BENCHMARK CALCULATIONS WITH CORRELATED MOLECULAR WAVE FUNCTIONS. III: CONFIGURATION INTERACTION CALCULATIONS ON FIRST ROW HOMONUCLEAR DIATOMICS

Using correlation consistent basis sets from double through quintuple zeta quality, potential energy functions have been calculated for the electronic ground states of the first row homonuclear diatomic molecules B2, C2, N2, O2, and F2 using single and double excitation configuration interaction (HF+1+2, GVB+1+2, and CAS+1+2) wave functions. Spectroscopic constants have been calculated for each species and compared to experiment. The dependence of the calculated spectroscopic constants on systematic extensions of the one‐particle basis set are, in general, found to be very regular. By fitting the directly calculated values with a simple exponential function, accurate estimates of the complete basis set (CBS) limit for Ee, De, and re have been obtained for each level of theory. The estimated CBS limits are compared to the available experimental results, and the intrinsic errors associated with each theoretical method are discussed. In addition, the accuracy of the internally contracted CAS+1+2 method is co...

[1]  Stephen R. Langhoff,et al.  Theoretical study of the spectroscopy of B2 , 1991 .

[2]  Stephen R. Langhoff,et al.  Full CI benchmark calculations on N2, NO, and O2: A comparison of methods for describing multiple bonds , 1987 .

[3]  K. P. Lawley,et al.  Ab initio methods in quantum chemistry , 1987 .

[4]  John D. Watts,et al.  Coupled‐cluster calculations on the C2 molecule and the C+2 and C−2 molecular ions , 1992 .

[5]  Russell M. Pitzer,et al.  A progress report on the status of the COLUMBUS MRCI program system , 1988 .

[6]  Julia E. Rice,et al.  Theoretical characterization of tetrahedral N4 , 1991 .

[7]  David Feller,et al.  Application of systematic sequences of wave functions to the water dimer , 1992 .

[8]  Peter J. Knowles,et al.  A new determinant-based full configuration interaction method , 1984 .

[9]  C. Bauschlicher,et al.  Accurate ab initio calculations for the ground states of N2, O2 and F2 , 1987 .

[10]  Peter R. Taylor,et al.  Accurate quantum chemical calculations , 2007 .

[11]  R. Ahlrichs,et al.  The impact of higher polarization basis functions on molecular AB initio results II. The ground states of CO, N2, O2, and F2 , 1985 .

[12]  J. L. Dunham.  The Energy Levels of a Rotating Vibrator , 1932 .

[13]  R. Ahlrichs,et al.  The impact of higher polarization basis functions on molecular ab initio results. I. The ground state of F2 , 1985 .

[14]  T. Dunning,et al.  Theoretical estimate of the enthalpy of formation of sulfhydryl radical (HSO) and HSO-SOH isomerization energy , 1993 .

[15]  R. Raffenetti,et al.  General contraction of Gaussian atomic orbitals: Core, valence, polarization, and diffuse basis sets; Molecular integral evaluation , 1973 .

[16]  Klaus Ruedenberg,et al.  MCSCF optimization through combined use of natural orbitals and the brillouin–levy–berthier theorem , 1979 .

[17]  G. Herzberg.  Molecular Spectra and Molecular Structure IV. Constants of Diatomic Molecules , 1939 .

[18]  H. Schaefer,et al.  Natural orbitals from single and double excitation configuration interaction wave functions: their use in second‐order configuration interaction and wave functions incorporating limited triple and quadruple excitations , 1992 .

[19]  Jan M. L. Martin.  On the performance of large Gaussian basis sets for the computation of total atomization energies , 1992 .

[20]  J. D. Bene.  Hydrogen bonding: Methodology and applications to complexes of HF and HCl with HCN and CH3CN , 1992 .

[21]  Isaiah Shavitt,et al.  Stabilities of hydrocarbons and carbocations. 1. A comparison of augmented 6-31G, 6-311G, and correlation consistent basis sets , 1992 .

[22]  Thom H. Dunning,et al.  Benchmark calculations with correlated molecular wave functions. I: Multireference configuration interaction calculations for the second row diatomic hydrides , 1993 .

[23]  Hans-Joachim Werner,et al.  The self‐consistent electron pairs method for multiconfiguration reference state functions , 1982 .

[24]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[25]  S. Langhoff,et al.  An initio calculations on C2, Si2, and SiC , 1987 .

[26]  A. D. McLean,et al.  Computed self‐consistent field and singles and doubles configuration interaction spectroscopic data and dissociation energies for the diatomics B2, C2, N2, O2, F2, CN, CP, CS, PN, SiC, SiN, SiO, SiP, and their ions , 1992 .

[27]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .

[28]  Rick A. Kendall,et al.  Benchmark calculations with correlated molecular wave functions. II. Configuration interaction calculations on first row diatomic hydrides , 1993 .

[29]  P. Knowles,et al.  An efficient internally contracted multiconfiguration–reference configuration interaction method , 1988 .

[30]  Hans-Joachim Werner,et al.  A comparison of variational and non-variational internally contracted multiconfiguration-reference configuration interaction calculations , 1990 .

[31]  D. Woon.  Accurate modeling of intermolecular forces: a systematic Møller-Plesset study of the argon dimer using correlation consistent basis sets , 1993 .

[32]  K. Jordan,et al.  An extended-valence MC SCF procedure: determination of the dissociation energies of C2, N2, O2, and F2 , 1987 .

[33]  Ernest R. Davidson,et al.  Configuration interaction calculations on the nitrogen molecule , 1974 .

[34]  Klaus Ruedenberg,et al.  Electronic rearrangements during chemical reactions. II. Planar dissociation of ethylene , 1979 .

[35]  P. Knowles,et al.  A second order multiconfiguration SCF procedure with optimum convergence , 1985 .

[36]  J. Bearden,et al.  Atomic energy levels , 1965 .

[37]  P. Knowles,et al.  Accurate multireference configuration interaction calculations of the potential energy function and the dissociation energy of N2 , 1991 .

[38]  P. Knowles,et al.  An efficient second-order MC SCF method for long configuration expansions , 1985 .

[39]  Peter J. Knowles,et al.  A determinant based full configuration interaction program , 1989 .

[40]  Per E. M. Siegbahn,et al.  Singlet and triplet energy surfaces of NiH2 , 1983 .

[41]  R. Bartlett,et al.  A coupled-cluster study of inversion symmetry breaking in the F+2 molecular ion , 1991 .

[42]  C. Bauschlicher,et al.  Theoretical study of the low-lying bound states of O2 , 1991 .

[43]  P. Knowles,et al.  An efficient method for the evaluation of coupling coefficients in configuration interaction calculations , 1988 .