Closed-shell molecules that ionize more readily than cesium

F. Albert Cotton, Nadine E. Gruhn, Jiande Gu, Penglin Huang, Dennis L Lichtenberger, Carlos A. Murillo, Laura O. Van Dorn, Chad C. Wilkinson

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Abstract

We report a class of molecules with extremely low ionization enthalpies, one member of which has been determined to have a gas-phase ionization energy (onset, 3.51 electron volts) lower than that of the cesium atom (which has the lowest gas-phase ionization energy of the elements) or of any other known closed-shell molecule or neutral transient species reported. The molecules are dimetal complexes with the general formula M2(hpp)4 (where M is Cr, Mo, or W, and hpp is the anion of 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine), structurally characterized in the solid state, spectroscopically characterized in the gas phase, and modeled with theoretical computations. The low-energy ionization of each molecule corresponds to the removal of an electron from the delta bonding orbital of the quadruple metal-metal bond, and a strong interaction of this orbital with a filled orbital on the hpp ligands largely accounts for the low ionization energies.

Original languageEnglish (US)
Pages (from-to)1971-1974
Number of pages4
JournalScience
Volume298
Issue number5600
DOIs
StatePublished - Dec 6 2002

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Cesium
Gases
Metals
Electrons
Anions
Ligands

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  • General

Cite this

Cotton, F. A., Gruhn, N. E., Gu, J., Huang, P., Lichtenberger, D. L., Murillo, C. A., ... Wilkinson, C. C. (2002). Closed-shell molecules that ionize more readily than cesium. Science, 298(5600), 1971-1974. https://doi.org/10.1126/science.1078721

Closed-shell molecules that ionize more readily than cesium. / Cotton, F. Albert; Gruhn, Nadine E.; Gu, Jiande; Huang, Penglin; Lichtenberger, Dennis L; Murillo, Carlos A.; Van Dorn, Laura O.; Wilkinson, Chad C.

In: Science, Vol. 298, No. 5600, 06.12.2002, p. 1971-1974.

Research output: Contribution to journalArticle

Cotton, FA, Gruhn, NE, Gu, J, Huang, P, Lichtenberger, DL, Murillo, CA, Van Dorn, LO & Wilkinson, CC 2002, 'Closed-shell molecules that ionize more readily than cesium', Science, vol. 298, no. 5600, pp. 1971-1974. https://doi.org/10.1126/science.1078721
Cotton FA, Gruhn NE, Gu J, Huang P, Lichtenberger DL, Murillo CA et al. Closed-shell molecules that ionize more readily than cesium. Science. 2002 Dec 6;298(5600):1971-1974. https://doi.org/10.1126/science.1078721
Cotton, F. Albert ; Gruhn, Nadine E. ; Gu, Jiande ; Huang, Penglin ; Lichtenberger, Dennis L ; Murillo, Carlos A. ; Van Dorn, Laura O. ; Wilkinson, Chad C. / Closed-shell molecules that ionize more readily than cesium. In: Science. 2002 ; Vol. 298, No. 5600. pp. 1971-1974.
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AU - Van Dorn, Laura O.

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