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Title: Theoretical study of the heats of formation of small silicon-containing compounds

Abstract

Heats of formation for nine small silicon-containing molecules were obtained from large basis set ab initio calculations using coupled cluster theory with a perturbative treatment of triple excitations. After adjusting the atomization energies for the finite basis set truncation error, core/valence correlation, scalar relativistic, higher order correlation, and atomic spin-orbit effects, the theoretical and experimental 0 K values of {Delta}H{sub f} values were in good agreement. Using 106.6 kcal/mol as the heat of formation of silicon, the authors obtain {Delta}H{sub f} values of SiH = 87.7 {+-} 0.4 vs 89.5 {+-} 0.7 (expt); SiH{sub 2}({sup 1}A{sub 1}) = 64.1 {+-} 0.4 vs 65.5 {+-} 0.7 (expt); SiH{sub 2}({sup 3}B{sub 1}{minus})= 85.4 {+-} 0.4 vs 86.5 {+-} 0.7 (expt); SiH{sub 3} = 47.3 {+-} 0.5 vs 47.7 {+-} 1.2 (expt); SiH{sub 4} = 8.7 {+-} 0.6 vs 9.5 {+-} 0.5 (expt); Si{sub 2} = 138.8 {+-} 0.4 vs 139.2 (expt); Si{sub 2}H{sub 6} = 19.7 {+-} 0.5 vs 20.9 {+-} 0.3 (expt); SiF = {minus}14.8 {+-} 0.4 vs {minus}5.2 {+-} 3 (expt); SiF{sub 2} = {minus}151.7 {+-} 0.5 vs {minus}140.3 {+-} 3 (expt); and SiF{sub 4} = {minus}384.5 {+-} 0.9 vs {minus}384.9 {+-} 0.2 (expt). Based on the present work, themore » authors suggest a number of revisions in the interpretation of the experimental data. Although a revision in {Delta}H{sub f}{degree}(Si) to 107.4 {+-} 0.6 kcal/mol at 0 K leads to improved agreement between theory and experiment for the SI{sub x}H{sub y} compounds, it worsens agreement for SiF{sub 4}. Given the remaining uncertainties in the theoretical approach, more definitive conclusions do not appear to be warranted.« less

Authors:
;
Publication Date:
Research Org.:
Pacific Northwest National Lab., Richland, WA (US)
Sponsoring Org.:
USDOE
OSTI Identifier:
20000060
DOE Contract Number:  
AC06-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 103; Journal Issue: 32; Other Information: PBD: 12 Aug 1999; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; SILANES; THERMODYNAMIC PROPERTIES; FORMATION HEAT; THEORETICAL DATA; SILICON FLUORIDES

Citation Formats

Feller, D., and Dixon, D.A. Theoretical study of the heats of formation of small silicon-containing compounds. United States: N. p., 1999. Web. doi:10.1021/jp990596g.
Feller, D., & Dixon, D.A. Theoretical study of the heats of formation of small silicon-containing compounds. United States. doi:10.1021/jp990596g.
Feller, D., and Dixon, D.A. Thu . "Theoretical study of the heats of formation of small silicon-containing compounds". United States. doi:10.1021/jp990596g.
@article{osti_20000060,
title = {Theoretical study of the heats of formation of small silicon-containing compounds},
author = {Feller, D. and Dixon, D.A.},
abstractNote = {Heats of formation for nine small silicon-containing molecules were obtained from large basis set ab initio calculations using coupled cluster theory with a perturbative treatment of triple excitations. After adjusting the atomization energies for the finite basis set truncation error, core/valence correlation, scalar relativistic, higher order correlation, and atomic spin-orbit effects, the theoretical and experimental 0 K values of {Delta}H{sub f} values were in good agreement. Using 106.6 kcal/mol as the heat of formation of silicon, the authors obtain {Delta}H{sub f} values of SiH = 87.7 {+-} 0.4 vs 89.5 {+-} 0.7 (expt); SiH{sub 2}({sup 1}A{sub 1}) = 64.1 {+-} 0.4 vs 65.5 {+-} 0.7 (expt); SiH{sub 2}({sup 3}B{sub 1}{minus})= 85.4 {+-} 0.4 vs 86.5 {+-} 0.7 (expt); SiH{sub 3} = 47.3 {+-} 0.5 vs 47.7 {+-} 1.2 (expt); SiH{sub 4} = 8.7 {+-} 0.6 vs 9.5 {+-} 0.5 (expt); Si{sub 2} = 138.8 {+-} 0.4 vs 139.2 (expt); Si{sub 2}H{sub 6} = 19.7 {+-} 0.5 vs 20.9 {+-} 0.3 (expt); SiF = {minus}14.8 {+-} 0.4 vs {minus}5.2 {+-} 3 (expt); SiF{sub 2} = {minus}151.7 {+-} 0.5 vs {minus}140.3 {+-} 3 (expt); and SiF{sub 4} = {minus}384.5 {+-} 0.9 vs {minus}384.9 {+-} 0.2 (expt). Based on the present work, the authors suggest a number of revisions in the interpretation of the experimental data. Although a revision in {Delta}H{sub f}{degree}(Si) to 107.4 {+-} 0.6 kcal/mol at 0 K leads to improved agreement between theory and experiment for the SI{sub x}H{sub y} compounds, it worsens agreement for SiF{sub 4}. Given the remaining uncertainties in the theoretical approach, more definitive conclusions do not appear to be warranted.},
doi = {10.1021/jp990596g},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 32,
volume = 103,
place = {United States},
year = {1999},
month = {8}
}