Thermochemistry of Molecules in the B−N−Cl−H System:  <i>Ab Initio </i>Predictions Using the BAC-MP4 Method

Allendorf, Mark D.; Melius, Carl F.

doi:10.1021/jp962905y

Cited by 67 publications

(49 citation statements)

References 56 publications

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“…Since it is not a pair of electrons but a single electron to be filled in one orbital of species of HBN (6), the B-N bond in it is thus weaker than that of BNH (5), which results in the B-N bond distance for HBN (6) being longer than that of BNH (5). The structure parameters are close to Allendorf and Melius's result [10,15].…”

Section: Stationary Pointssupporting

confidence: 85%

Triplet potential energy surface for BH₂N: A DFT study

Zhang

2005

Int J of Quantum Chemistry

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ABSTRACT:The triplet potential energy surfaces (PES) for the isomerization and dissociation reactions of BH 2 N isomers was investigated using the DFT/B3LYP method of theory. Thirteen BH 2 N isomer species and two dissociated products were identified, in which five isomerization reactions and four dissociation pathways were found. On the triplet PES, the nonplanar trans-iminoborane (1) can isomerize to the lowest triplet state of planar aminoboranylidene (3) and the triplet state planar borylnitrene (4) directly by two three-membered ring transition states (TS 1-3 and TS 1-4 ), respectively. The cis-trans isomerization of iminoborane (1 and 2) by transition state (TS 1-2 ), the internal conversion of 1 and that of 2 by two transition states (TS 1a-1b and TS 2a-2b ) are also considered in the triplet PES. On the other hand, the dissociation product of B-N-H (5) and H atom can be predicted by the dissociation reaction of nonplanar cisiminoborane (2) and a planar structure aminoboranylidene (3) with the transition state of TS 2-5 and TS [3][4][5] . At the same time, the dissociation product H-B-N (6) and H atom can be predicted by the dissociation reaction of nonplanar cis-iminoborane (2) and a planar structure borylnitrene (4) with the transition state of TS 2-6 and TS 4 -6 . By analysis of the whole potential energy surface, we can find the isomerization from planar the triplet state aminoboranylidene (3) to the triplet state planar borylnitrene (4) is not carried out in one step directly, but achieved in multistep reactions of

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Section: Stationary Pointssupporting

confidence: 85%

Triplet potential energy surface for BH₂N: A DFT study

Zhang

2005

Int J of Quantum Chemistry

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“…Theoretical research found in the literature includes thermodynamic equilibrium calculations for mixtures involving B/F/N/H [1][2][3][4][5], B/Cl/N/H [4,5], and B/N/H [4], as well as limited kinetics studies of the reactions between BCl 3 and NH 3 [6,7]. P. R. P. Barreto developed a kinetic and surface mechanism to explain the growth of boron nitride [8 -11] (private communication, 2000); this mechanism is constantly upgrading, including new reaction and new species.…”

Section: Introduction Tmentioning

confidence: 99%

Thermochemistry of molecules in the B/F/H/N system

Barreto

Albernaz

Gargano

2005

Int J of Quantum Chemistry

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ABSTRACT:A self-consistent set of thermochemical data for 88 chemical species in the B/F/H/N system is obtained from ab initio electronic structure calculation. Calculations were performed for both stable and radical species. The quantities calculated include the atomization energy (¥ D 0 ), heat of formation (⌬H f ) at 0 K and 298.15 K, and bond dissociation energies (BDE) for all species. Good agreement is found between the calculation data and experimental or theoretical reference data for the quantities analyzed in this work for several species containing B, F, H, and N atoms. We also present a compilation of experimental and theoretical atomization energies (16 experimental ϫ 26 theoretical data), heat of formation at 0 K (25 experimental ϫ 26 theoretical data), heat of formation at 298 K (29 experimental ϫ 36 theoretical data), and bond dissociation energy for several species. Polynomial fits of the predicted thermodynamic data (heat capacity, entropy, and enthalpy) over the 200 -6000 K temperature range are also included, for the 88 species. The species analyzed in this study are important in a kinetic mechanism for growth boron nitride films in a Chemical Vapour Deposition (CVD) reactor. It is generally difficult to optimize conditions in a CVD reactor because films properties depend on complex interactions involving heat and mass transport, chemical kinetics, and thermochemistry. Developing a reliable set of thermodynamic data is a necessary first step for system optimization, since it provides important constraints on the possible reaction mechanism. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem 103: 659 -684, 2005

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“…13 Dissociation of the first Al-CH 3 bond in trimethylaluminum is more than 20 kcal mol -1 weaker than the same bond in trimethylborane. Dissociation energies for bonds between boron and chlorine, 21 however, are very similar to those between aluminum and chlorine. Data for boron hydroxides are sparse, but heats of formation reported by Gurvich et al 2 indicate that the analogous aluminum bonds are weaker as well.…”

Section: Amentioning

confidence: 89%

“…In the Supporting Information (Tables S7 -S11), we also provide raw electronic energies at the G2 level, atomic coordinates, vibrational frequencies, moments of inertia, and polynomial fits of the thermodynamic data suitable for use with the CHEMKIN software. 17 As has been typical in previous publications involving the BAC-MP4 series, 15,16,[18][19][20][21][22][23][24][25] we focus our discussion on the predicted thermochemical parameters, rather than on the ab initio calucations themselves. .…”

Section: Amentioning

confidence: 99%

BAC-G2 Predictions of Thermochemistry for Gas-Phase Aluminum Compounds

Allendorf¹

2001

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A self-consistent set of thermochemical data for 55 molecules in the Al-H-C-O-F-Cl system are obtained from ab initio quantum-chemistry calculations using the BAC-G2 method. Calculations were performed for both stable and radical species. Good agreement is found between the calculations and experimental heats of formation in most cases where data are available for comparison. Electronic energies, molecular geometries, moments of inertia, and vibrational frequencies are provided in the Supporting Information, as are polynomial fits of the thermodynamic data (heat of formation, entropy, and heat capacity) over the 300-3000 K temperature range. (This page intentionally left blank)5

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Thermochemistry of Molecules in the B−N−Cl−H System: Ab Initio Predictions Using the BAC-MP4 Method

Cited by 67 publications

References 56 publications

Triplet potential energy surface for BH₂N: A DFT study

Triplet potential energy surface for BH₂N: A DFT study

Thermochemistry of molecules in the B/F/H/N system

BAC-G2 Predictions of Thermochemistry for Gas-Phase Aluminum Compounds

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Thermochemistry of Molecules in the B−N−Cl−H System: Ab Initio Predictions Using the BAC-MP4 Method

Cited by 67 publications

References 56 publications

Triplet potential energy surface for BH2N: A DFT study

Triplet potential energy surface for BH2N: A DFT study

Thermochemistry of molecules in the B/F/H/N system

BAC-G2 Predictions of Thermochemistry for Gas-Phase Aluminum Compounds

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Triplet potential energy surface for BH₂N: A DFT study

Triplet potential energy surface for BH₂N: A DFT study