Transferability of electron pairs between H2O and H2O2

The transferability of strongly orthogonal geminals between H2O and H2O2 is investigated. Wavefunctions for H2O are constructed from the appropriate geminals in H2O2. Likewise, except for optimization of the oxygen‐oxygen bond geminal (ΛOO), wavefunctions for H2O2 are constructed from the appropriate geminals in H2O. The results are encouraging. In all cases, the energies of the wavefunctions constructed from the transferred geminals are actually lower than the energies of the optimum MO wavefunctions and are close to the energies of the optimum geminal wavefunctions. The optimum geminals of H2O are compared with those of H2O2. The corresponding geminals are found to be almost identical. Some factors which influence the success of geminal transferability are examined. In particular, a view of geminal localization is presented, and shielding and inductive effects are discussed. Owing to substantial shielding of the secondary oxygen nucleus in H2O2, the effective fields seen by the OH geminals turn out to b...

[1]  M. Gordon,et al.  Localized Charge Distributions. III. Transferability and Trends of Carbon-Hydrogen Moments and Energies in Acyclic Hydrocarbons , 1972 .

[2]  D. Peters.  Localized molecular orbitals in methane and ethane and the transferability of the chemical bond between these molecules , 1972 .

[3]  B. Nelander.  On the Quantum Mechanical Basis for Bond Energy Schemes , 1971 .

[4]  W. Niessen.  A theory of molecules in molecules , 1971 .

[5]  H. Shull,et al.  The overlap of two independently determined geminal representations for the OH bond , 1971 .

[6]  E. Switkes,et al.  Localized Bonds in SCF Wavefunctions for Polyatomic Molecules. III C-H and C-C Bonds , 1970 .

[7]  W. J. Stevens,et al.  Transferability of Strongly Orthogonal Geminals between H2O and H2O2 , 1970 .

[8]  K. Ruedenberg,et al.  Electron Correlation and Separated Pair Approximation in Diatomic Molecules. III. Imidogen , 1970 .

[9]  R. Stevens,et al.  Geometry Optimization in the Computation of Barriers to Internal Rotation , 1970 .

[10]  S. Rothenberg.  Localized Orbitals for Polyatomic Molecules. I. The Transferability of the C–H Bond in Saturated Molecules , 1969 .

[11]  J. D. Petke,et al.  Ab Initio Studies of Orbital Hybridization in Polyatomic Molecules , 1969 .

[12]  M. Maestro,et al.  SCF MO's and Molecular Properties of Methyl Fluoride , 1969 .

[13]  Klaus Ruedenberg,et al.  Electron Correlation and Separated‐Pair Approximation. An Application to Berylliumlike Atomic Systems , 1968 .

[14]  Joseph G. Hoffman,et al.  Quantum Theory of Atoms, Molecules and the Solid State: A Tribute to John C. Slater , 1967 .

[15]  W. E. Palke,et al.  On the Internal Rotation Potential in H2O2 , 1967 .

[16]  M. Klessinger.  Triple Bond in N2 and CO , 1967 .

[17]  Klaus Ruedenberg,et al.  Localized Atomic and Molecular Orbitals. II , 1965 .

[18]  V. H. Smith,et al.  Lower Bounds for the Eigenvalues of First‐Order Density Matrices , 1965 .

[19]  R. H. Hunt,et al.  Internal-Rotation in Hydrogen Peroxide: The Far-Infrared Spectrum and the Determination of the Hindering Potential , 1965 .

[20]  R. C. Henderson,et al.  STUDY OF SEPARATED ELECTRON PAIRS IN THE LiH MOLECULE , 1965 .

[21]  C. E. Reid,et al.  On the Calculations of Real Wave Functions In Natural Form for Two-Electron Systems , 1963 .

[22]  Thomas L. Allen,et al.  The Chemical Bond in Molecular Quantum Mechanics , 1961 .

[23]  Tadashi Arai,et al.  Theorem on Separability of Electron Pairs , 1960 .

[24]  R. Mcweeny,et al.  The density matrix in many-electron quantum mechanics I. Generalized product functions. Factorization and physical interpretation of the density matrices , 1959, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[25]  Thomas L. Allen,et al.  Bond Energies and the Interactions between Next‐Nearest Neighbors. I. Saturated Hydrocarbons, Diamond, Sulfanes, S8, and Organic Sulfur Compounds , 1959 .

[26]  H. Shull.  Natural Spin Orbital Analysis of Hydrogen Molecule Wave Functions , 1959 .

[27]  Robert G. Parr,et al.  Theory of Separated Electron Pairs , 1958 .

[28]  Harrison Shull,et al.  NATURAL ORBITALS IN THE QUANTUM THEORY OF TWO-ELECTRON SYSTEMS , 1956 .

[29]  John Edward Lennard-Jones,et al.  The molecular orbital theory of chemical valency XVI. A theory of paired-electrons in polyatomic molecules , 1953, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[30]  G. G. Hall.  The molecular orbital theory of chemical valency. XI. Bond energies, resonance energies and triplet state energies , 1952, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[31]  P. Löwdin.  On the Non‐Orthogonality Problem Connected with the Use of Atomic Wave Functions in the Theory of Molecules and Crystals , 1950 .

[32]  O. Sǐnanoğlu,et al.  Sigma molecular orbital theory , 1970 .

[33]  D. Silver.  Bilinear Orbital Expansion of Geminal‐Product Correlated Wavefunctions , 1970 .

[34]  W. H. Adams.  TRANSFERABILITY OF ATOMIC HARTREE--FOCK VALENCE-SHELL ORBITALS AND CHEMICAL PERIODICITY. , 1970 .

[35]  R. Mcweeny.  Methods Of Molecular Quantum Mechanics , 1969 .

[36]  Werner Kutzelnigg,et al.  Direct Determination of Natural Orbitals and Natural Expansion Coefficients of Many‐Electron Wavefunctions. I. Natural Orbitals in the Geminal Product Approximation , 1964 .

[37]  William F. Meggers,et al.  Quantum Theory of Atomic Structure , 1960 .