Energy-consistent pseudopotentials and correlation consistent basis sets for the 5d elements Hf-Pt.

New relativistic energy-consistent pseudopotentials have been generated for the 5d transition metals Hf-Pt. The adjustment was done in numerical two-component multiconfiguration Hartree-Fock calculations, using atomic valence-energy spectra from four-component multiconfiguration Dirac-Hartree-Fock calculations as reference data. The resulting two-component pseudopotentials replace the [Kr]4d(10)4f(14) cores of the 5d transition metals and can easily be split into a scalar-relativistic and a spin-orbit part. They reproduce the all-electron reference energy data with deviations of approximately 0.01 eV for configurational averages and approximately 0.05 eV for individual relativistic states. Full series of correlation consistent basis sets from double to quintuple-zeta have also been developed in this work for use with the new pseudopotentials. In addition, all-electron triple-zeta quality correlation consistent basis sets are also reported in order to provide calibration for the pseudopotential treatment. The accuracy of both the pseudopotentials and basis sets are assessed in extensive coupled cluster benchmark calculations of atomic ionization potentials, electron affinities, and selected excitation energies of all the 5d metal atoms, including the effects of spin-orbit coupling.

[1]  Mihály Kállay,et al.  Higher excitations in coupled-cluster theory , 2001 .

[2]  H. Tatewaki,et al.  Chemically reliable uncontracted Gaussian-type basis sets for atoms H to Lr , 2000 .

[3]  B. J. McKenzie,et al.  The transverse electron-electron interaction in atomic structure calculations , 1980 .

[4]  Hans-Joachim Werner,et al.  Coupled cluster theory for high spin, open shell reference wave functions , 1993 .

[5]  Cristina Puzzarini,et al.  Systematically convergent basis sets for transition metals. II. Pseudopotential-based correlation consistent basis sets for the group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements , 2005 .

[6]  M. Reiher,et al.  Correlated ab initio calculations of spectroscopic parameters of SnO within the framework of the higher-order generalized Douglas-Kroll transformation. , 2004, The Journal of chemical physics.

[7]  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.

[8]  T. Tsuchiya,et al.  Accurate relativistic Gaussian basis sets for H through Lr determined by atomic self-consistent field calculations with the third-order Douglas–Kroll approximation , 2001 .

[9]  Trygve Helgaker,et al.  Basis-set convergence in correlated calculations on Ne, N2, and H2O , 1998 .

[10]  B. Shepler,et al.  Ab initio thermochemistry involving heavy atoms: an investigation of the reactions Hg + IX (X = I, Br, Cl, O). , 2005, The journal of physical chemistry. A.

[11]  M. Head‐Gordon,et al.  A fifth-order perturbation comparison of electron correlation theories , 1989 .

[12]  Roland Lindh,et al.  New relativistic ANO basis sets for transition metal atoms. , 2005, The journal of physical chemistry. A.

[13]  K. Dyall.  Relativistic double-zeta, triple-zeta, and quadruple-zeta basis sets for the 5d elements Hf–Hg , 2004 .

[14]  W. C. Martin,et al.  Handbook of Basic Atomic Spectroscopic Data , 2005 .

[15]  Gustavo E. Scuseria,et al.  The open-shell restricted Hartree—Fock singles and doubles coupled-cluster method including triple excitations CCSD (T): application to C+3 , 1991 .

[16]  Jürgen Gauss,et al.  Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients , 1993 .

[17]  Markus Reiher,et al.  Exact decoupling of the Dirac Hamiltonian. I. General theory. , 2004, The Journal of chemical physics.

[18]  P. Knowles,et al.  Erratum: “Coupled cluster theory for high spin, open shell reference wave functions” [ J. Chem. Phys. 99, 5219 (1993)] , 2000 .

[19]  G. A. Petersson,et al.  On the optimization of Gaussian basis sets , 2003 .

[20]  E. Miyoshi,et al.  Relativistic correlating basis sets for the sixth-period d-block atoms from Lu to Hg. , 2004, The Journal of chemical physics.

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

[22]  H. Stoll,et al.  Energy-consistent pseudopotentials for the 5d elements--benchmark calculations for oxides, nitrides, and Pt(2). , 2009, Journal of Physical Chemistry A.

[23]  Russell M. Pitzer,et al.  Spin-Orbit Configuration Interaction Using the Graphical Unitary Group Approach and Relativistic Core Potential and Spin-Orbit Operators , 1999 .

[24]  Bernd A. Hess,et al.  Revision of the Douglas-Kroll transformation. , 1989, Physical review. A, General physics.

[25]  F. A. Parpia,et al.  GRASP: A general-purpose relativistic atomic structure program , 1989 .

[26]  Markus Reiher,et al.  Exact decoupling of the Dirac Hamiltonian. II. The generalized Douglas-Kroll-Hess transformation up to arbitrary order. , 2004, The Journal of chemical physics.

[27]  M. Dolg.  Relativistic Effective Core Potentials , 2002 .

[28]  Trygve Helgaker,et al.  Basis-set convergence of correlated calculations on water , 1997 .

[29]  K. Peterson.  Systematically convergent basis sets with relativistic pseudopotentials. I. Correlation consistent basis sets for the post-d group 13–15 elements , 2003 .

[30]  Kirk A Peterson,et al.  Systematically convergent basis sets for transition metals. I. All-electron correlation consistent basis sets for the 3d elements Sc-Zn. , 2005, The Journal of chemical physics.

[31]  Michael Dolg,et al.  Energy-consistent relativistic pseudopotentials and correlation consistent basis sets for the 4d elements Y-Pd. , 2007, The Journal of chemical physics.

[32]  Guntram Rauhut,et al.  Energy-consistent pseudopotentials for group 11 and 12 atoms: adjustment to multi-configuration Dirac–Hartree–Fock data , 2005 .

[33]  Markus Reiher,et al.  The generalized Douglas–Kroll transformation , 2002 .

[34]  Michael Dolg,et al.  Relativistic energy‐consistent pseudopotentials—Recent developments , 2002, J. Comput. Chem..

[35]  K. Peterson,et al.  Basis set limit electronic excitation energies, ionization potentials, and electron affinities for the 3d transition metal atoms: Coupled cluster and multireference methods. , 2006, The Journal of chemical physics.

[36]  H. Stoll,et al.  Energy-consistent relativistic pseudopotentials for the 4d elements: atomic and molecular applications. , 2008, The Journal of chemical physics.

[37]  K. Hirao,et al.  Extended Douglas–Kroll transformations applied to the relativistic many-electron Hamiltonian , 2003 .

[38]  Y. Ishikawa,et al.  Open-shell relativistic coupled-cluster method with Dirac-Fock-Breit wave functions: Energies of the gold atom and its cation. , 1994, Physical review. A, Atomic, molecular, and optical physics.

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

[40]  F. Weigend,et al.  Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. , 2005, Physical chemistry chemical physics : PCCP.

[41]  W. C. Martin,et al.  Handbook of Basic Atomic Spectroscopic Data (version 1.0) , 2003 .

[42]  H. Stoll,et al.  Energy-adjustedab initio pseudopotentials for the second and third row transition elements , 1990 .