Theoretical investigation on the acceptor role of MOs in three and four-membered ring thio compounds and their open chain analogues. Comparison of ground state, lowest energy triplet state and anion properties

Dézarnaud-Dandine, Christine; Sevin, A.

doi:10.1016/0166-1280(94)04109-6

Cited by 9 publications

(3 citation statements)

References 32 publications

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“…More recently, Kirchner et al (10) observed the Fourier transform microwave spectrum of ethylene sulfide for 32 S and 33 S isotopic species. Molecules with three membered rings, like ethylene sulfide, have been the subject of various calculations (10,11) in order to study ring strain.…”

Section: Note the R 0 Structure Of Ethylene Sulfidementioning

confidence: 99%

The r0 Structure of Ethylene Sulfide

Hirao

Ohteki

Tanimoto

2001

Journal of Molecular Spectroscopy

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Section: Note the R 0 Structure Of Ethylene Sulfidementioning

confidence: 99%

The r0 Structure of Ethylene Sulfide

Hirao

Ohteki

Tanimoto

2001

Journal of Molecular Spectroscopy

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“…It was reported previously [8,20] and attributed to the (CH 3 ) 2 S − ground state anion. Ab initio SCF-CI computations [24] at the MP4 level give an optimized 2 B 2 ground anion state energy of 3.27 eV, with the extra electron trapped in a σ * (S-C) MO having a strong sulphur 3p contribution (antisymmetric valence, plus Rydberg character). In dimethyldisulphide and dimethyltrisulphide this resonance is shifted to lower energy by 0.5 and 1.0 eV, respectively, which cannot be related to a S-C bond length variation [25].…”

mentioning

confidence: 99%

resonances in electron transmission (ETS) and x-ray absorption (XAS) spectroscopies of dimethyl(poly)sulphides (, 2, 3)

Dézarnaud-Dandine

Bournel

Tronc

et al. 1998

J. Phys. B: At. Mol. Opt. Phys.

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σ * shape resonances involving S-C and S-S antibonding levels have been observed in low-energy electron transmission spectroscopy (ETS) and sulphur 1s excitation spectra (XAS) of dimethylsulphide (DMS), dimethyldisulphide (DMDS) and dimethyltrisulphide (DMTS). A correlation diagram is established for ionization energies (IEs) of valence occupied molecular orbitals, term values (TVs) of sulphur K-shell excited states and electron attachment energies (AEs) for temporary negative ion resonance states of these molecules showing a strong decrease of the HOMO-LUMO energy gap with the sulphur atom chain length.

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“…Their actual nature will not be discussed here. In a previous theoretical study, we have shown that the electron acceptor properties of a given thio compound to some extent depend on the actual CS bond length(s): long CS bonds are associated with low-energy σ* MOs, with a good propensity for accommodating an extra electron at low energy cost . When dealing with molecules 1 − 4 , no important bond length variation is observed and, accordingly, no clear-cut trend is observed in the vertical energies of the lowest energy anion state, calculated by the VP method.…”

Section: Discussion Of Resultsmentioning

confidence: 92%

Theoretical Study of the Formation of Three-Electron Bonds in Some F-Substituted Thiol and Sulfide Anions

Dézarnaud-Dandine

Sevin

1996

J. Am. Chem. Soc.

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The possibility of formation of stable unsymmetrical three-electron (3e) bonds of the type {RS‚‚(-)‚‚R′} was theoretically studied by ab initio SCF-CI quantum calculations. It was predicted, on the basis of a classical resonance scheme, that a 3e bond was the most likely to be observed when both constituting fragments RS and R′ had the same electron affinity (EA). In this context the CH 3-n F n SH and CH 3-n F n SCH 3-n F n (n ) 0, 3) molecules were tested. The results support the prediction for the CF 3 /SHand CF 3 /SCH 3 -anions. By comparing results from different types of basis sets, for describing the valence part of the reaction coordinate or providing the system with the possibility of electron attachment (or detachment) via a very diffuse available space, we were able to propose a qualitative model which accounts for the general features of these processes, in each type of molecule. Semiquantitative data are offered for further experimental testing of our findings with molecules such as CH n X 3-n SH and CH n X 3-n SCH 3 (X ) F, Cl, Br; n ) 0,1).

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Theoretical investigation on the acceptor role of MOs in three and four-membered ring thio compounds and their open chain analogues. Comparison of ground state, lowest energy triplet state and anion properties

Cited by 9 publications

References 32 publications

The r0 Structure of Ethylene Sulfide

The r0 Structure of Ethylene Sulfide

resonances in electron transmission (ETS) and x-ray absorption (XAS) spectroscopies of dimethyl(poly)sulphides (, 2, 3)

Theoretical Study of the Formation of Three-Electron Bonds in Some F-Substituted Thiol and Sulfide Anions

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