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DFT Flavor of Coordination Chemistry

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DFT Flavor of Coordination Chemistry Coordination Chemistry Reviews 272 (2014) 1–29 Contents lists available at ScienceDirect Coordination Chemistry Reviews j ournal homepage: www.elsevier.com/locate/ccr Review DFT flavor of coordination chemistry ∗ Athanassios C. Tsipis Laboratory of Inorganic and General Chemistry, Department of Chemistry, University of Ioannina, 451 10 Ioannina, Greece Contents 1. Introduction . 3 2. DFT at work in the coordination chemistry lab. 4 2.1. Capabilities of DFT . 4 2.2. DFT at a glance (basics of the theory) . 4 2.3. DFT tools available (DFT machinery) . 5 2.3.1. LDA DFs . 5 2.3.2. GGA DFs. 5 2.3.3. Meta-GGA DFs . 5 2.3.4. Hybrid DFs . 5 2.3.5. Double hybrid DFs . 6 2.3.6. Range-separated DFs . 6 2.4. General comments on the most popular density functionals . 6 2.5. Solvent effects on molecular properties of coordination compounds . 8 2.6. Relativistic effects on molecular properties of coordination compounds . 8 2.7. General instructions for successful application of DFT in coordination chemistry . 9 3. Selected most recent successful applications of DFT in coordination chemistry . 9 3.1. Mechanistic studies – catalysis. 9 3.1.1. Catalytic reactions catalyzed by group 8 (Fe, Ru, Os) metal complexes . 10 3.1.2. Catalytic reactions catalyzed by group 9 (Co, Rh, Ir) metal complexes . 11 3.1.3. Catalytic reactions catalyzed by group 10 (Ni, Pd, Pt) metal complexes . 13 3.1.4. Catalytic reactions catalyzed by group 11 (Cu, Ag, Au) metal complexes . 15 3.2. Electronic and bonding character in coordination chemistry – conceptual DFT. 15 3.3. Simulation of the absorption and emission spectra of coordination compounds by TD-DFT . 21 3.4. Simulation of heavy-nucleus NMR chemical shifts of coordination compounds by DFT . 24 4. Concluding remarks . 26 References . 26 a r t i c l e i n f o a b s t r a c t Article history: An overview of recent progress in DFT application to coordination chemistry is presented. Some recent Received 21 December 2013 applications that best illustrate the promise of DFT in a number of very active areas of coordination Accepted 19 February 2014 chemistry, such as catalysis (mechanistic studies), bonding (electronic and bonding character) electronic Available online 21 March 2014 spectroscopy (absorption and emission spectra) and heavy-nucleus NMR spectroscopy are reviewed. Particular emphasis was given to the practical aspects that may be interesting for experimentalists that Keywords: wish to employ DFT alongside to their experimental work. General instructions of how to select the DFT proper DFT computational protocol for a particular study are outlined. Coordination compounds Mechanisms © 2014 Elsevier B.V. All rights reserved. Bonding Electronic spectra Heavy nucleus NMR spectra ∗ Tel.: +30 2651008333. E-mail address: [email protected] http://dx.doi.org/10.1016/j.ccr.2014.02.023 0010-8545/© 2014 Elsevier B.V. All rights reserved. 2 A.C. Tsipis / Coordination Chemistry Reviews 272 (2014) 1–29 Nomenclature EPR electron paramagnetic resonance ACFD adiabatic connection fluctuation-dissipation theo- ESID energy splitting in Dimer model rem GC gas chromatography AE adiabatic energies GGA generalized-gradient approximation AHS atomic Hirshfeld surface GIAO Gauge-including atomic orbital AIM atoms in molecules GIPAW Gauge including projection augmented wave aiMD ab initio molecular dynamics HAHA heavy-atom effects on heavy atoms B2PLYP double hybrid functional HALA heavy-atom effects on light atoms B3LYP Becke’s three-parameter exchange with Lee, Yang, HF Hartree–Fock approximation and Parr correlation functional HFCCs hyperfine coupling constants BLYP Becke’s 1988 exchange functional with the correla- HOFs heat of formations tion functional of Lee, Yang, and Parr HOMO highest occupied molecular orbital BP86 Becke–Perdew GGA HS high spin B97-D3 dispersion-corrected B97 functional IEF-PCM integral-equation-formalism versions of PCM B97XD range-separated functional IM intermediate ␻ -B97XD range-separated functional IMOMO integrated molecular orbital plus molecular orbital BLYP-D3 dispersion-corrected BLYP functional method BCP bond critical point IPCM isodensity PCM BS broken Symmetry IR infra red CAM-B3LYP Coulomb-attenuating method-B3LYP IRC intrinsic reaction coordinate CASPT2 complete active space second-order