The structure of the free MnF3 molecule - A beautiful example of the Jan-Teller effect

M. Hargittai, Balázs Réffy, M. Kolonits, Colin J. Marsden, Jean Louis Heully

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Abstract

A new high-temperature gas-phase electron diffraction analysis of manganese trifluoride, combined with high-level quantum chemical calculations, provides direct geometrical evidence of a Jahn-Teller distortion in a free molecule. The potential energy surface of the molecule was scanned extensively by computation at the SCF level. CASSCF and CASPT2 calculations established that of the many C(2v) symmetry stationary points on the potential energy surface the lowest energy ones are quintets. The global minimum is a quintet state of 5A1 symmetry. in this planar C(2v) symmetry structure there are two longer and one somewhat shorter Mn-F bonds, with two bond angles close to 106°and one bond angle of about 148°. The second lowest energy state was of 5B2 symmetry, which turned out to be a transition state with an imaginary b2 (in plane) bending frequency. A constrained planar structure of D(3h) molecular symmetry has appreciably higher energy than the 5B2 symmetry structure. The experimental data are in complete agreement with the results of the computations in giving the best agreement with a C(2v) structure characterized by r(g)(Mn-Fe) = 1.278 ± 0.014 Å (once), r(g)(Mn-F) = 1.754 ± 0.008 Å (twice), 3.

Original languageEnglish
Pages (from-to)9042-9048
Number of pages7
JournalJournal of the American Chemical Society
Volume119
Issue number38
DOIs
Publication statusPublished - Sep 24 1997

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Manganese
Gases
Electrons
Potential energy surfaces
Molecules
Temperature
Jahn-Teller effect
Crystal symmetry
Electron diffraction
Electron energy levels

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

The structure of the free MnF3 molecule - A beautiful example of the Jan-Teller effect. / Hargittai, M.; Réffy, Balázs; Kolonits, M.; Marsden, Colin J.; Heully, Jean Louis.

In: Journal of the American Chemical Society, Vol. 119, No. 38, 24.09.1997, p. 9042-9048.

Research output: Contribution to journalArticle

Hargittai, M. ; Réffy, Balázs ; Kolonits, M. ; Marsden, Colin J. ; Heully, Jean Louis. / The structure of the free MnF3 molecule - A beautiful example of the Jan-Teller effect. In: Journal of the American Chemical Society. 1997 ; Vol. 119, No. 38. pp. 9042-9048.
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