Closed-shell molecules that ionize more readily than cesium

Science

Volumn 298, Issue 5600, 2002, Pages 1971-1974

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

^a TEXAS A AND M UNIVERSITY   (United States)

^b University of Arizona   (United States)

^c Shanghai Jiao Tong University Affiliated Sixth People s Hospital   (China)

Author keywords

[No Author keywords available]

Indexed keywords

CESIUM; CHEMICAL BONDS; ENTHALPY; ORGANOMETALLICS; SPECTROSCOPIC ANALYSIS;

DELTA BONDING ORBITAL;

IONIZATION;

CESIUM; CHROMIUM; METAL COMPLEX; MOLYBDENUM; TUNGSTEN;

ELECTRON; ION;

ARTICLE; CALCULATION; CHEMICAL BINDING; ELECTRON; ENERGY; ENTHALPY; GAS; IONIZATION; MOLECULAR MODEL; PRIORITY JOURNAL; SOLID STATE; SPECTROSCOPY;

EID: 2242466603     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.1078721     Document Type: Article

References (38)

1. C. E. Davies et al., Inorg. Chem. 31, 3779 (1992).
2. F. A. Cotton, G. Wilkinson, C. A. Murillo, M. Bochmann, Advanced Inorganic Chemistry (Wiley, New York, ed. 6, 1999).
3. C. E. Moore, Ionization Potentials and Ionization Limits Derived from the Analysis of Optical Spectra (NSRDS-NBS 34, National Bureau of Standards, Washington, DC, 1970).
4. It is to be emphasized that the molecules reported here are real molecules, which can be made in gram quantities and stored in inert atmosphere at room temperature indefinitely. Previous discussions of so-called "superatkati" compounds are purely theoretical discussions of molecules not known to exist (5, 6).
5. G. L. Gutsev, A. I. Boldyrev, Chem. Phys. Lett. 9, 262 (1982)
6. D. Moran et al., J. Phys. Chem. A 106, S 144 (2002)
7. F. A. Cotton, D. J. Timmons, Polyhedron 17, 179 (1998).
8. F. A. Cotton, L. M. Daniels, C. A. Murillo, D. J. Timmons, C. C. Wilkinson, J. Am. Chem. Soc. 124, 9249 (2002).
9. C. Lin, J. D. Protasiewicz, E. T. Smith, T. Ren, Inorg. Chem. 35, 6422 (1996).
10. F. A. Cotton et al., unpublished data.
11. F. A. Cotton, R. A. Walton, Multiple Bonds Between Metal Atoms (Oxford Univ. Press, New York, ed. 2, 1992).
12. F. A. Cotton, P. Huang, C. A. Murilo, D. J. Timmons, Inorg. Chem. Comm. 5, 501 (2002).
13. F. A. Cotton, P. Huang C. A. Murillo, X. Wang, Inorg. Chem. Comm., in press.
14. 4Mo bonds, see F. A. Cotton, L. M. Daniels, E. A. Hillard, C. A. Murillo, Inorg. Chem. 41, 2466 (2002).
15. B. L. Westcott, N. E. Gruhn, J. H. Enemark, J. Am. Chem. Soc. 120, 3382 (1998).
16. 4 molecule was also obtained with the He II photon source, showing that the first ionization band is not produced indirectly by any absorptive or other resonance process dependent on the energy of the excitation source.
17. M. E. Jatcko, thesis, The University of Arizona, Tucson, AZ (1989).
18. I. Novak, W. Wei, J. Phys. Chem. A 105, 1783 (2001).
19. D. L. Lichtenberger, A. S. Copenhaver, J. Electron Spectrosc. Relat. Phenom. 50, 335 (1990).
20. 1/2 ionization at 9.538 eV was used to calibrate the IE scale. For a convenient additional internal calibration of the energy scale close to the Low first IEs of these molecules, the discharge lamp was operated under conditions that allowed observation of the He self-ionization produced by He II photons (40.814 eV) from the source ionizing He atoms (IE, 24.587 eV) in the sample cell The 16.227 eV kinetic energy of these electrons produce a peak at an apparent binding energy of 4.992 eV on the He I photoelectron spectrum scale.
21. D. L. Lichtenberger, M. A. Lynn, M. H. Chisholm, J. Am. Chem. Soc. 121, 12167 (1999).
22. W. C. Martin, W. L. Wiese, in Atomic, Molecular & Optical Physics Handbook; G. W. F. Drake, Ed. (American Institute of Physics, Woodbury, NY, 1996), pp. 135-153.
23. W. C. Martin, A. Musgrove, S. Kotochigova, Ground Levels and Ionization Energies for the Neutral Atoms (National Institute of Standards and Technology, Gaithersburg MD) (see http://physics.nist.gov/ IonEnergy).
24. J. C. Green et al., Organometallics 2, 211 (1983).
25. C. Cauletti et al., J. Electron. Spectrosc. Relat. Phenom. 19, 327 (1980).
26. D. O'Hare et al., Organometallics 11, 48 (1992).
27. M. M. Kappes, M. Schär, E. Schumacher, J. Phys. Chem. 89, 1499 (1985)
28. M. M. Kappes, P. Radi, M. Schär, E. Schumacher, Chem. Phys. Lett. 113, 243 (1985).
29. Standard 6-31G(d) basis sets were used for the non-metal elements (30). A [7s5p3d] contraction of the (16s10p7d) primitive set by Huzinaga plus one p polarization function was used for Mo, and a [8s6p4d2f] contraction of the (15s10p9d3f) with one p function was used for W in the calculations (31).
30. W. J. Hehre, L. Radom, P. R. Schleyer, J. A. Pople, Ab initio Molecular Orbital Theory (Wiley, New York, 1986).
31. S. Huzinaga, Gaussian Basis Sets for Molecular Calculations (Elsevier, Amsterdam, 1984)
32. A. D. Becke, J. Chem. Phys. 98, 5648 (1993)
33. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 37, 785 (1988).
34. B. Miehlich, A. Sacin, H. Stoll, H. Preuss, Chem. Phys. Lett. 157, 200 (1989).
35. The Gaussian 98 package (36) of programs was used in the calculations.
36. M. J. Frisch, et al., Gaussian 98, Revision A.9 (Gaussian, Pittsburgh PA, 1998).
37. 2 compounds is in excellent accord with the experimental observation of 0.095 Å.
38. Supported at Texas A&M University by the Robert A. Wetch Foundation, the Laboratory for Molecular Structure and Bonding; at the University of Arizona by the Department of Energy (Division of Chemical Science, Office of Basic Energy Sciences, Office of Energy Research, grant DE-FG03-95ER14574); by NSF (grant no. 0078457); by the Materials Characterization Program, Department of Chemistry, the University of Arizona; and in Shanghai by the Knowledge Innovation Program and the Introducing Outstanding Overseas Scientists Project, Chinese Academy of Sciences.