A B3LYP-DBLOC empirical correction scheme for ligand removal enthalpies of transition metal complexes: parameterization against experimental and CCSD(T)-F12 heats of formation.

Average ligand removal enthalpies of 30 differently coordinated mono-nuclear fourth-row transition metal complexes taken from a database recently considered by Johnson and Becke [Can. J. Chem., 2009, 8, 1369] have been computed in the gas phase using unrestricted pseudo-spectral (LACV3P) and fully analytic (qzvp(-g)) B3LYP including a recently developed empirical dispersion correction. Heats of formation of neutral singlet reactants and neutral, potentially high spin, products have been taken from NIST's Organometallic Thermochemistry Database. Comparison of B3LYP-MM//qzvp(-g) and experimental average ligand removal enthalpies reveals a systematic error in the reported experimental enthalpies for manganese-containing complexes which is verified with high-level, CCSD(T)-F12//family of cc-pVTZ, explicitly correlated coupled-cluster methods. Other B3LYP-MM//qzvp(-g) error patterns give rise to a d-block localized orbital correction (DBLOC) scheme containing six transferable parameters that correct the functional's description of metal-ligand bonding, cation-π, and dispersion interactions as well as metal and/or ligand multi-reference effects. Metal-ligand cation-π and dispersion interactions have been fit to the monopole/induced-dipole, C(4)/R(4), and induced-dipole/induced-dipole, C(6)/R(6), interaction functions, respectively. This DBLOC model has been built upon a previously determined set of metal atom parameters which are necessary to properly describe the free metal atom reaction products. The final DBLOC model brings the mean unsigned error of B3LYP-MM//qzvp(-g) from 3.74 ± 3.51 kcal/mol to 0.94 ± 0.68 kcal/mol and corrects the functional's under binding in nearly every case. Several important connections among DBLOC parameters have been made.

[1]  G. Frenking,et al.  Chemical bonding in phosphane and amine complexes of main group elements and transition metals. , 2006, Inorganic chemistry.

[2]  O. Novaro,et al.  Theoretical study of the activation of methane by photoexcited zinc atoms , 1994 .

[3]  R. Friesner,et al.  Localized Orbital Corrections for the Barrier Heights in Density Functional Theory , 2009 .

[4]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

[5]  Louis Noodleman,et al.  Valence bond description of antiferromagnetic coupling in transition metal dimers , 1981 .

[6]  L. Ziurys,et al.  Activation of methane by zinc: gas-phase synthesis, structure, and bonding of HZnCH3. , 2010, Journal of the American Chemical Society.

[7]  Hans-Joachim Werner,et al.  A simple and efficient CCSD(T)-F12 approximation. , 2007, The Journal of chemical physics.

[8]  Hans-Joachim Werner,et al.  Simplified CCSD(T)-F12 methods: theory and benchmarks. , 2009, The Journal of chemical physics.

[9]  Lai‐Sheng Wang,et al.  Electronic structure of chromium oxides, CrOn- and CrOn (n=1-5) from photoelectron spectroscopy and density functional theory calculations , 2001 .

[10]  Krishnan Raghavachari,et al.  Investigation of Gaussian4 theory for transition metal thermochemistry. , 2009, The journal of physical chemistry. A.

[11]  F. Weigend,et al.  Gaussian basis sets of quadruple zeta valence quality for atoms H–Kr , 2003 .

[12]  F. Grein.  Density functional theory and multireference configuration interaction studies on low-lying excited states of TiO2. , 2007, The Journal of chemical physics.

[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]  Timothy J. Lee,et al.  Binding energies and bond distances of Ni(CO)x, x=1–4: An application of coupled‐cluster theory , 1991 .

[15]  J. Uddin,et al.  Computational Studies of Metal-Ligand Bond Enthalpies across the Transition Metal Series , 2006 .

[16]  G J Williams,et al.  The Protein Data Bank: a computer-based archival file for macromolecular structures. , 1977, Journal of molecular biology.

[17]  Richard A Friesner,et al.  Correcting Systematic Errors in DFT Spin-Splitting Energetics for Transition Metal Complexes. , 2011, Journal of chemical theory and computation.

[18]  A. Becke,et al.  Tests of an exact-exchange-based density-functional theory on transition-metal complexes , 2009 .

