Kinetic and thermochemical study of the silyl + hydrogen bromide .dblharw. silane + bromine atom and silyl + hydrogen iodide .dblharw. silane + iodine atom equilibria

Seetula, Jorma A.; Feng, Yong; Gutman, David; Seakins, Paul W.; Pilling, M. J.

doi:10.1021/j100157a030

Cited by 72 publications

(27 citation statements)

References 2 publications

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“…For comparison, the calculated reaction enthalpy of reaction SiH(CH 3 ) 3 with SiH 3 at the MC‐QCISD//MP2/6‐31+G(d,p) level as well as the available experimental reaction enthalpy is also listed in Table 3. The theoretical Δ H

_{298}^{0}

value 3.1 kcal/mol, for the reaction SiH(CH 3 ) 3 + SiH 3 is in good agreement with the corresponding experimental value 3.3 ± 1.7 kcal/mol, which was derived from the standard heats of formation [SiH(CH 3 ) 3 , −39.00 ± 0.96 kcal/mol28; SiH 4 , 8.21 kcal/mol29; SiH 3 , 47.97 ± 0.60 kcal/mol30; Si(CH 3 ) 3 , 4.07 ± 1.67 kcal/mol31]. In view of this good agreement obtained above, it is expected that the enthalpy of the title reactions calculated at the same level is reliable.…”

Section: Resultssupporting

confidence: 90%

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Theoretical study and rate constants calculation for the reactions of SiH₃radical with SiH₃CH₃and SiH₂(CH₃)₂

Zhang

Liu

et al. 2009

J Comput Chem

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The multiple-channel reactions SiH(3) + SiH(3)CH(3) --> products and SiH(3) + SiH(2)(CH(3))(2) --> products are investigated by direct dynamics method. The minimum energy path (MEP) is calculated at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD method. The rate constants for individual reaction channels are calculated by the improved canonical variational transition state theory (ICVT) with small-curvature tunneling (SCT) correction over the temperature range of 200-2400 K. The theoretical three-parameter expression k(1)(T) = 2.39 x 10(-23)T(4.01)exp(-2768.72/T) and k(2)(T) = 9.67 x 10(-27)T(4.92)exp(-2165.15/T) (in unit of cm(3) molecule(-1) s(-1)) are given. Our calculations indicate that hydrogen abstraction channel from SiH group is the major channel because of the smaller barrier height among eight channels considered.

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_{298}^{0}

Section: Resultssupporting

confidence: 90%

“… Experimental value derived from the standard heats of formation (in kcal/mol): SiH(CH 3 ) 3 , –39.00 ± 0.96 kcal/mol28; SiH 4 , 8.21 kcal/mol29; SiH 3 , 47.97 ± 0.60 kcal/mol30; Si(CH 3 ) 3 , 4.07 ± 1.67 kcal/mol 31…”

Section: Resultsmentioning

confidence: 99%

Theoretical study and rate constants calculation for the reactions of SiH₃radical with SiH₃CH₃and SiH₂(CH₃)₂

Zhang

Liu

et al. 2009

J Comput Chem

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“…Seetula et al 72 have recently determined the H3Si-H bond dissociation energy and associated heat of formation of the SiH 3 radical to relatively high precision. These values, converted from 298 to 0 K via data in Table I, (b) (49.8 ± 1.6 kcal mol-I).…”

Section: Eepl/ 2 ) -E Av (2p) =Heepl/ 2 ) -Eep 3/2 )]mentioning

confidence: 99%

Thermochemistry of CHn, SiHn (n=0–4), and the cations SiH+, SiH2+, and SiH3+: A converged quantum mechanical approach

Grev

Schaefer

1992

The Journal of Chemical Physics

104

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Articles you may be interested inEight-dimensional quantum reaction rate calculations for the H+CH4 and H2+CH3 reactions on recent potential energy surfaces Communication: A six-dimensional state-to-state quantum dynamics study of the H + CH4 → H2 + CH3 reaction (J = 0) J. Chem. Phys. 138, 011101 (2013); 10.1063/1.4774116 Accurate ab initio potential energy surface, thermochemistry, and dynamics of the Cl(2P, 2P3/2) + CH4 → HCl + CH3 and H + CH3Cl reactions J. Chem. Phys. 136, 044307 (2012); 10.1063/1.3679014Rate constants for the reactions of metastable NO+ (a 3Σ+) ions with SO2, CO2, CH4, N2, Ar, H2, D2, and O2 at relative kinetic energies 0.04-2.5 eVWe have determined 0 K heats of formation of as well as the cations SiH+, SiHi, and SiHt using large atomic natural orbital basis sets and coupled cluster methods including all single, double, and (perturbatively) triple excitations [CCSD(T)]. Core-correlation effects on the bond dissociation energies have been explicitly evaluated. For the intermediate hydrides CHn and SiH n (n = 1-3), heats of formation are determine.d from theoretical bond dissociation energies in two ways: using experimental heats of formation of the Hand C (or Si) atoms; and using experimental heats of formation of the H atom and the parent hydrides CH 4 (or SiH 4 ). In principle, this procedure allows us to place rigorous upper and lower bounds on the heats of formation of the intermediate hydrides. Because our theoretically predicted atomization energies are already of high quality, estimation of remaining deficiencies in the one-particle basis sets can be obtained from extrapolation of observed trends in atomization energies upon basis set expansion. These extrapolated results are in outstanding agreement with experimental values where they are known to high accuracy. For the SiHn compounds, a serious problem occurs: our predicted atomization energy of SiH 4 is larger than that obtained from experimental heats of formation for the silicon atom and silane. Thus either relativistic effects on the atomization energy of SiH 4 are large, or the experimental heats of formation of Si and SiH 4 are incompatible. Excepting the atomization energy of SiH 4 , and thus the heats of formation of Si and SiH 4 , none of our other SiH n thermochemical predictions (properly interpreted) are clearly incompatible with experiment. Furthermore, our theoretical predictions are again in outstanding agreement with experimental determinations that are most certain.De' ofCH n and SiHn (n= 1-4) as well as the cations SiH+, SiRt, and SiRt, using CCSD and CCSD(T) energies, in conjunction with large ANO basis sets. Theoretically determined De's, corrected for the effects of core correlation, are converted to heats of formation for the CHn and SiHn species in two ways: using the heat of formation of the atoms; and using the heat of formation of the parent hydrides CH 4 and SiR 4 . We show that if (1) relativistic effects are unimportant and (2) the individual De's converge to the exact De's from below, and (3) the wave f...

