Gaussian‐1 theory: A general procedure for prediction of molecular energies

A general procedure is developed for the computation of the total energies of molecules at their equilibrium geometries. Ab initio molecular orbital theory is used to calculate electronic energies by a composite method, utilizing large basis sets (including diffuse‐sp, double‐d and f‐polarization functions) and treating electron correlation by Mo/ller–Plesset perturbation theory and by quadratic configuration interaction. The theory is also used to compute zero‐point vibrational energy corrections. Total atomization energies for a set of 31 molecules are found to agree with experimental thermochemical data to an accuracy greater than 2 kcal mol−1 in most cases. Similar agreement is achieved for ionization energies, electron and proton affinities. Residual errors are assessed for the total energies of neutral atoms.

[1]  Steven K. Pollack,et al.  Effect of electron correlation on theoretical equilibrium geometries , 1979 .

[2]  M. Plesset,et al.  Note on an Approximation Treatment for Many-Electron Systems , 1934 .

[3]  Martin Head-Gordon,et al.  Quadratic configuration interaction. A general technique for determining electron correlation energies , 1987 .

[4]  L. Curtiss,et al.  A theoretical study of the energies of BHn compounds , 1988 .

[5]  Krishnan Raghavachari,et al.  An augmented coupled cluster method and its application to the first‐row homonuclear diatomics , 1985 .

[6]  L. Radom,et al.  The evaluation of molecular electron affinities , 1986 .

[7]  J. Pople,et al.  Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions , 1980 .

[8]  L. Radom,et al.  Slow convergence of the møller-plesset perturbation series: the dissociation energy of hydrogen cyanide and the electron affinity of the cyano radical , 1987 .

[9]  Paul von Ragué Schleyer,et al.  Accurate theoretical estimates of the electron affinities of AHn molecules by isogyric comparisons. Proton affinities of AHn− anions , 1988 .

[10]  L. Curtiss,et al.  Theoretical thermochemistry. 3. A modified procedure for ionization energies of AH/sub n/ species , 1987 .

[11]  Michael J. Frisch,et al.  Theoretical thermochemistry. 1. Heats of formation of neutral AHn molecules (A = Li to Cl) , 1985 .

[12]  Michael J. Frisch,et al.  Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets , 1984 .

[13]  M. Yoshimine,et al.  Configuration-interaction study of atoms. I. Correlation energies of B, C, N, O, F, and Ne , 1974 .

[14]  P. C. Hariharan,et al.  The influence of polarization functions on molecular orbital hydrogenation energies , 1973 .

[15]  Peter J. Knowles,et al.  On the convergence of the Møller-Plesset perturbation series , 1985 .