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Ab Initio Thermochemistry Beyond Chemical Accuracy for First-and Second-Row Compounds

  • Jan M. L. Martin
Part of the NATO Science Series book series (ASIC, volume 535)

Abstract

By judicious use of extrapolations to the 1-particle basis set limit and n-particle calibration techniques, total atomization energies of molecules with up to four heavy atoms can be obtained with calibration accuracy (1 kJ/mol or better, on average) without any empirical correction. For the SCF energy a 3-point geometric extrapolation is the method of choice. For the MP2 correlation energy, a 2-point A+B/(l+1/2)3 extrapolation is recommended, while for CCSD and CCSD(T) correlation energies we prefer the 3-point A + B/(l + l/2) C formula. Addition of high-exponent ‘inner polarization functions’ to second-row atoms is essential for reliable results. For the highest accuracy, accounts are required of inner-shell correlation, atomic spin-orbit splitting, anharmonicity in the zero-point energy, and scalar relativistic effects.

Keywords

Correlation Energy Triple Excitation Core Correlation Atomic Natural Orbital Valence Correlation 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© Springer Science+Business Media Dordrecht 1999

Authors and Affiliations

  • Jan M. L. Martin
    • 1
  1. 1.Department of Organic ChemistryWeizmann Institute of ScienceRehovotIsrael

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