Reactions of hydrogen and deuterium with silane and mono-, di-, and trimethylsilanes at room temperature

Cowfer, Joseph A.; Lynch, Kyle P.; Michael, J. V.

doi:10.1021/j100579a001

Cited by 38 publications

(32 citation statements)

References 5 publications

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“…(VIII) and (IX) requires a knowledge of the potentials of interaction. In this work the Lennard-Jones [12,6] potential has been adopted. The theory of the C,j coefficients is well-established, and values have been calculated with the approximations and combining rules of Kramer and Herschbach [28].…”

Section: Photometer Characterizationmentioning

confidence: 99%

Lyman‐α absorption photometry at high pressure and atom density kinetic results for H recombination

Lynch

Schwab

Michael

1976

Int J of Chemical Kinetics

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Atomic absorption and fluorescence spectrophotometry have been routinely used in kinetic investigations as probes of relative, rather than absolute, atom concentration. The calibration of a Lyman-a photometer for measurement of absolute hydrogen atom concentrations at levels [HI 1 5 1.8 X 1014 atoms/cmz and total pressure of 1.3 torr He is described. The photometer is characterized in terms of a two-level emission source and an absorption region in which only Doppler broadening of the transition is considered. The modifications due to pressure broadening by high pressures (500 5 P 6 1500 torr) in the absorption region are discussed in detail. Application of the technique is reported for the recombination of hydrogen atoms in the presence of six nonreactive heat bath gases. Experiments were performed in a static reaction cell at pressures of 500-1500 torr of heat bath gas, and hydrogen atoms were produced by HgThe technique is critically evaluated and the mechanistic implications of the hydrogen atom recombination results are examined. The measured room temperature recombination rate constants in H,, He, Ne, Ar, Kr, and N 1 are 8.3 f 1.2, 6.9 f 1.5, 5.9 =k 1.5, 8.0 f 0.8, 10.2 0.9, and 9.6 f 1.4, respectively, where the units are cm6/molecz . sec. photosensitization of HP.

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Section: Photometer Characterizationmentioning

confidence: 99%

Lyman‐α absorption photometry at high pressure and atom density kinetic results for H recombination

Lynch

Schwab

Michael

1976

Int J of Chemical Kinetics

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“…The rate coefficients have been measured with a wide variety of experimental methods, [5][6][7][8][9][10][11][12][13][14][15][16] but most work has been carried out at room temperature and only a few recent studies 10,11,16 reported the temperature dependence of the rate coefficient. For example, Arthur [10][11][12][13][14][15][16] However, a detailed state-resolved dynamical experimental investigation is still lacking for the title reaction.…”

Section: Introductionmentioning

confidence: 99%

Quasiclassical trajectory study of the SiH4+H→SiH3+H2 reaction on a global ab initio potential energy surface

Wang

Sun

Bian

2008

The Journal of Chemical Physics

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The SiH 4 +H→ SiH 3 +H 2 reaction has been investigated by the quasiclassical trajectory ͑QCT͒ method on a recent global ab initio potential energy surface ͓M. Wang et al., J. Chem. Phys. 124, 234311 ͑2006͔͒. The integral cross section as a function of collision energy and thermal rate coefficient for the temperature range of 300-1600 K have been obtained. At the collision energy of 9.41 kcal/ mol, product energy distributions and rovibrational populations are explored in detail, and H 2 rotational state distributions show a clear evidence of two reaction mechanisms. One is the conventional rebound mechanism and the other is the stripping mechanism similar to what has recently been found in the reaction of CD 4 +H ͓J. P. Camden et al., J. Am. Chem. Soc. 127, 11898 ͑2005͔͒. The computed rate coefficients with the zero-point energy correction are in good agreement with the available experimental data.

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“…Based on our knowledge at present it is improbable that silane and the methylsilanes activated by (2) decompose as suggested by [3]. Energetically much lower fragmentation pathways -silylene formation with concomitant loss of H 2 or CH 4 -are available and are not only realized in thermally activated systems [5,6,7] but also in chemically activated methylsilanes, produced by methylene insertion into the Si-H bond [8].…”

Section: Introductionmentioning

confidence: 99%

“…the primary step is inevitably followed by a very fast reaction (2) H + R 3 Si -> R 3 SiH(v) (2) not only under the condition of atoms in excess but also when the substrate is introduced in ten to hundred fold excess, due to the small rate constant for the dimerisation of the silylradicals compared to (2) [2]. The fate of the silane molecule generated in (2) and possessing approximately 375 kJ/mol excess energy has been investigated by Michael and coworkers [3]. In the case of trimethylsilane complete stabilization of the molecule activated by ( was found under flow conditions.…”

Section: Introductionmentioning

confidence: 99%

The Reaction of Hydrogen Atoms with Silyl Radicals; the Decomposition Pathways of Chemically Activated Silanes

Reimann

Potzinger

1983

Zeitschrift Für Naturforschung A

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The reactions of hydrogen atoms with silane and the methylated silanes -with the exception of tetramethylsilane -have been investigated in a fast flow reactor. Under our experimental conditions hydrogen abstraction from the Si-H bond is followed by combination of hydrogen atoms with the corresponding silyl radicals. The molecules formed in this way are activated by about 375 kJ/mol of vibrational energy. Two decomposition channels have been unequivocally identified, namely the elimination of molecular hydrogen and of methane, both with concomittant formation of the respective silylenes. In a subsequent step, silylene inserts into the substrate under formation of disilanes. With increasing degree of methylation. stabilization of the activated molecule competes with decomposition and dominates the kinetics in the case of trimethylsilane. With methyl-and dimethyl-silane, methyl radicals are observed as an additional reaction product. On the basis of RRKM calculations it is unlikely that they originate from a direct decomposition of the activated molecules.Absolute values for the room temperature rate constants of the abstraction reactions are given; for H + CH 3 SiH 3 , Arrhenius parameters have been determined.

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Reactions of hydrogen and deuterium with silane and mono-, di-, and trimethylsilanes at room temperature

Cited by 38 publications

References 5 publications

Lyman‐α absorption photometry at high pressure and atom density kinetic results for H recombination

Lyman‐α absorption photometry at high pressure and atom density kinetic results for H recombination

Quasiclassical trajectory study of the SiH4+H→SiH3+H2 reaction on a global ab initio potential energy surface

The Reaction of Hydrogen Atoms with Silyl Radicals; the Decomposition Pathways of Chemically Activated Silanes

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