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Collisions of O(1D) with HCl, Cl2, and COCl2: Total quenching, channel specific rate constants, and yields of Cl(2P1/2)
The method of time-resolved laser magnetic resonance was used to monitor Cl atoms produced by the reactions of O(1D)  with HCl, Cl2, and COCl2 at room temperature. For these reactions, the m...
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Electronic structure, ground state, and electron paramagnetic resonance spectroscopy of the matrix-isolated (eta6-C6H6)V and (eta6-C6D6)V half-sandwich transients
The electron paramagnetic resonance (EPR) spectra of the (6-C6H6)V, (6-C6D6)V transients and (6-C6H6)2V, (6-C6D6)2V molecules are obtained by codepositing C6H6 and C6D6 with vanadium atoms in an Ar ma...

Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation

J. Chem. Phys. 106, 1063 (1997); doi:10.1063/1.473182

Issue Date: 15 January 1997

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Larry A. Curtiss
Chemical Technology/Materials Science Divisions, Argonne National Laboratory, Argonne, Illinois 60439

Krishnan Raghavachari
Bell Laboratories, Lucent Technologies, Murray Hill, New Jersey 07974

Paul C. Redfern
Chemical Technology/Materials Science Divisions, Argonne National Laboratory, Argonne, Illinois 60439

John A. Pople
Department of Chemistry, Northwestern University, Evanston, Illinois 60208
A set of 148 molecules having well-established enthalpies of formation at 298 K is presented. This set, referred to as the G2 neutral test set, includes the 55 molecules whose atomization energies were used to test Gaussian-2 (G2) theory [J. Chem. Phys. 94, 7221 (1991)] and 93 new molecules. The G2 test set includes 29 radicals, 35 nonhydrogen systems, 22 hydrocarbons, 47 substituted hydrocarbons, and 15 inorganic hydrides. It is hoped that this new test set will provide a means for assessing and improving new theoretical models. From an assessment of G2 and density functional theories (DFT) on this test set it is found that G2 theory is the most reliable method both in terms of average absolute deviation (1.58 kcal/mol) and maximum deviation (8.2 kcal/mol). The largest deviations between experiment and G2 theory occur for molecules having multiple halogens. Inclusion of spin–orbit effects reduces the average absolute deviation to 1.47 kcal/mol and significantly improves the results for the chlorine substituted molecules, but little overall improvement is seen for the fluorine substituted molecules. Of the two modified versions of G2 theory examined in this study, G2(MP2,SVP) theory (average absolute deviation=1.93 kcal/mol) performs better than G2(MP2) theory (2.04 kcal/mol). The G2(MP2,SVP) theory is found to perform very well for hydrocarbons, radicals, and inorganic hydrides. Of the seven DFT methods investigated, the B3LYP method has the smallest average absolute deviation (3.11 kcal/mol). It also has a significantly larger distribution of error than the G2 methods with a maximum deviation of 20.1 kcal/mol. ©1997 American Institute of Physics.
History: Received 4 September 1996; accepted 4 October 1996
Permalink: http://link.aip.org/link/?JCPSA6/106/1063/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.60.Cx
    Physical Chemistry Chemical thermodynamics Enthalpies of combustion, reaction, and formation
  • 31.15.Ew
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Density-functional theory
  • YEAR: 1996-97

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (42)
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