A.I. Kuramshin a)*, M.V. Zimaliev b)**, E.V. Kolpakova a)***, V.I. Galkin a)****
a) Kazan Federal University, Kazan, 420008 Russia
b) The “Fix” Companies Group, Kazan, 420111 Russia
E-mail: *email@example.com, **firstname.lastname@example.org, ***email@example.com, ****Vladimir.Galkin@kpfu.ru
Received January 18, 2016
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The selection of a pair of functional/basis for the most adequate quantum-chemical determination of the geometric and electronic properties of chromium group metal complexes with polydent heterocyclic ligands has been carried out. When selecting a suitable model, such parameters as allowable accuracy and acceptable time of calculation have been taken into account.
It has been found that the accuracy of calculations depends on the number of basis functions involved in the calculation model – the error tends to decrease with the increase in their number. The accuracy of calculations also increases with introduction of the polarized orbitals 2d2p and 3df3pd in the quantum-chemical model and the diffuse orbitals p, pp, ppp in the basis, respectively. The results obtained by using non-hybrid functionals with large basis functions are comparable to the calculations performed in less time with the help of hybrid functionals.
The optimal ratio for the accuracy of calculation results compared to the time for study of the coordination compounds can be achieved by using the PBE0 hybrid functional and TZVPP basis functions.
TZVPP basis set
Keywords: quantum-chemical calculations, coordination compounds of chromium group metals, combinatorial methods, density functional (DFT)
- Chuvylkin N.D., Smolenskii E.A., Zefirov N.S. Quantum-chemical methods for the construction of wave functions of many-electron systems alternative to the Hartree–Fock approximation. Russ. Chem. Rev., 2005, vol. 74, no. 11, pp. 1027–1038.
- Kuramshin A.I., Mushkin V.B., Karpenko E.A., Cherkasov, R.A. Theoretical study of 3-penten-2-one complexes of iron and chromium subgroup metals with various modes of the enone coordination. Russ. J. Gen. Chem., 2001, vol. 71, no. 3, pp. 348–353.
- Krauss M., Stevens W.J. Effective potentials in molecular quantum chemistry. Annu. Rev. Phys. Chem., 1984, vol. 35, pp. 357–385.
- Jones R.O., Gunnarsson O. The density functional formalism, its applications and prospects. Rev. Mod. Phys., 1989, vol. 61, no. 3, pp. 689–746.
- Buhl M., Reimann C., Pantazis D.A., Bredow T., Neese F. Geometries of third-row transition-metal complexes from density-functional theory. J. Chem. Theory Comput., 2008, vol. 4, no. 2, pp. 1449–1459. doi: 10.1021/ct800172j.
- Becke A.D. A new mixing of Hartree-Fock and local density-functional theories. J. Chem. Phys., 1993, vol. 98, no. 2, pp. 1372–1377.
- Tirado-Rives J., Jorgensen W.L. Performance of B3LYP density functional methods for a large set of organic molecules. J. Chem. Theory Comput., 2008, vol. 4, no. 2, pp. 297–306.
- Perdew J.P., Ernzerhof M., Burke K. Rationale for mixing exact exchange with density functional approximations. J. Chem. Phys., 1996, vol. 105, no. 22, pp. 9982–9985.
- Brockway L.O., Ewens R.V.G., Lister M.W. An electron diffraction investigation of the hexacarbonyls of chromium, molybdenum and tungsten. Trans. Faraday Soc., 1938, vol. 34, pp. 1350–1357.
- Colebatch A.L., Hill A.F., Shang R., Willis A.C. Synthesis of a thiocarbamoyl alkylidyne complex and caveats associated with the use of [Mo(≡CLi)(CO)2(Tp*)] (Tp* = Hydrotris(3,5-dimethylpyrazol-1-yl)borate). Organometallics, 2010, vol. 29, no. 23, pp. 6482–6487. doi: 10.1021/om1008296.
- Neese F. The ORCA program system. WIREs Comput. Mol. Sci., 2012, vol. 2, no. 1, pp. 73–78. doi: 10.1002/wcms.81.
For citation: Kuramshin A.I., Zimaliev M.V., Kolpakova E.V., Galkin V.I. Selection of appropriate quantum-chemical model for calculations of properties of chromium group complexes via DFT. Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2016, vol. 158, no. 1, pp. 34–43. (In Russian)
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