Vibrational corrections to geometries of transition metal complexes from density functional theory

Zero‐point vibrational corrections are computed at the BP86/AE1 level for the set of 50 transition‐metal/ligand bonds that have recently been proposed as testing ground for DFT methods, because of the availability of precise experimental gas‐phase geometries (Bühl and Kabrede, J Chem Theory Comput 2006, 2, 1282). These corrections are indicated to be transferable to a large extent between various density‐functional/basis‐set combinations, so that they can be used to estimate zero‐point averaged r  0g distances from re values optimized at other theoretical levels. Applying this approach to a number of popular DFT levels does not, in general, improve their overall accuracy in terms of mean and standard deviations from experiment. The hybrid variant of the meta‐functional TPSS is confirmed as promising choice for computing structures of transition‐metal complexes. © 2007 Wiley Periodicals, Inc. J Comput Chem 28: 1531–1537, 2007

[1]  P. Åstrand,et al.  An efficient approach for calculating vibrational wave functions and zero-point vibrational corrections to molecular properties of polyatomic molecules , 2000 .

[2]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[3]  Vincenzo Barone,et al.  Vibrational zero-point energies and thermodynamic functions beyond the harmonic approximation. , 2004, The Journal of chemical physics.

[4]  Vincenzo Barone,et al.  Anharmonic vibrational properties by a fully automated second-order perturbative approach. , 2005, The Journal of chemical physics.

[5]  Hans W. Horn,et al.  Fully optimized contracted Gaussian basis sets for atoms Li to Kr , 1992 .

[6]  P. Åstrand,et al.  A modified variation–perturbation approach to zero-point vibrational motion , 2000 .

[7]  Jianmin Tao,et al.  Erratum: “Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes” [J. Chem. Phys. 119, 12129 (2003)] , 2004 .

[8]  M. Bühl,et al.  Thermal effects and vibrational corrections to transition metal NMR chemical shifts. , 2004, Chemistry.

[9]  Michael Dolg,et al.  Energy‐adjusted ab initio pseudopotentials for the first row transition elements , 1987 .

[10]  P. Åstrand,et al.  Zero-point vibrational effects on proton shieldings: functional-group contributions from ab initio calculations. , 2001, Journal of the American Chemical Society.

[11]  Paweł Sałek,et al.  Dalton, a molecular electronic structure program , 2005 .

[12]  A. Schäfer,et al.  Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr , 1994 .

[13]  W. R. Wadt,et al.  Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals , 1985 .

[14]  K. Ruud,et al.  Vibrational corrections to indirect nuclear spin–spin coupling constants calculated by density-functional theory , 2003 .

[15]  G. Scuseria,et al.  Climbing the density functional ladder: nonempirical meta-generalized gradient approximation designed for molecules and solids. , 2003, Physical review letters.

[16]  Michael Bühl,et al.  Geometries of Transition-Metal Complexes from Density-Functional Theory. , 2006, Journal of chemical theory and computation.

[17]  A. Wachters,et al.  Gaussian Basis Set for Molecular Wavefunctions Containing Third‐Row Atoms , 1970 .

[18]  Filipp Furche,et al.  The performance of semilocal and hybrid density functionals in 3d transition-metal chemistry. , 2006, The Journal of chemical physics.

[19]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[20]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[21]  P. Åstrand,et al.  Calculation of the vibrational wave function of polyatomic molecules , 2000 .

[22]  G. Scuseria,et al.  Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes , 2003 .

[23]  Jürgen Gauss,et al.  The prediction of molecular equilibrium structures by the standard electronic wave functions , 1997 .

[24]  J. Pople,et al.  Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules , 1972 .

[25]  P. C. Hariharan,et al.  The influence of polarization functions on molecular orbital hydrogenation energies , 1973 .

[26]  J. Perdew,et al.  Erratum: Density-functional approximation for the correlation energy of the inhomogeneous electron gas , 1986, Physical review. B, Condensed matter.

[27]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[28]  T. Oka,et al.  Effect of vibration and rotation on the internuclear distance , 1964 .

[29]  P. Jeffrey Hay,et al.  Gaussian basis sets for molecular calculations. The representation of 3d orbitals in transition‐metal atoms , 1977 .

[30]  P. Imhof,et al.  Rovibrational corrections to transition metal NMR shielding constants. , 2004, Chemphyschem : a European journal of chemical physics and physical chemistry.