Photochemistry of silicon compounds. III. Vacuum-ultraviolet photolysis of methylsilane

Obi, Kinichi; Clement, A.; Gunning, H. E.; Strausz, O. P.

doi:10.1021/ja01035a007

Cited by 37 publications

(9 citation statements)

References 7 publications

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“…Because low-energy shape resonances are almost always associated with virtual valence orbitals, insight into them can often be gained from a consideration of the number, type, and energies of RHF virtual orbitals computed in a minimal basis set, though the RHF orbital energies typically must be shifted downward by several eV or more to obtain reasonable agreement with resonance positions. In the present case, minimal-basis-set RHF calculations ͑obtained with GAMESS and its internal STO-6G basis͒ place the virtual valence orbitals at 12.2 eV (8a 1 , Si-C *), 12.7 eV (4e, Si-H *), 14 Fig. 1 suggests that any such resonances must be very weak and/or broad.…”

Section: Resultsmentioning

confidence: 54%

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Low-energy electron scattering by methylsilane

Bettega

Winstead

McKoy

2003

The Journal of Chemical Physics

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We report calculated elastic and inelastic cross sections for low-energy electron collisions with methylsilane, CH 3 SiH 3 , obtained using the Schwinger multichannel method. The elastic cross sections, obtained within the static-exchange approximation, are compared with elastic results for C 2 H 6 and Si 2 H 6 . Electron-impact excitation cross sections were computed for sixteen electronic states arising from excitation out of the two highest-lying valence orbitals. The dissociation of the lowest few states was examined through limited electronic-structure calculations, which indicated that the 2 1,3 A 1 states dissociate to CH 3 SiHϩH 2 while the 1 1,3 E states dissociate to CH 3 ϩSiH 3 .

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Section: Resultsmentioning

confidence: 54%

“…However, a few studies have been done of the ultraviolet photoabsorption spectrum [9][10][11] and photodissociation chemistry. [13][14][15] To our knowledge, no electron cross sections, experimental or theoretical, are yet available for CH 3 SiH 3 ͑a preliminary account of our elastic results appears elsewhere 12 …”

Section: Introductionmentioning

confidence: 99%

Low-energy electron scattering by methylsilane

Bettega

Winstead

McKoy

2003

The Journal of Chemical Physics

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“…The generation of silenes at lower temperatures has been accomplished photolytically (6,33,(78)(79)(80)(81)(82)(83)(86)(87)(88)(89)(90)(91)(92)(93)(94)(95)(96)(97)(98) Koob and co-workers (80) recently reported the vacuum photolysis of 1,1-dimethyl-l-silacyclobutane ^ (R = Me) (Scheme 5)-Evidence for 2-methyl-2-silapropene was also reported as formation of the methanol adduct, methyltrimethylsilylether ^ (R = Me). In the absence of traps, only a very low yield of 1,3-disilacyclobutane, the dimer normally found in thermal reactions, is observed.…”

Section: Methods Of Silene Generationmentioning

confidence: 99%

Evidence for the generation and trapping of a silabenzene

Barton¹,

Banasiak²

1977

J. Am. Chem. Soc.

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“…Silaethene has been the subject of numerous experimental and theoretical studies. This molecule has been pyrolytically generated as a transient species from cyclic silicon derivatives, 15,16 produced by gas-phase photolysis of CH 3 SiH 3 , 17 and formed on a Pd(110) surface. 18 Silaethene easily reacts with many molecules, including silaethene itself.…”

Section: Introductionmentioning

confidence: 99%

A Tandem Mass Spectrometry Study of [C,H₂,X₂,Si]^+• Ions (X = H, D, Cl) and the Generation of Their Neutral Counterparts

Zagorevski

Aubry

Holmes

2000

Eur J Mass Spectrom (Chichester)

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Two [Si,C,H4]+• isomers, having similar stabilities and a relatively low barrier for their interconversion, have been separately generated in mass spectrometric experiments. CH2SiD2+• and D2-CH3SiH+• ions were produced from the same ionic precursor, namely ionized 1,1-dideutero-silacyclobutane (D2-I). Dissociation of the latter in the ion source resulted in the silaethene structure, whereas metastable dissociation gave rise to the dideuterated methylsilylene. Appearance energy measurements confirmed the formation of the two [Si,C,H2,D2]+• isomers, whose heats of formation were estimated to be 1017 and 1038 kJ mol−1 for CH3SiH+• and CH2SiH2+•, respectively. Both ion-source and metastable dissociations of ionized D2-I resulted in [Si,C,H3,D]+• and [Si,C,H4]+• ions possessing the methylsilylene structure. The collision-induced dissociation (CID) and neutralization–reionization (NR) mass spectra of CH2SiD2+• and D2-CH3SiH+• ions were distinctively different. The characteristic dissociation channel for the CH2SiD2 structure was the loss of CH2. Some dissociations of the ionized silaethene involved the formation of the methylsilylene intermediate. However, CH3SiH+• ions produced by this isomerization appeared to be unstable and did not survive neutralization–reionization. As a result, the CID mass spectra of CH2SiD2+• ions prior to neutralization and surviving the NR event were almost identical. Strong recovery signals in the NR mass spectra were consistent with the intrinsic stability of neutral silaethene and methylsilylene. The interconversion of these structures generated by neutralization of their positively-charged counterparts seems to be very unlikely. The CID, NR and NR/CID mass spectra of [Si,C,H2,Cl2]+• ions produced from various precursors and in different time frames were indistinguishable. They corresponded to the CH2SiCl2 connectivity of the atoms. The heat of formation for CH2SiCl2+• ions was estimated to be ∼732 kJ mol−1, based on appearance energy measurements. The presence of a strong recovery signal in the NR mass spectra was consistent with the formation of stable neutral 1,1-dichlorosilaethene in the gas phase on the microsecond time frame.

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Photochemistry of silicon compounds. III. Vacuum-ultraviolet photolysis of methylsilane

Cited by 37 publications

References 7 publications

Low-energy electron scattering by methylsilane

Low-energy electron scattering by methylsilane

Evidence for the generation and trapping of a silabenzene

A Tandem Mass Spectrometry Study of [C,H₂,X₂,Si]^+• Ions (X = H, D, Cl) and the Generation of Their Neutral Counterparts

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Photochemistry of silicon compounds. III. Vacuum-ultraviolet photolysis of methylsilane

Cited by 37 publications

References 7 publications

Low-energy electron scattering by methylsilane

Low-energy electron scattering by methylsilane

Evidence for the generation and trapping of a silabenzene

A Tandem Mass Spectrometry Study of [C,H2,X2,Si]+• Ions (X = H, D, Cl) and the Generation of Their Neutral Counterparts

Contact Info

Product

Resources

About

A Tandem Mass Spectrometry Study of [C,H₂,X₂,Si]^+• Ions (X = H, D, Cl) and the Generation of Their Neutral Counterparts