Comparison of ab initio and density functional methods for vibrational analysis of TeCl4

Attila Kovács, G. Csonka, György M. Keseru

Research output: Contribution to journalArticle

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Abstract

Vibrational analysis of tellurium tetrachloride, TeCl4, was performed with Hartree-Fock (HF), MP2, and generalized gradient approximation density functional theory (DFT) methods supplemented with polarized double-zeta split valence (DZVP) basis sets and relativistic effective core potentials (RECP) of Hay and Wadt. The molecular geometry is best reproduced at the HF and MP2/RECP + DZVP [polarized Hay and Wadt RECP for Te and 6-31G(d) basis set for Cl] levels of theory. The DFT methods gave rise to poorer results, especially those using Becke's 1988 exchange functional. Generally, the vibrational frequencies calculated by the MP2 and B3-type DFT methods with the all electron and RECP + DZVP basis sets as well as at the HF/RECP level were in satisfactory accord with the experimental data. The agreement was good enough to assist the assignment of the measured vibrational spectra. The best agreement with the experimental vibrational frequencies was achieved with the scaled HF/RECP force field. Consistent results were obtained for the unobserved A2 (v4) fundamental, where the results of the best methods were within 4 cm-1. The best force fields were obtained with the following methods: Becke3-Lee-Yang-Parr and Becke3-Perdew/all electron basis, MP2 and Becke3-Perdew/RECP + DZVP, and HF/RECP. The methods using RECPs are advantageous for large-scale computations. The RECP basis set effectively compensates the errors of the HF method for TeCl4; however, it provides poor results with correlated methods.

Original languageEnglish
Pages (from-to)308-318
Number of pages11
JournalJournal of Computational Chemistry
Volume19
Issue number3
Publication statusPublished - Feb 1998

Fingerprint

Vibrational spectra
Density Functional
Density functional theory
Tellurium
Electrons
Force Field
Geometry
Electron
Generalized Gradient
Potential Field
Assignment
Experimental Data
Approximation

Keywords

  • Ab initio calculations
  • Density functional theory
  • Scaled quantum mechanical method
  • Tellurium tetrachloride
  • Vibrational analysis

ASJC Scopus subject areas

  • Chemistry(all)
  • Safety, Risk, Reliability and Quality

Cite this

Comparison of ab initio and density functional methods for vibrational analysis of TeCl4. / Kovács, Attila; Csonka, G.; Keseru, György M.

In: Journal of Computational Chemistry, Vol. 19, No. 3, 02.1998, p. 308-318.

Research output: Contribution to journalArticle

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