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“…Doncaster and Walsh [20] have measured the reaction rates ratio: (15) where k 16 is the rate constant for the reaction (16) For reaction (16) the Arrhenius expression was obtained by Seetula et al [21]: (17) After substitution of this expression into eq. (15), we obtain In particular, k 3 (300 K) ca.…”

Section: Discussionmentioning

confidence: 99%

“…While most of these parameters are available from the literature, the dipole polarizabilities ␣ R for Si k H n Cl m radicals are unknown. By fitting the dipole polarizabilities for H 2 [29] all in units of Å 3 ), we obtain the empirical correlation: (21) Mean square error of this correlation is 0.12 Å 3 . The dipole polarizability for I 2 was not found, therefore it is calculated by the formula ␣ calc (I 2 ) ϭ (4⑀r 0 6 /3I I 2 )…”

Section: Discussionmentioning

confidence: 99%

Rate constants for the reactions of molecular iodine with Cl, SiCl3, and SiH3 at 298 K

Baklanov

Чесноков

Chichinin

1997

Int. J. Chem. Kinet.

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The angular and velocity distribution of the ICl product from reaction (1) at 4.5 kcal/mol collision energy has been obtained by Cross and Blais in a crossed-molecular-beam study [1]. It was concluded that the angular distribution is consistent with that arising from short range attractive forces and that the reaction time is less than one rotational period. Reactions (2,3) present some special interest because chloro-silanes are used in technological processes of microelectronics. EXPERIMENTALReactions (1 -3) were studied by pulsed laser photolysis followed by a time-resolved detection of inter- INTRODUCTIONIn the present article we report the results of kinetics studies of reaction (1 -3) at room temperature:To our knowledge the rate constants for these reactions are not available from the literature. Kinetics and Combustion, 630090 Novosibirsk, Russia Received 26 January 1996; accepted 22 May 1996 ABSTRACT: Rate constants k 1 , k 2 , and k 3 have been measured at 298 K by means of a laser photolysis-laser magnetic resonance technique and (or) by a laser photolysis-infrared chemiluminescence detection technique (LMR and IRCL, respectively).

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Kinetic and thermochemical study of the silyl + hydrogen bromide .dblharw. silane + bromine atom and silyl + hydrogen iodide .dblharw. silane + iodine atom equilibria

Cited by 72 publications

References 2 publications

Theoretical study and rate constants calculation for the reactions of SiH₃radical with SiH₃CH₃and SiH₂(CH₃)₂

Theoretical study and rate constants calculation for the reactions of SiH₃radical with SiH₃CH₃and SiH₂(CH₃)₂

Thermochemistry of CHn, SiHn (n=0–4), and the cations SiH+, SiH2+, and SiH3+: A converged quantum mechanical approach

Rate constants for the reactions of molecular iodine with Cl, SiCl3, and SiH3 at 298 K

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Kinetic and thermochemical study of the silyl + hydrogen bromide .dblharw. silane + bromine atom and silyl + hydrogen iodide .dblharw. silane + iodine atom equilibria

Cited by 72 publications

References 2 publications

Theoretical study and rate constants calculation for the reactions of SiH3radical with SiH3CH3and SiH2(CH3)2

Theoretical study and rate constants calculation for the reactions of SiH3radical with SiH3CH3and SiH2(CH3)2

Thermochemistry of CHn, SiHn (n=0–4), and the cations SiH+, SiH2+, and SiH3+: A converged quantum mechanical approach

Rate constants for the reactions of molecular iodine with Cl, SiCl3, and SiH3 at 298 K

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Theoretical study and rate constants calculation for the reactions of SiH₃radical with SiH₃CH₃and SiH₂(CH₃)₂

Theoretical study and rate constants calculation for the reactions of SiH₃radical with SiH₃CH₃and SiH₂(CH₃)₂