Ab initio study of the individual interaction energy components in the ground state of the mercury dimer

Relativistic and non-relativistic all-electron, ab initio methods are used to investigate the role of the individual energy components in the total interaction energy involved in the formation of the weakly bound ground state X1Sigma+g of the Hg2 molecule. The interaction energy is partitioned according to a hybrid approach into a supermolecular repulsive potential and the damped dispersion energy derived from perturbation theory. Both parts are then computed individually and their dependence on relativity and electron correlation investigated. From this analysis, hybrid potentials that comprise different physical interactions are constructed and the importance of specific features is evaluated by comparison of the appropriate hybrid potentials with each other and with the experimental curve. The most detailed model is based on a CASSCF supermolecular potential to which the damped intramonomer correlated dispersion energy series is added. In the relativistic case it yields a potential with quantitatively ...

[1]  S. Sinha,et al.  Calculations of ion-atom interactions relating to resonant charge-transfer collisions , 1975 .

[2]  B. A. Hess,et al.  The two-electron terms of the no-pair Hamiltonian , 1992 .

[3]  G. Scoles,et al.  Intermolecular forces via hybrid Hartree–Fock–SCF plus damped dispersion (HFD) energy calculations. An improved spherical model , 1982 .

[4]  M. Morse.  Clusters of transition-metal atoms , 1986 .

[5]  W. C. Ermler,et al.  Ab initio calculations of potential energy curves of Hg2 and TlHg , 1984 .

[6]  W. Stwalley,et al.  Long‐Range Interactions of Mercury Atoms , 1968 .

[7]  G. Chałasiński.  Perturbation calculations of the interaction energy between closed-shell Hartree-Fock atoms , 1983 .

[8]  M. Gleichmann,et al.  Relativistic all-electron ab initio calculations for the ground and excited states of the mercury atom , 1994 .

[9]  C. Herring,et al.  Asymptotic Exchange Coupling of Two Hydrogen Atoms , 1964 .

[10]  A. T. Amos,et al.  THEORY OF WEAK ATOMIC AND MOLECULAR INTERACTIONS. , 1967 .

[11]  Galli,et al.  Accurate pseudopotential local-density-approximation computations for neutral and ionized dimers of the IB and IIB groups. , 1990, Physical review. B, Condensed matter.

[12]  R. Gerber,et al.  Relativistic effects on interactions between heavy atoms: the HgHg potential , 1977 .

[13]  K. Rademann,et al.  Direct absorption spectra of jet‐cooled Hg2 , 1989 .

[14]  T. Zwier,et al.  Direct spectroscopic determination of the Hg2 bond length and an analysis of the 2540 Å band , 1988 .

[15]  P. Wormer,et al.  Anisotropy of long range interactions between linear molecules: H2-H2 and H2-He , 1979 .

[16]  Marvin Douglas,et al.  Quantum electrodynamical corrections to the fine structure of helium , 1971 .

[17]  P. W. Langhoff,et al.  Aspects of Time-Dependent Perturbation Theory , 1972 .

[18]  V. Kellö,et al.  Polarized basis sets for high-level-correlated calculations of molecular electric properties , 1995 .

[19]  K. D. Carlson,et al.  Interatomic Potential Energy Functions for Mercury, Cadmium, and Zinc from Vapor Viscosities , 1964 .

[20]  L. H. Lund,et al.  An Atomic Distribution Function , 1951 .

[21]  P. Pyykkö,et al.  The polarisability of Hg and the ground-state interaction potential of Hg2 , 1994 .

[22]  Tang,et al.  Accurate analytical He-He van der Waals potential based on perturbation theory. , 1995, Physical review letters.

[23]  C. Hättig,et al.  Correlated frequency-dependent polarizabilities and dispersion coefficients in the time-dependent second-order Møller-Plesset approximation , 1995 .

[24]  K. Balasubramanian,et al.  Spectroscopic constants and potential energy curves for Hg2 , 1992 .

[25]  R. Drullinger,et al.  A theoretical analysis of mercury molecules , 1977 .

[26]  B. Jeziorski,et al.  On the exchange polarization effects in the interaction of two helium atoms , 1976 .

[27]  Ballone,et al.  Pseudopotentials for non-local-density functionals. , 1991, Physical review. B, Condensed matter.

[28]  Patrick W. Fowler,et al.  Theoretical studies of van der Waals molecules and intermolecular forces , 1988 .

[29]  R. Mcweeny,et al.  Methods Of Molecular Quantum Mechanics , 1969 .

[30]  M. Jaszuński.  Coupled Hartree-Fock calculation of the induction energy , 1980 .

[31]  K. Tang,et al.  The damping function of the van der Waals attraction in the potential between rare gas atoms and metal surfaces , 1992 .

[32]  H. Wakeham,et al.  The Intermolecular Potential of Mercury , 1939 .

[33]  K. Szalewicz,et al.  Symmetry forcing and convergence properties of perturbation expansions for molecular interaction energies , 1978 .

[34]  J. Winans.  The Energy of Dissociation of Mercury Molecules , 1931 .

[35]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[36]  A. J. Sadlej,et al.  Medium-size polarized basis sets for high-level-correlated calculations of molecular electric properties , 1991 .

[37]  Robert Moszynski,et al.  Perturbation Theory Approach to Intermolecular Potential Energy Surfaces of van der Waals Complexes , 1994 .

[38]  H. Casimir,et al.  The Influence of Retardation on the London-van der Waals Forces , 1948 .

[39]  C. Herring.  CRITIQUE OF THE HEITLER-LONDON METHOD OF CALCULATING SPIN COUPLINGS AT LARGE DISTANCES , 1962 .

[40]  K. Tang,et al.  An improved simple model for the van der Waals potential based on universal damping functions for the dispersion coefficients , 1984 .

[41]  Hess,et al.  Relativistic electronic-structure calculations employing a two-component no-pair formalism with external-field projection operators. , 1986, Physical review. A, General physics.

[42]  P. Taylor,et al.  General contraction of Gaussian basis sets. II. Atomic natural orbitals and the calculation of atomic and molecular properties , 1989 .

[43]  P. Pyykkö,et al.  Finite-difference Dirac-Fock calculations of electric dipole polarisabilities for (ns)1 and (ns)2 atoms , 1981 .

[44]  R. Drullinger,et al.  Experimental studies of mercury molecules , 1977 .

[45]  J. Murrell,et al.  Intermolecular Forces in the Region of Small Orbital Overlap , 1967 .

[46]  E. Baerends,et al.  All-electron Dirac-Fock-Slater SCF calculations for electronic and geometric structures of the Hg₂ and Hg₃ molecules. , 1995 .

[47]  J. Sethian.  Turbulent combustion in open and closed vessels , 1984 .

[48]  R. Gordon,et al.  Theory for the Forces between Closed‐Shell Atoms and Molecules , 1972 .

[49]  K. Tang,et al.  A simple theoretical model for the van der Waals potential at intermediate distances. III. Anisotropic potentials of Ar–H2, Kr–H2, and Xe–H2 , 1978 .

[50]  E. A. Moelwyn-Hughes.  The Determination of Intermolecular Energy Constants from Common Physicochemical Properties of Liquids. , 1951 .

[51]  Bonding properties of mercury dimers in the pseudopotential local-density-approximation scheme. , 1989, Physical review. B, Condensed matter.