A theoretical study of tetrabutylammonium [bis(1,3-dithiole-2-thione-4,5-dithiolato)bismuthate], [NBu4][Bi(dmit)2]: infrared spectrum in the solid state and solvation effects on the molecular geometry

• Published in: Inorganica Chimica Acta 2004-03, Vol.357 (4), p.1047-1053
• Main Authors: Maria Rocco, Ana, Pacheco Pereira, Robson, Bonapace, José A.P., Comerlato, Nadia M., Wardell, James L., Milne, Bruce F., Wardell, Solange M.S.V.
• Format: Article
• Language: English
• Subjects: Bismuth; Dmit; Hartree–Fock; Vibrational spectra
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2003.09.026

The vibrational spectrum and the molecular orbitals of {[NBu4][Bi(dmit)2]}n have been calculated at the Hartree–Fock level of theory with the pseudo-potential SBKJC for Bi and a basis set of 6-31G or 6-31G(d,p) for the other atoms. A theoretical study of tetrabutylammonium [bis(1,3-dithiole-2-thione-4,5-dithiolato)bismuthate], [NBu4][Bi(dmit)2] is reported. The vibrational spectrum and the molecular orbitals were calculated at the Hartree–Fock level of theory with the pseudo-potential SBKJC for Bi and a basis set of 6-31G or 6-31G(d,p) for the other atoms. The molecular geometry of the anion, [Bi(dmit)2]−, was optimised with the same level of theory and basis sets, but utilising the polarisable continuum method, for simulation of acetone and benzene media. Molecular geometries of solvated and solid-state species are compared: solvation effects are discussed in terms of anisotropy or isotropy of the media. Analysis of the molecular orbitals allowed a qualitative description of the anion–anion intermolecular interactions.