Benchmarking approximate density functional theory for s/d excitation energies in 3d transition metal cations

Holthausen has recently provided a comprehensive study of density functional theory for calculating the s/d excitation energies of the 3d transition metal cations. This study did not include the effects of scalar relativistic effects, and we show here that the inclusion of scalar relativistic effects significantly alters the conclusions of the study. We find, contrary to the previous study, that local functionals are more accurate for the excitation energies of 3d transition method cations than hybrid functionals. The most accurate functionals, of the 38 tested, are SLYP, PBE, BP86, PBELYP, and PW91. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008

[1]  R. Poli.  Open shell organometallics: a general analysis of their electronic structure and reactivity , 2004 .

[2]  R. Bartlett,et al.  A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples , 1982 .

[3]  T. Van Voorhis,et al.  Accurate magnetic exchange couplings in transition-metal complexes from constrained density-functional theory. , 2006, The Journal of chemical physics.

[4]  F. Himo,et al.  Density functional methods applied to metalloenzymes , 2003 .

[5]  Vincenzo Barone,et al.  Toward reliable adiabatic connection models free from adjustable parameters , 1997 .

[6]  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.

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

[8]  Robert G. Parr,et al.  Density Functional Theory of Electronic Structure , 1996 .

[9]  V. Barone,et al.  An accurate density functional method for the study of magnetic properties: the PBE0 model , 1999 .

[10]  Kevin M. Smith,et al.  Understanding the reactivity of transition metal complexes involving multiple spin states , 2003 .

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

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

[13]  Sason Shaik,et al.  Quantum mechanical/molecular mechanical investigation of the mechanism of C-H hydroxylation of camphor by cytochrome P450cam: theory supports a two-state rebound mechanism. , 2004, Journal of the American Chemical Society.

[14]  Steven D. Brown,et al.  High-spin and low-spin iron(II) complexes with facially-coordinated borohydride ligands. , 2006, Dalton transactions.

[15]  D. Case,et al.  Metal substitution in the active site of nitrogenase MFe7S9 (M = Mo4+, V3+, Fe3+) , 2002 .

[16]  D. Jenkins,et al.  Spin-state tuning at pseudotetrahedral d(7) ions: examining the structural and magnetic phenomena of four-coordinate [BP3]CoII-X systems. , 2005, Journal of the American Chemical Society.

[17]  E. Davidson,et al.  Semiempirical local spin: Theory and implementation of the ZILSH method for predicting Heisenberg exchange constants of polynuclear transition metal complexes , 2003 .

[18]  Frank Neese,et al.  Theoretical spectroscopy of model-nonheme [Fe(IV)OL5]2+ complexes in their lowest triplet and quintet states using multireference ab initio and density functional theory methods. , 2006, Journal of inorganic biochemistry.

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

[20]  D. C. Griffin,et al.  Approximate relativistic corrections to atomic radial wave functions , 1976 .

[21]  F. Cotton,et al.  Structure and magnetism of [M3](6/7+) metal chain complexes from density functional theory: analysis for copper and predictions for silver. , 2006, Inorganic Chemistry.

[22]  Donald G Truhlar,et al.  Density functionals for inorganometallic and organometallic chemistry. , 2005, The journal of physical chemistry. A.

[23]  Jean-Paul Malrieu,et al.  Analysis of the magnetic coupling in binuclear complexes. II. Derivation of valence effective Hamiltonians from ab initio CI and DFT calculations , 2002 .

[24]  M. Reiher,et al.  Reparameterization of hybrid functionals based on energy differences of states of different multiplicity , 2001 .

[25]  D. Truhlar,et al.  Thermochemical analysis of core correlation and scalar relativistic effects on molecular atomization energies , 2000 .

[26]  F. Neese,et al.  Noninnocence of the ligand glyoxal-bis(2-mercaptoanil). The electronic structures of [Fe(gma)]2, [Fe(gma)(py)] x py, [Fe(gma)(CN)]1-/0, [Fe(gma)I], and [Fe(gma)(PR3)(n)] (n = 1, 2). Experimental and theoretical evidence for "excited state" coordination. , 2003, Journal of the American Chemical Society.

[27]  Donald G Truhlar,et al.  Databases for transition element bonding: metal-metal bond energies and bond lengths and their use to test hybrid, hybrid meta, and meta density functionals and generalized gradient approximations. , 2005, The journal of physical chemistry. A.

[28]  Jiří Čížek,et al.  On the Use of the Cluster Expansion and the Technique of Diagrams in Calculations of Correlation Effects in Atoms and Molecules , 2007 .

[29]  Max C. Holthausen,et al.  Benchmarking approximate density functional theory. I. s/d excitation energies in 3d transition metal cations , 2005, J. Comput. Chem..

[30]  W. J. Stevens,et al.  Effective Potentials in Molecular Quantum Chemistry , 1984 .

[31]  Donald G Truhlar,et al.  PdnCO (n = 1,2): accurate Ab initio bond energies, geometries, and dipole moments and the applicability of density functional theory for fuel cell modeling. , 2006, The journal of physical chemistry. B.

[32]  Marvin L. Cohen,et al.  Electronic structure of solids , 1984 .

[33]  John C. Slater,et al.  Quantum Theory of Molecules and Solids , 1951 .

[34]  M. Reiher,et al.  Assertion and validation of the performance of the B3LYP* functional for the first transition metal row and the G2 test set , 2002 .

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

[36]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[37]  F. Neese,et al.  Calculating the electron paramagnetic resonance parameters of exchange coupled transition metal complexes using broken symmetry density functional theory: application to a MnIII/MnIV model compound. , 2004, Journal of the American Chemical Society.

[38]  J. Harvey,et al.  Do spin state changes matter in organometallic chemistry? A computational study. , 2004, Journal of the American Chemical Society.

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

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

[41]  M. Frisch,et al.  Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields , 1994 .

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

[43]  Y. Kitagawa,et al.  Theoretical studies of magnetic interactions in Mn(II)(hfac)(2)[di(4-pyridyl)phenylcarbene] and Cu(II)(hfac)(2)[di(4-pyridyl)phenylcarbene]. , 2002, Journal of the American Chemical Society.

[44]  F. Neese,et al.  Theoretical evidence for the singlet diradical character of square planar nickel complexes containing two o-semiquinonato type ligands. , 2002, Inorganic chemistry.

[45]  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.

[46]  Walter Kohn,et al.  Nobel Lecture: Electronic structure of matter-wave functions and density functionals , 1999 .

[47]  Vincenzo Barone,et al.  Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW models , 1998 .

[48]  A. Becke.  A New Mixing of Hartree-Fock and Local Density-Functional Theories , 1993 .

[49]  Richard L. Martin,et al.  Relativistic contributions to the low‐lying excitation energies and ionization potentials of the transition metals , 1981 .

[50]  J. McGrady,et al.  Mutual interdependence of spin crossover and metal-metal bond formation in M2Cl9(3-) (M = Fe, Ru, Os). , 2001, Inorganic chemistry.