Communication: DFT treatment of strong correlation in 3d transition-metal diatomics.

Bonds between, and to, transition-metal atoms often involve strong electron correlation which cannot be handled by conventional density-functional-theory approximations. The recent "B13" functional of Becke [J. Chem. Phys. 138, 074109 (2013) and J. Chem. Phys. 138, 161101 (2013)] models dynamic, static, and strong correlation in an exact-exchange-based framework. We test B13 on bond energies of transition-metal diatomics in this work, with promising results.

[1]  Weitao Yang,et al.  A challenge for density functionals: Self-interaction error increases for systems with a noninteger number of electrons , 1998 .

[2]  Fred A. Hamprecht,et al.  Development and assessment of new exchange-correlation functionals , 1998 .

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

[4]  Axel D. Becke,et al.  Density functionals for static, dynamical, and strong correlation. , 2013, The Journal of chemical physics.

[5]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

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

[7]  A. Becke.  A real-space model of nondynamical correlation , 2003 .

[8]  A. Becke.  Real-space post-Hartree-Fock correlation models. , 2005, The Journal of chemical physics.

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

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

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

[12]  Weitao Yang,et al.  Fractional spins and static correlation error in density functional theory. , 2008, The Journal of chemical physics.

[13]  Adrienn Ruzsinszky,et al.  Spurious fractional charge on dissociated atoms: pervasive and resilient self-interaction error of common density functionals. , 2006, The Journal of chemical physics.

[14]  Weitao Yang,et al.  Insights into Current Limitations of Density Functional Theory , 2008, Science.

[15]  A. Becke,et al.  Cr2 in density-functional theory: approximate spin projection , 1995 .

[16]  Donald G Truhlar,et al.  Do Practical Standard Coupled Cluster Calculations Agree Better than Kohn-Sham Calculations with Currently Available Functionals When Compared to the Best Available Experimental Data for Dissociation Energies of Bonds to 3d Transition Metals? , 2015, Journal of chemical theory and computation.

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

[18]  A. Becke,et al.  Density functionals and transition-metal atoms. , 2007, The Journal of chemical physics.

[19]  A. Ruzsinszky,et al.  Reference Determinant Dependence of the Random Phase Approximation in 3d Transition Metal Chemistry. , 2017, Journal of chemical theory and computation.

[20]  G. Scuseria,et al.  Assessment of a long-range corrected hybrid functional. , 2006, The Journal of chemical physics.

[21]  Artur F Izmaylov,et al.  Influence of the exchange screening parameter on the performance of screened hybrid functionals. , 2006, The Journal of chemical physics.

[22]  Heather J Kulik,et al.  Systematic study of first-row transition-metal diatomic molecules: a self-consistent DFT+U approach. , 2010, The Journal of chemical physics.

[23]  Angela K. Wilson,et al.  Comparative Study of Single and Double Hybrid Density Functionals for the Prediction of 3d Transition Metal Thermochemistry. , 2012, Journal of chemical theory and computation.

[24]  Communication: Calibration of a strong-correlation density functional on transition-metal atoms. , 2013, The Journal of chemical physics.

[25]  A. Becke.  Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionals , 1997 .

[26]  Eunji Sim,et al.  Understanding and reducing errors in density functional calculations. , 2012, Physical review letters.

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

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

[29]  Axel D. Becke,et al.  Numerical solution of Schrödinger’s equation in polyatomic molecules , 1990 .

[30]  Y. Shao,et al.  Improved self-consistent and resolution-of-identity approximated Becke'05 density functional model of nondynamic electron correlation. , 2012, The Journal of chemical physics.

[31]  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.

[32]  Nashali M. Ferrara,et al.  Thermochemistry and Geometries for Transition-Metal Chemistry from the Random Phase Approximation. , 2016, Journal of chemical theory and computation.

[33]  Jörg Meyer,et al.  Diffusion Monte Carlo for Accurate Dissociation Energies of 3d Transition Metal Containing Molecules. , 2016, Journal of chemical theory and computation.

[34]  V. Barone,et al.  Toward reliable density functional methods without adjustable parameters: The PBE0 model , 1999 .

[35]  A. Otero-de-la-Roza,et al.  Extreme density-driven delocalization error for a model solvated-electron system. , 2013, The Journal of chemical physics.