectively. Although the singlet PES lies systematically below the triplet PES, there are regions where both surfaces approach each other significantly. The spin−orbit coupling between them, evaluated at the corresponding minimum energy crossing point, indicates that a fast transition between both PESs should take place, implying the possibility of having “spin-forbidden” reactions. From our calculations, the heat of formation for FPH2 was estimated to be −58.2 ± 2.5 kcal/mol.

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Section: Resultssupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Thermochemistry of the Reactions F⁺(³P, ¹D) + PH₃ in the Gas Phase

et al. 2000

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“…In the first place, the interaction between N + ( 3 P) and formaldehyde yields covalently bound species. This is at variance with what was found for other triplet state cations as F + and Cl + , where the interactions yield systematically weakly bound species. 4c,e-g The interaction between N + and neutral formaldehyde can be envisaged as a two-steps process. The first one corresponds to a charge transfer, due to the high recombination energy of N + ( 3 P).…”

Section: Resultsmentioning

confidence: 75%

“…In our group we have paid some attention to these kinds of reactions in particular when the reactant monocation is an open-shell species.…”

Section: Introductionmentioning

confidence: 99%

A Theoretical Study of the Reaction between N⁺(³P) and Formaldehyde and Related Processes in the Gas Phase

et al. 2000

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The [H2, C, N, O]+ potential energy surface (PES) in its triplet state multiplicity has been explored by means of high-level ab initio calculations, carried out in the framework of the G2 theory. From the PES survey we conclude that some of the products of the N+(3P) + H2CO reaction are the result of a competitive dissociation of the H2CON+ cation into NO+ + H2C or N + H2CO+. Although the first process is more exothermic than the second one, it involves a conical intersection, and as a consequence N + H2CO+ are the dominant products. NH + HCO+, which are also experimentally observed products, can be formed either by the dissociation of the HCONH+ cation, through another conical intersection, or by the fragmentation of a quite stable HN···HCO+ complex. Other possible products, such as CNH + OH+, HCN + OH+, and CO + NH2 +, although exothermic, should not be observed since the corresponding reaction pathways involve high activation barriers. These conclusions are in good agreement with the experimental evidence. The topology of the [H2, C, N, O]+ PES also explains why no reaction is observed when NH2 + and CO or CH2 and NO+ interact in the gas phase, while in CH2 + + NO reactions, only the charge exchange channel is open. We also predict that the dominant products in OH+ + HCN reactions should be NH + HCO+. However, when this reaction involves the CNH isomer the observed products should be not only NH + HCO+ but also NH2 + + CO.

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“…This is the case of the halogen cations and N + where the first excited 1 D state is relatively close in energy to the ground 3 P state . Quite importantly, however, when the ion is attached to a neutral molecule, a reverse stability order is often found and singlets become lower in energy than triplets, ,,− reflecting the stronger bonds between the ion and the neutral in the former. Accordingly, different crossovers between singlet and triplet PESs can be envisaged, ,, and therefore in many of these processes spin-forbidden reaction mechanisms play an important role, as has been suggested before for N + + SH 2 and N + + H 2 CO reactions. , In this paper we will focus our attention on the reactions between N + ( 3 P, 1 D) and ethylene, because hydrocarbons are ubiquitous in the aforementioned media and therefore they usually play an important role in the generation of new molecular systems. , As a matter of fact, ethylene is one of the main components of Titan's atmosphere, , where both N + ( 3 P) and N + ( 1 D) can be also produced from the existing N 2 molecules via cosmic ray absorption.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Survey of the Potential Energy Surfaces Associated with the N⁺(³P,D) + C₂H₄Reactions in the Gas Phase

2004

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The potential energy surfaces (PESs) associated with the reactions between ethylene and N+(3P,1D) ions have been investigated through the use of high-level G2(MP2) ab initio calculations. Although the N+(3P) + C2H4 entrance channel lies 46.7 kcal mol-1 below the N+(1D) + C2H4, most of the singlet-state cations are more stable than their triplet-state counterparts because, in general, the bonds in the former are stronger than those in the latter, favoring the crossover between both PESs. Several minimum energy crossing points between both hypersurfaces have been located, and the corresponding spin−orbit couplings indicate that spin-forbidden processes in N+ + C2H4 reactions cannot be discarded. According to our survey, the product distribution in both N+(3P) + C2H4 and N+(1D) + C2H4 reactions should be quite different. While for the triplets the CNH+, HCNH+, HCCH2 +, and HCCH+ product ions should be observed, in agreement with the available experimental information, for the singlets the formation of CH3 + should be the dominant process.

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The reactions of Cl⁺(³P) and Cl⁺(¹D) with hydrogen sulphide. A G2 molecular orbital study

Cited by 4 publications

References 48 publications

Thermochemistry of the Reactions F⁺(³P, ¹D) + PH₃ in the Gas Phase

Thermochemistry of the Reactions F⁺(³P, ¹D) + PH₃ in the Gas Phase

A Theoretical Study of the Reaction between N⁺(³P) and Formaldehyde and Related Processes in the Gas Phase

Theoretical Survey of the Potential Energy Surfaces Associated with the N⁺(³P,D) + C₂H₄Reactions in the Gas Phase

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The reactions of Cl+(3P) and Cl+(1D) with hydrogen sulphide. A G2 molecular orbital study

Cited by 4 publications

References 48 publications

Thermochemistry of the Reactions F+(3P, 1D) + PH3 in the Gas Phase

Thermochemistry of the Reactions F+(3P, 1D) + PH3 in the Gas Phase

A Theoretical Study of the Reaction between N+(3P) and Formaldehyde and Related Processes in the Gas Phase

Theoretical Survey of the Potential Energy Surfaces Associated with the N+(3P,D) + C2H4Reactions in the Gas Phase

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The reactions of Cl⁺(³P) and Cl⁺(¹D) with hydrogen sulphide. A G2 molecular orbital study

Thermochemistry of the Reactions F⁺(³P, ¹D) + PH₃ in the Gas Phase

Thermochemistry of the Reactions F⁺(³P, ¹D) + PH₃ in the Gas Phase

A Theoretical Study of the Reaction between N⁺(³P) and Formaldehyde and Related Processes in the Gas Phase

Theoretical Survey of the Potential Energy Surfaces Associated with the N⁺(³P,D) + C₂H₄Reactions in the Gas Phase