ISSN:
0192-8651
Keywords:
Computational Chemistry and Molecular Modeling
;
Biochemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Computer Science
Notes:
Relativistic and electron correlation effects in thallium halides TlX and TlX3 (X=F, Cl, Br, and I) are investigated by extensive ab initio configuration interaction calculations. Spin-orbit coupling is included at the Hartree-Fock level for the diatomic TlBr and TlI. At the best level of treatment of electron correlation (quadratic configuration interaction), the calculated molecular properties are in good agreement with experimental results, i.e., for the diatomic thallium halides deviations from experimental values are 〈0.06 Å for bond distances, 〈0.14 mdyn/Å for force constants, 〈35 kJ/mol for dissociation energies, and 〈0.3 D for dipole moments. The convergence of the Møller-Plesset series up to the fourth order is discussed. Two alternative structures of TlI3 are compared. At the Møller-Plesset level of theory, the trigonal planar structure with thallium in the oxidation state + 3 is the preferred gas phase arrangement compared with the bent arrangement containing a linear I3- unit and thallium in the oxidation state + 1, the difference being ca. 95 kJ/mol. Vibrational frequencies are predicted for all trigonal planar thallium(III) halides. © 1993 John Wiley & Sons, Inc.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jcc.540140806
