PNO-CI and PNO-CEPA studies of electron correlation effects

Dipole moments and static dipole polarizabilities are calculated for neon and the molecules HF, H2O, NH3, CH4 and CO from SCF and correlated wavefunctions. The construction of appropriate gaussian-type basis sets is discussed and the convergence of the correlation contributions to the polarizability is analysed. The effect of vibrational averaging is also investigated. The polarizabilities as obtained from the coupled electron pair approximation (CEPA) with the most extended basis sets differ from experimental values by less than 1·5 per cent in all cases. The calculated polarizability anisotropies appear to be correct to about 5–15 per cent. The correlation contributions to the polarizabilities are found to vary from 3 to 12 per cent.

[1]  G. Arrighini,et al.  SCF MO's and Molecular Properties of H2O , 1970 .

[2]  Wilfried Meyer,et al.  PNO-CI and CEPA studies of electron correlation effects , 1974 .

[3]  R. P. Hurst,et al.  HYPERPOLARIZABILITIES FOR HARTREE--FOCK ATOMS. , 1972 .

[4]  N. Bridge,et al.  The polarization of laser light scattered by gases , 1964, Proceedings of the Royal Society of London. Series A, Mathematical and physical sciences.

[5]  Jon Thorhallsson,et al.  Physical properties of many-electron atomic systems evaluated from analytical Hartree-Fock functions , 1968 .

[6]  A. L. McClellan,et al.  Tables of experimental dipole moments , 1963 .

[7]  J. W. Moskowitz,et al.  Polarizabilities and Hyperpolarizabilities of Small Polyatomic Molecules in the Uncoupled Hartree–Fock Approximation , 1971 .

[8]  W. Lipscomb,et al.  Perturbed Hartree—Fock Calculations. III. Polarizability and Magnetic Properties of the HF Molecule , 1964 .

[9]  I. Epstein.  Optical Properties of Atoms and Diatomic Molecules Calculated by a Time‐Dependent Coupled Hartree–Fock Method , 1970 .

[10]  W. C. Ermler,et al.  Zero‐Point Vibrational Corrections to One‐Electron Properties of the Water Molecule in the Near‐Hartree—Fock Limit , 1971 .

[11]  A. D. Buckingham,et al.  The quadrupole moment of the carbon dioxide molecule , 1963, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[12]  Pavel Rosmus,et al.  PNO–CI and CEPA studies of electron correlation effects. III. Spectroscopic constants and dipole moment functions for the ground states of the first‐row and second‐row diatomic hydrides , 1975 .

[13]  P. W. Langhoff,et al.  Multipole Polarizabilities and Shielding Factors from Hartree-Fock Wave Functions , 1965 .

[14]  J. F. Harrison.  Electric‐Dipole Polarizability of H2O and NH3 , 1968 .

[15]  John C. Slater,et al.  The Van Der Waals Forces in Gases , 1931 .

[16]  Per E. M. Siegbahn,et al.  Polarization functions for first and second row atoms in Gaussian type MO-SCF calculations , 1970 .

[17]  H. D. Cohen.  Electric Dipole Polarizability of Atoms by the Hartree—Fock Method. III. The Isoelectronic 10‐Electron Series , 1966 .

[18]  J. Muenter.  Polarizability Anisotropy of Hydrogen Fluoride , 1972 .

[19]  A. C. Hurley,et al.  The electrostatic calculation of molecular energies - II. Approximate wave functions and the electrostatic method , 1954, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[20]  C. Roothaan,et al.  Electric Dipole Polarizability of Atoms by the Hartree—Fock Method. I. Theory for Closed‐Shell Systems , 1965 .

[21]  N. S. Ostlund,et al.  Self‐Consistent Perturbation Theory. I. Finite Perturbation Methods , 1968 .

[22]  Klaus Ruedenberg,et al.  Even-tempered atomic orbitals. III. Economic deployment of Gaussian primitives in expanding atomic SCF orbitals , 1973 .

[23]  A. D. McLean,et al.  Higher Polarizabilities of Linear Molecules , 1967 .

[24]  R. Saxon.  Neon polarizability and C (6) coefficient from oscillator strength distribution , 1973 .

[25]  S. Arai,et al.  Electric Dipole Polarizabilities and Dipole Shielding Factors of Neon, Magnesium and Argon Atoms from the Hartree-Fock Wave Functions , 1969 .

[26]  A. D. McLean,et al.  Computed Ground‐State Properties of FH and CH , 1967 .

[27]  M. Yoshimine,et al.  Atomic Dipole Polarizabilities from the Uncoupled Hartree-Fock Approximation , 1964 .

[28]  W. Donath.  Atomic Calculations. II. Polarizabilities and London Force Constants for F—, Ne, and Na+ , 1963 .

[29]  H. Seidel.  Zahlenwerte und Funktionen , 1965 .

[30]  N. C. Dutta,et al.  Brueckner-Goldstone Many-Body Theory for Dynamic Polarizabilities: Application to Ne , 1970 .

[31]  J. Pople,et al.  Correlation energies for AH n molecules and cations , 1975 .

[32]  M. Karplus,et al.  Electric Polarizability of Some Diatomic Molecules , 1963 .

[33]  R. Mcweeny.  Perturbation Theory for the Fock-Dirac Density Matrix , 1962 .

[34]  M. Doran.  The multipole long-range (Van der Waals) interaction coefficients for neon, argon, krypton and xenon , 1974 .

[35]  E. Davidson,et al.  A study of the ground state wave function of carbon monoxide , 1970 .

[36]  J. Muenter,et al.  Hyperfine Structure Constants of HF and DF , 1970 .

[37]  M. Karplus,et al.  Perturbed Hartree–Fock Theory. I. Diagrammatic Double‐Perturbation Analysis , 1969 .

[38]  C. W. Kern,et al.  Nuclear Corrections to Electronic Expectation Values: Zero‐Point Vibrational Effects in the Water Molecule , 1968 .

[39]  K. T. Chung,et al.  FULLY COUPLED HARTREE--FOCK CALCULATIONS OF THE REFRACTIVE INDEX, DYNAMIC POLARIZABILITY, AND VERDET COEFFICIENTS OF HELIUM, BERYLLIUM, AND NEON. , 1968 .

[40]  H. Lischka.  Ab initio calculations on intermolecular forces. III. Effect of electron correlation on the hydrogen bond in the hydrofluoric acid dimer , 1974 .

[41]  R. Nesbet.  Atomic Bethe-Goldstone Equations. III. Correlation Energies of Ground States of Be, B, C, N, O, F, and Ne , 1968 .

[42]  R. Moccia.  Perturbed SCF MO calculations. Electrical polarizability and magnetic susceptibility of HF, H2O, NH3 and CH4 , 1967 .

[43]  Wilfried Meyer,et al.  PNO–CI Studies of electron correlation effects. I. Configuration expansion by means of nonorthogonal orbitals, and application to the ground state and ionized states of methane , 1973 .

[44]  Ch. Schlier.  Magnetische Effekte in zweiatomigen 1Σ‐Molekülen , 1961 .

[45]  M. Maestro,et al.  SCF‐MO's and Molecular Properties of Methane , 1968 .

[46]  M. Maestro,et al.  Electric polarizability of polyatomic molecules , 1967 .

[47]  J. O'hare,et al.  Hyperpolarizabilities of Some Polar Diatomic Molecules , 1967 .