The molecular spectra and structure of the oxides of boron and aluminium

Nemukhin, Alexander V.; Serebrennikov, L. V.

doi:10.1070/rc1993v062n06abeh000031

Cited by 10 publications

(8 citation statements)

References 46 publications

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“…Most of the available quantum chemical studies on boron oxides are for clusters containing up to three boron atoms. [24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] For example, Drummond et al 39 investigated the molecular structure and stability of a larger set of B n O m compounds, with m ) 1-3 and n ) 1-7, using molecular dynamics techniques in conjunction with plane-wave periodic density functional theory (DFT). Both gas-phase and solid bulk structures were considered.…”

Section: Introductionmentioning

confidence: 99%

Thermochemistry and Electronic Structure of Small Boron and Boron Oxide Clusters and Their Anions

et al. 2009

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Thermochemical properties of a set of small boron (B(n)) and boron oxide (B(n)O(m)) clusters, with n = 1-4 and m = 0-3, their anions, and the B(4)(2-) dianion, were calculated by using coupled-cluster theory CCSD(T) calculations with the aug-cc-pVnZ (n = D, T, Q, 5) basis sets extrapolated to the complete basis set limit with additional corrections. Enthalpies of formation, bond dissociation energies, singlet-triplet or doublet-quartet separation gaps, adiabatic electron affinities (EA), and both vertical electron attachment and detachment energies were evaluated. The predicted heats of formation show agreement close to the error bars of the literature results for boron oxides with the largest error for OBO. Our calculated adiabatic EAs are in good agreement with recent experiments: B (calc, 0.26 eV; exptl, 0.28 eV), B(2) (1.95, 1.80), B(3) (2.88, 2.820 +/- 0.020), B(4) (1.68, 1.60 +/- 0.10), BO (2.50, 2.51), BO(2) (4.48, 4.51), BOB (0.07), B(2)O(2) (0.37), B(3)O (2.05), B(3)O(2) (2.94, 2.94), B(4)O (2.58), and B(4)O(2) (3.14, 3.160 +/- 0.015). The BO bond is strong, so this moiety is maintained in most of the clusters. Thermochemical parameters of clusters are not linearly additive with respect to the number of B atoms. The EA tends to be larger in the dioxides. The growth mechanism of small boron oxides should be determined by a number of factors: (i) formation of BO bonds, (ii) when possible, formation of a cyclic B(3) or B(4), and (iii) combination of a boron cycle and a BO bond. When these factors compete, the strength of the BO bonds tends to compensate the destabilization arising from a loss of binding in the cyclic boron clusters, in such a way that a linear boron oxide prevails. When the B(2) moiety is present in these linear clusters, the oxide derivatives prefer a high spin state.

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Section: Introductionmentioning

confidence: 99%

Thermochemistry and Electronic Structure of Small Boron and Boron Oxide Clusters and Their Anions

et al. 2009

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“…Wang and co-workers used experimental photoelectron spectroscopy coupled with quantum chemical calculations to probe the electronic structures of small anions including B 3 O 2 − , B 4 O 2 − , B 4 O 3 − , and B 4 O 2 2− and their neutral counterparts. Most of the theoretical studies have focused on B n O m species with n as large as 5. – Recently, we predicted the enthalpies of formation and determined the electronic structures of a series of small B n O m compounds and their anions with n = 1−4 and m = 1−3 using high accuracy computational methods at the coupled-cluster theory CCSD(T) level with the correlation consistent aug-cc-pV n Z ( n = D, T, Q, 5) basis sets extrapolated to the complete basis set limits (CBS) with additional corrections . The calculated detachment energies are in good agreement with the available experimental data.…”

Section: Introductionmentioning

confidence: 99%

“…Most of the theoretical studies have focused on B n O m species with n as large as 5. [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] Recently, we predicted the enthalpies of formation and determined the electronic structures of a series of small B n O m compounds and their anions with n ) 1-4 and m ) 1-3 using high accuracy computational methods at the coupled-cluster theory CCSD(T) level with the correlation consistent aug-cc-pVnZ (n ) D, T, Q, 5) basis sets extrapolated to the complete basis set limits (CBS) with additional corrections. 23 The calculated detachment energies are in good agreement with the available experimental data.…”

Section: Introductionmentioning

confidence: 99%

Thermochemical Properties and Electronic Structure of Boron Oxides B_nO_m (n = 5−10, m = 1−2) and Their Anions