[19]  M. Rodgers,et al.  Noncovalent interactions of Cu+ with N-donor ligands (pyridine, 4,4-dipyridyl, 2,2-dipyridyl, and 1,10-phenanthroline): collision-induced dissociation and theoretical studies. , 2007, The journal of physical chemistry. A.

[20]  F. Weinhold,et al.  Natural population analysis , 1985 .

[21]  F. Allen.  The Cambridge Structural Database: a quarter of a million crystal structures and rising. , 2002, Acta crystallographica. Section B, Structural science.

[22]  M. Fojta,et al.  Effect of spin-orbit coupling on reduction potentials of octahedral ruthenium(II/III) and osmium(II/III) complexes. , 2008, Journal of the American Chemical Society.

[23]  R. Friesner,et al.  Localized orbital corrections applied to thermochemical errors in density functional theory: The role of basis set and application to molecular reactions. , 2008, The Journal of chemical physics.

[24]  Richard A Friesner,et al.  Parameterization of a B3LYP specific correction for non-covalent interactions and basis set superposition error on a gigantic dataset of CCSD(T) quality non-covalent interaction energies. , 2011, Journal of chemical theory and computation.

[25]  J. Harvey,et al.  Modelling spin-forbidden reactions: recombination of carbon monoxide with iron tetracarbonyl. , 2003, Faraday discussions.

[26]  J. Paldus,et al.  A truncated version of reduced multireference coupled-cluster method with singles and doubles and noniterative triples: application to F2 and Ni(CO)n (n=1, 2, and 4). , 2006, The Journal of chemical physics.

[27]  Mihály Kállay,et al.  Computing coupled-cluster wave functions with arbitrary excitations , 2000 .

[28]  R. Friesner,et al.  Development of Accurate DFT Methods for Computing Redox Potentials of Transition Metal Complexes: Results for Model Complexes and Application to Cytochrome P450. , 2012, Journal of chemical theory and computation.

[29]  F. Grein.  DFT and MRCI studies on ground and excited states of CrO2 , 2008 .

[30]  Yixiang Cao,et al.  A localized orbital analysis of the thermochemical errors in hybrid density functional theory: achieving chemical accuracy via a simple empirical correction scheme. , 2006, The Journal of chemical physics.

[31]  George Vacek,et al.  Advanced initial-guess algorithm for self-consistent-field calculations on organometallic systems , 1999 .

[32]  Nathan J DeYonker,et al.  Toward accurate theoretical thermochemistry of first row transition metal complexes. , 2012, The journal of physical chemistry. A.

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

[34]  R. Friesner,et al.  Density functional localized orbital corrections for transition metals. , 2008, The Journal of chemical physics.

[35]  S. Grimme,et al.  A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. , 2010, The Journal of chemical physics.

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

[37]  Frederick R. Manby,et al.  Fast linear scaling second-order Møller-Plesset perturbation theory (MP2) using local and density fitting approximations , 2003 .

[38]  Richard L. Lord,et al.  Spin crossover-coupled electron transfer of [M(tacn)(2)](3+/2+) complexes (tacn = 1,4,7-triazacyclononane; M = Cr, Mn, Fe, Co, Ni). , 2009, Journal of the American Chemical Society.

[39]  J. Harvey,et al.  Computational study of the energetics of 3Fe(CO)4, 1Fe(CO)4 and 1Fe(CO)4(L), L = Xe, CH4, H2 and CO. , 2006, Physical chemistry chemical physics : PCCP.

[40]  T. Cundari,et al.  Calculation of the enthalpies of formation for transition metal complexes , 2005 .

[41]  R. Friesner,et al.  Localized orbital corrections for the calculation of ionization potentials and electron affinities in density functional theory. , 2006, The journal of physical chemistry. B.

[42]  J. M. Simoes,et al.  Transition metal-hydrogen and metal-carbon bond strengths: the keys to catalysis , 1990 .

[43]  D. Truhlar,et al.  A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions. , 2006, The Journal of chemical physics.

[44]  Kevin E. Riley,et al.  Assessment of density functional theory methods for the computation of heats of formation and ionization potentials of systems containing third row transition metals. , 2007, The journal of physical chemistry. A.