Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)5−CO and (CO)5Mn−Mn(CO)5

Rosa, Angela; Ehlers, A.W.; Baerends, E. J.; Snijders, J.G.; Velde, G. te

doi:10.1021/jp953381p

Cited by 132 publications

(154 citation statements)

References 51 publications

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“…These basis sets are given in Ref. 36, where also basis set superposition errors for these basis sets in the Cr͑CO͒ 6 and Mn 2 ͑CO͒ 10 complexes have been investigated. Comparing the SR ZORA calculations we conclude from Table V that the results of the frozen core calculations compare very well with our largest calculations, the all electron ͑ae͒ calculations.…”

Section: Resultsmentioning

confidence: 99%

Geometry optimizations in the zero order regular approximation for relativistic effects

Lenthe

Ehlers

Baerends

1999

The Journal of Chemical Physics

2,274

1,591

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Analytical expressions are derived for the evaluation of energy gradients in the zeroth order regular approximation ͑ZORA͒ to the Dirac equation. The electrostatic shift approximation is used to avoid gauge dependence problems. Comparison is made to the quasirelativistic Pauli method, the limitations of which are highlighted. The structures and first metal-carbonyl bond dissociation energies for the transition metal complexes W͑CO͒ 6 , Os͑CO͒ 5 , and Pt͑CO͒ 4 are calculated, and basis set effects are investigated.

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Section: Resultsmentioning

confidence: 99%

Geometry optimizations in the zero order regular approximation for relativistic effects

Lenthe

Ehlers

Baerends

1999

The Journal of Chemical Physics

2,274

1,591

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“…For Ni-(CO) 4 , we used the geometry given in ref 69 with a Ni-C distance of 1.838 Å and a C-O distance of 1.141 Å. For Mn 2 -(CO) 10 , we assumed, as usual, 70 a D 4d symmetry, in which the two sets of equatorial CO's are in a staggered configuration with respect to each other. Three different geometries were used as the results appeared to be strongly geometry dependent.…”

Section: Technical Details Of the Calculationmentioning

confidence: 99%

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

et al. 1999

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The first time-dependent density functional theory (TDDFT) calculations on the spectra of molecules containing transition metals are reported. Three prototype systems are considered, of which the assignments are controversial: MnO 4 -, Ni(CO) 4 , and Mn 2 (CO) 10 . The TDDFT results are shown to be comparable in accuracy to the most elaborate ab initio calculations and lead to new insights in the spectra of these molecules. In some cases, the presented TDDFT results differ substantially, in both the ordering and the values for the excitation energies, from the older DFT method for the calculation of excitation energies: the ∆SCF approach. For the Mn 2 (CO) 10 molecule, the presented results are the highest-level theoretical results published so far. Over all, the results show that TDDFT can be a very useful tool in the calculation and interpretation of the spectra of transition metal compounds.

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“…It has been shown that the basis set error of such a ''triple '' basis set for the first bond dissociation energy of Cr͑CO͒ 6 is only a few hundredths of an eV. 30 We have tested the effect of adding f functions to the basis set by doing scalar relativistic calculations with CO at the preferred adsorption sites on Ni, Pd, and Pt. The adsorption energy was affected less than 0.1 eV, and therefore we have found it reasonable to remove the f functions from the basis sets.…”

Section: Computational Detailsmentioning

confidence: 99%

Relativistic calculations on the adsorption of CO on the (111) surfaces of Ni, Pd, and Pt within the zeroth-order regular approximation

et al. 1997

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In this paper we first describe the implementation of the zeroth-order regular approximation ͑ZORA͒ for relativistic effects in our density-functional program for extended systems. The ZORA formalism affords approximations, which are discussed and tested, that reduce the computational effort of scalar relativistic calculations to that of nonrelativistic calculations, the inclusion of spin-orbit coupling requiring additional effort. Second, we present the outcome of nonrelativistic, scalar relativistic, and spin-orbit coupling calculations on the adsorption energy of CO on the ͑111͒ surfaces of Ni, Pd, and Pt. Relativity has a modest effect for CO on Pd, but proves to be essential for CO on Pt. The relativistic correction for the CO/Pt adsorption energy is as large as 70% at the scalar relativistic level and 55% when including spin-orbit coupling. In addition, relativity changes the preferred adsorption site for CO/Pt from hollow to top. We have examined the effects of spin polarization and of different exchange-correlation functionals, i.e., the local-density approximation ͑LDA͒ versus two generalized gradient approximations ͑GGA͒. The GGA's correct the severe overbinding by LDA of CO to the metal surfaces, and yield good agreement with experiment for adsorption energies and sites.

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Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)₅−CO and (CO)₅Mn−Mn(CO)₅

Cited by 132 publications

References 51 publications

Geometry optimizations in the zero order regular approximation for relativistic effects

Geometry optimizations in the zero order regular approximation for relativistic effects

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀

Relativistic calculations on the adsorption of CO on the (111) surfaces of Ni, Pd, and Pt within the zeroth-order regular approximation

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Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)5−CO and (CO)5Mn−Mn(CO)5

Cited by 132 publications

References 51 publications

Geometry optimizations in the zero order regular approximation for relativistic effects

Geometry optimizations in the zero order regular approximation for relativistic effects

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO4-, Ni(CO)4, and Mn2(CO)10

Relativistic calculations on the adsorption of CO on the (111) surfaces of Ni, Pd, and Pt within the zeroth-order regular approximation

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Basis Set Effects in Density Functional Calculations on the Metal−Ligand and Metal−Metal Bonds of Cr(CO)₅−CO and (CO)₅Mn−Mn(CO)₅

Excitation Energies for Transition Metal Compounds from Time-Dependent Density Functional Theory. Applications to MnO₄^-, Ni(CO)₄, and Mn₂(CO)₁₀