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2007 | 112 | S | S-19-S-38
Article title

Proton Transfer in Strong Hydrogen Bonds Revealed by Infrared Spectra - Correlations between Structure and Spectra for the BrH : NH_3 Complex

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Our scope is to achieve an understanding of the relation between the infrared spectrum and structure of a strong hydrogen-bonded complex, BrH : NH$_3$, and how and why this relationship is affected by the environment surrounding the complex. A series of DFT/B3LYP/6-31G(d,p) calculations was carried out for this system to obtain its structure and spectrum in different dielectric fields characterized by their relative permittivities. Changes in structure and spectrum (both frequencies and intensities) as the relative permittivity changes are explored. Calculations of spectra are made first under the harmonic approximation. In the next step the effect of anharmonicity was estimated for several different dielectric fields. The calculated anharmonic spectrum (for ε_r = 1.6) is compared with the experimentally observed infrared spectrum of the complex isolated in an Ar matrix at 10 K, obtained in our laboratory. The calculated frequencies and relative intensities for all normal modes agree with the corresponding experimental data surprisingly well. The potential usefulness of structure-spectra correlations is explored.
  • Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, Florida, 32611, USA
  • Department of Chemistry, University of Florida, P.O. Box 117200, Gainesville, Florida, 32611, USA
  • 1. J.E. Del Bene, M.J.T. Jordan, P.M.W. Gill, A.D. Buckingham, Mol. Phys., 92, 429, 1997
  • 2. A.J. Barnes, Z. Latajka, M. Biczysko, J. Mol. Struct., 614, 11, 2002
  • 3. M.J.T. Jordan, J.E. Del Bene, J. Am. Chem. Soc., 122, 2101, 2000
  • 4. A. Abkowicz-Bienko, M. Biczysko, Z. Latajka, Comput. Chem., 24, 303, 2000
  • 5. L. Andrews, X. Wang, J. Phys. Chem. A, 105, 6420, 2001
  • 6. K. Szczepaniak, P. Chabrier, W.B. Person, J.E. Del Bene, J. Mol. Struct., 436-437, 367, 1997
  • 7. K. Szczepaniak, P. Chabrier, W.B. Person, J.E. Del Bene, J. Mol. Struct., 520, 1, 2000
  • 8. K. Szczepaniak, M.M. Szczesniak, W.B. Person, J. Phys. Chem. A, 104, 3852, 2000
  • 9. W.B. Person, K. Szczepaniak, J.S. Kwiatkowski, Int. J. Quant. Chem., 90, 995, 2002
  • 10. K. Szczepaniak, W.B. Person, D. Hadzi, J. Phys. Chem. A, 109, 6710, 2005
  • 11. Gaussian 98, Revision A.9, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, V.G. Zakrzewski, J.A. Montgomery, Jr., R.E. Stratmann, J.C. Burant, S. Dapprich, J.M. Millam, A.D. Daniels, K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G.A. Petersson, P.Y. Ayala, Q. Cui, K. Morokuma, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. Cioslowski, J.V. Ortiz, A.G. Baboul, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, J.L. Andres, C. Gonzalez, M. Head-Gordon, E.S. Replogle, J.A. Pople, Gaussian, Inc., Pittsburgh PA, 1998
  • 12. I. Mills, T. Cvitas, K. Homann, N. Kallay, K. Kuchitsu, Quantities, Units and Symbols in Physical Chemistry, 2nd ed., International Union of Pure and Applied Chemistry, Blackwell Science, Oxford 1993
  • 13. A.E. Frisch, M.J. Frisch, Gaussian 98, User's Reference, 2nd ed., Gaussian Inc., Pittsburgh, PA 1999
  • 14. R.I. Somorjai, D.F. Hornig, J. Chem. Phys., 36, 1980, 1962
  • 15. P. Chabrier, Ph.D. Thesis, University of Florida, 1998
  • 16. L. Abouaf-Marguin, M.E. Jacox, D.E. Milligan, J. Mol. Spectrosc., 67, 34, 1977
  • 17. A.J. Barnes, M.P. Wright, J. Chem. Soc., Faraday Trans. 2, 82, 153, 1986
  • 18. H.E. Hallam, G.F. Scrimshaw, in: Vibrational Spectroscopy of Trapped Species, Ed. H.E. Hallam, Wiley, New York 1973, p. 45
  • 19. D.M. Kolb, F. Forstmann, in: Matrix Isolation Spectroscopy, Eds. A.J. Barnes, W.J. Orville-Thomas, A. Muller, R. Gaufres, NATO ASI Series C, Vol. 76, D. Reidel, Dordrecht, The Netherlands 1981, p. 350
  • 20. S. Pilla, J.A. Hameda, K.A. Muttalib, N.S. Sullivan, Phys. Lett. A, 256, 75, 1999
  • 21. G. Herzberg, Molecular Spectra and Molecular Structure I. Diatomic Molecules, 2nd ed., Van Nostrand, New York 1950, p. 534
  • 22. E.L. Wagner, D.F. Hornig, J. Chem. Phys., 18, 305, 1950
  • 23. W.C. Hamilton, J.A. Ibers, Hydrogen Bonding in Solids, W.A. Benjamin, Inc., New York 1961, p. 224-6
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