perturbation IPs ionization potentials theory KS Kohn–Sham CASSCF complete active space self-consistent field KS-DFT Kohn–Sham density functional theory CBS complete basis set LACVP basis sets combining the 6-31G basis set with the ccCA-TM correlation consistent Composite Approach for LANL2DZ effective core basis set transition metals LANL2DZ Los Alamos National Laboratory 2-Double-Z CC coupled cluster LC-␻PBE long-range corrected PBE functional CCP cage critical point LDA local density approximation CCSD coupled cluster with singles and doubles LED light emitting diodes 3 CCSD(T) CC with single and double excitations augmented LLCT triplet ligand-to-ligand charge transfer with perturbatively calculated triples LMCT ligand-to-metal charge transfer CDA charge decomposition analysis LMOs localized molecular orbitals CEP-31G(5d,7f) Stevens/Basch/Krauss ECP split valance LR linear response theory basis set LR-ESC linear response elimination of small component CMD concerted metalation-deprotonation pathway LR-TD-DFT linear response-time dependent density func- COSMO conductor-like screening model tional theory COSMO-RS COSMO for realistic solvation RSCF-CV-DFT relaxed and self-consistent extension of con- C-PCM conductor-like PCM solvation model stricted variational DFT CPs critical points LSDA local spin density approximation CR completely renormalized LUMO lowest unoccupied molecular orbital CS chemical Shift tensor M05-2X Minnesota group of functionals CTCs cyclic trinuclear complexes M06-2X Minnesota group of functionals DE diabatic energies MBPT many-body perturbation theory def2-SVP basis set of the def2-type MC metal centered excitations 3 DFs density functionals MC Thriplet metal centered excitations DFT density functional theory MCSCF multi-configurational self-consistent-field DFT-D3 dispersion-corrected conventional DFs MD molecular dynamics DFT-dDXDM density dependent dispersion corrected con- MEP molecular electrostatic potential ventional DFs MLCT metal-to-ligand charge transfer 3 DFT-dDsC density-dependent energy correction of a conven- MLCT) triplet metal-to-ligand charge transfer tional functional MO molecular orbital DHDFs double-hybrid density functionals MPA Mulliken population analysis DKH Douglas–Kroll–Hess Hamiltonian MP2 Möller-Plesset perturbation theory of the second D-PCM dielectric version of PCM order DSD-BLYP dispersion corrected, spin-component scaled MS magnetic shielding tensor double hybrid-BLYP MSBCT metal-to-sigma-bond-charge-transfer ECP efective-core potential MS-CASPT2 multi-state complete active space second order EDA energy decomposition analysis perturbation theory EF Eigenvalue-following NBO natural bond orbital analysis ELF electron localization function NCP nuclear critical point ELI-D electron localizability indicator based on D- NICS nucleus-independent chemical shift restricted partitioning NLMOs natural localized molecular orbitals EOM equation of motion NMR nuclear magnetic resonance A.C. Tsipis / Coordination Chemistry Reviews 272 (2014) 1–29 3 1. Introduction NPA natural population analysis Over the last few decades density functional theory (DFT) has NTOs natural transition orbitals developed to a stage that can provide invaluable help in the OEL organic electro-luminescence interpretation of experimental measurements of a broad range OEP optimized effective potential of molecular properties of coordination compounds. In this con- OLED organic light emitting diodes text DFT provides a numerical “virtual coordination chemistry OLYP GGA functional consisting of OptX exchange and LYP lab” able to compute even properties difficult or impossible to correlation functionals measure experimentally. Nowadays, DFT has become a general PBE the Perdew–Burke–Ernzerhof exchange-correlation tool to understand and predict the behavior of a broad range functional of chemical, physical, and biological phenomena of importance PCM polarizable continuum model in chemical reactivity, catalytic activity, bioactivity, photophysics, PES potential energy surface electronic and nuclear-magnetic resonance spectroscopy, lin- PT2 second order perturbation theory ear and nonlinear optics etc. in the realm of coordination PW91 Perdew–Wang 91 correlation functional chemistry. PW6B95-D3 hybrid PW6B95 functional in combination with Transition metal computational chemistry has been covered D3 diepersion corrections quite extensively in special.
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