High-accuracy extrapolated ab initio thermochemistry. II. Minor improvements to the protocol and a vital simplification

Journal of Chemical Physics

Volumn 125, Issue 6, 2006, Pages

  Bomble, Yannick J ^a   Vázquez, Juana ^a   Kállay, Mihály ^b   Michauk, Christine ^c   Szalay, Péter G ^d   Császár, Attila G ^d   Gauss, Jürgen ^c   Stanton, John F ^a  

^a UNIVERSITY OF TEXAS AT AUSTIN   (United States)

^b BUDAPEST UNIVERSITY OF TECHNOLOGY AND ECONOMICS   (Hungary)

^c JOHANNES GUTENBERG UNIVERSITY   (Germany)

^d EÖTVÖS LORÁND UNIVERSITY   (Hungary)

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRON CORRELATION EFFECTS; FOCAL POINT APPROACHE; PENTUPLE EXCITATIONS; THERMOCHEMISTRY;

APPROXIMATION THEORY; COMPUTATION THEORY; ELECTRONS; ENTHALPY; EXTRAPOLATION;

PHYSICAL CHEMISTRY;

EID: 33747293832     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.2206789     Document Type: Article

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53. Λ), 1.12 (CCSDTQ-la), 0.32 (CCSDTQ-1b), 0.33 (CC4), and 0.69 (CCSDTQ-3). The conclusions concerning the performance of the approximate quadruples methods for heats of formation are similar to those for total energies; however, the difference between CCSDT(Q) and the more expensive methods is, ultimately, negligible (their use is consequently not justified). We note in passing that heats of formation were also computed using CCSDTQ as well as the aforementioned approximate methods with the cc-pVTZ basis set. However, no significant improvement has been achieved with respect to the experimental values, meaning that again the extra computational cost is not justified.
54. It is interesting to note that both the HF-SCF and CCSD(T) energies extrapolated with the 345 sequence are more negative than their 456 counterparts, although the former extrapolation tends to give smaller atomization energies in one case (HF-SCF) and larger in the other (CCSD(T)). The latter is rather obvious and sensible: correlation energy always tends to increase atomization energies, and a method that tends to overestimate correlation energies would tend to overestimate binding energies, if the extrapolation error were somewhat systematic. However, for the HF-SCF cases, the extrapolation error (as measured by the difference between 345- and 456-based extrapolations) is larger for free atoms than those in molecules in the cases we have investigated, which is in turn responsible for the underestimated atomization energies. Differences between 345- and 456-based extrapolations(in μH) are 269 (oxygen atom), 111 (nitrogen atom), 35 (carbon atom), 22 (hydrogen atom) [atoms], 239 (OH), 109 (CN), and 190 (CO). It is interesting, indeed a bit odd, that the error for the oxygen atom is the largest.
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