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Accurate Quantum‐Chemical Prediction of Enthalpies of Formation of Small Molecules in the Gas Phase
Author(s) -
Klopper Wim,
Noga Jozef
Publication year - 2003
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200390006
Subject(s) - coupled cluster , anharmonicity , basis set , wave function , chemistry , atomic orbital , gaussian , scalar (mathematics) , electronic correlation , atomic physics , full configuration interaction , molecule , physics , density functional theory , electron , computational chemistry , configuration interaction , quantum mechanics , geometry , mathematics
The coupled‐cluster approach, including single and double excitations and perturbative corrections for triple excitations, is capable of predicting molecular electronic energies and enthalpies of formation of small molecules in the gas phase with very high accuracy (specifically, with error bars less than 5 kJ mol −1 ), provided that the electronic wavefunction is dominated by the Hartree–Fock configuration. This capability is illustrated by calculations on molecules containing O–H and O–F bonds, namely OH, FO, H 2 O, HOF, and F 2 O. To achieve this very high accuracy, it is imperative to account for electron‐correlation effects in a quantitative manner, either by using explicitly correlated two‐particle basis functions (R12 functions) or by extrapolating to the limit of a complete basis. Besides taking into account harmonic zero‐point vibrational energies, it is also necessary to account for anharmonic corrections to the zero‐point vibrational energies, to include the core orbitals into the coupled‐cluster calculations, and to account for spin–orbit corrections and scalar relativistic effects. These additional corrections constitute small but significant contributions in the range of 1–4 kJ mol −1 to the enthalpies of formation of the aforementioned molecules. The highly accurate coupled‐cluster results, obtained by employing R12 functions and by including various corrections, are compared with standard Kohn–Sham density‐functional calculations as well as with the Gaussian‐2 and complete‐basis‐set model chemistries.