2010

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The molecular and electronic structures of a series of small boron monoxide and dioxide clusters B(n)O(m) (n = 5-10, m = 1, 2) plus their anions were predicted. The enthalpies of formation (DeltaH(f)'s), electron affinities (EAs), vertical detachment energies, and energies of different fragmentation processes are predicted using the G3B3 method. The G3B3 results were benchmarked with respect to more accurate CCSD(T)/CBS values for n = 1-4 with average deviations of +/-1.5 kcal/mol for DeltaH(f)'s and +/-0.03 eV for EAs. The results extend previous observations on the growth mechanism for boron oxide clusters: (i) The low spin electronic state is consistently favored. (ii) The most stable structure of a neutral boron monoxide B(n)O is obtained either by condensing O on a BB edge of a B(n) cycle, or by binding one BO group to a B(n-1) ring. The balance between both factors is dependent on the inherent stability of the boron cycles. (iii) A boron dioxide is formed by incorporating the second O atom into the corresponding monoxide to form BO bonds. (iv) A B(n)O(m)(-) anion is constructed with BO groups bound to the B(n-1) or B(n-2) rings (yielding the B(n-2)(BO)(2)(-) species). This becomes the preferred geometry for the larger boron dioxides, even in the neutral state. The boronyl group mainly behaves as an electron-withdrawing substituent reducing the binding energy and resonance energy of the oxides. (v) The boron oxides conserve some of the properties of the parent boron clusters such as the planarity and multiple aromaticity.

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“…Boron reactions have also been studied in rare gas matrixes in order to trap transient species and characterize them by FTIR spectroscopy. 10 For the B + O 2 reaction, the principal products were B 2 O 2 and B 2 O 3 . 11 Complexes of boron with carbon monoxide, 12 acetylene, 13 methane, 14 nitrogen, 15 carbon dioxide, 16 and hydrogen 17 have also been detected.…”

Section: Introductionmentioning

confidence: 99%

“…Rate constants for boron atom reactions with other small molecules, such as H 2 O, H 2 O 2 , alcohols, ethers, and halomethanes, have also been measured. Boron reactions have also been studied in rare gas matrixes in order to trap transient species and characterize them by FTIR spectroscopy . For the B + O 2 reaction, the principal products were B 2 O 2 and B 2 O 3 .…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Studies of the Reaction of Al Atoms with OCS and CS₂

1997

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The temperature (295−382 K) and pressure (5−50 Torr) dependences of the rate constants of the Al + OCS and Al + CS2 reactions have been studied by using time-resolved laser-induced fluorescence spectroscopy. The temperature dependence of the Al + OCS reaction is characterized by the rate expression = (4.2 ± 2.1) × 10-11 exp[5.3 ± 1.4 kJ mol-1/RT] cm3 molecule-1 s-1. The rate expression for the former reaction was found to be independent of total pressure up to 50 Torr. The pressure dependent rate expression for the reaction of Al + CS2 obeys = (1.2 ± 0.3) × 10-28 cm6 molecule-2 s-1. Ab initio correlated calculations have been performed to determine the relative stability of the Al−CS2 and Al−OCS collision complexes as well as the relative energetics of reactants and products.

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The molecular spectra and structure of the oxides of boron and aluminium

Cited by 10 publications

References 46 publications

Thermochemistry and Electronic Structure of Small Boron and Boron Oxide Clusters and Their Anions

Thermochemistry and Electronic Structure of Small Boron and Boron Oxide Clusters and Their Anions

Thermochemical Properties and Electronic Structure of Boron Oxides B_nO_m (n = 5−10, m = 1−2) and Their Anions

Experimental and Theoretical Studies of the Reaction of Al Atoms with OCS and CS₂

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The molecular spectra and structure of the oxides of boron and aluminium

Cited by 10 publications

References 46 publications

Thermochemistry and Electronic Structure of Small Boron and Boron Oxide Clusters and Their Anions

Thermochemistry and Electronic Structure of Small Boron and Boron Oxide Clusters and Their Anions

Thermochemical Properties and Electronic Structure of Boron Oxides BnOm (n = 5−10, m = 1−2) and Their Anions

Experimental and Theoretical Studies of the Reaction of Al Atoms with OCS and CS2

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Thermochemical Properties and Electronic Structure of Boron Oxides B_nO_m (n = 5−10, m = 1−2) and Their Anions

Experimental and Theoretical Studies of the Reaction of Al Atoms with OCS and CS₂