Empirical potential energy surface for the Hg+I2 reaction

T. M. Mayer, James Muckerman, B. E. Wilcomb, R. B. Bernstein

Research output: Contribution to journalArticle

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Abstract

The general features of the ground state adiabatic potential energy hypersurface for the Hg+I2 system have been deduced using results of recent molecular beam scattering experiments, spectroscopic and structural data, and electronic state correlation diagrams. The key element of the potential energy surface (p.e.s.) is a deep attractive "basin," implied from the reactive scattering data which provided evidence for the existence of a long-lived intermediate complex, believed to be IHgI. This empirical p.e.s. is characterized by the following features: (a) a shallow well in the entrance valley corresponding to the weakly bound (by ∼0.06 eV) van der Waals adduct Hg-I2; (b) a subsequent barrier of ∼0.7 eV in the entrance valley due to avoided crossings of diabatic potential curves, followed by a "falloff" leading to insertion of the Hg(1S0) into the I2(1g +) molecule; (c) a deep potential well (-1.45 eV) corresponding to the stable IHgI complex, taken to be gaseous mercuric iodide in its ground electronic state, 1A1(1g +); (d) an exit valley with a minimum energy path rising essentially monotonically, with a negligible intrinsic arrier (≲0.03 eV) from -1.45 to +1.15 eV to yield HgI(X 2+)+I(2P3/2); (e) an essentially monotonic exit path rising to the threshold (+1.54 eV) for collision-induced dissociation; (f) a barrier to reaction in the collinear configuration (Hg-I-I) in which IHgI complex formation is sterically precluded.

Original languageEnglish
Pages (from-to)3522-3529
Number of pages8
JournalJournal of Chemical Physics
Volume67
Issue number8
Publication statusPublished - 1977

Fingerprint

Potential energy surfaces
Electronic states
valleys
potential energy
Scattering
entrances
Molecular beams
Potential energy
Ground state
scattering
electronics
iodides
molecular beams
adducts
Molecules
insertion
diagrams
dissociation
collisions
ground state

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Mayer, T. M., Muckerman, J., Wilcomb, B. E., & Bernstein, R. B. (1977). Empirical potential energy surface for the Hg+I2 reaction. Journal of Chemical Physics, 67(8), 3522-3529.

Empirical potential energy surface for the Hg+I2 reaction. / Mayer, T. M.; Muckerman, James; Wilcomb, B. E.; Bernstein, R. B.

In: Journal of Chemical Physics, Vol. 67, No. 8, 1977, p. 3522-3529.

Research output: Contribution to journalArticle

Mayer, TM, Muckerman, J, Wilcomb, BE & Bernstein, RB 1977, 'Empirical potential energy surface for the Hg+I2 reaction', Journal of Chemical Physics, vol. 67, no. 8, pp. 3522-3529.
Mayer, T. M. ; Muckerman, James ; Wilcomb, B. E. ; Bernstein, R. B. / Empirical potential energy surface for the Hg+I2 reaction. In: Journal of Chemical Physics. 1977 ; Vol. 67, No. 8. pp. 3522-3529.
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