The microwave spectrum, ab initio analysis, and structure of the fluorobenzene–hydrogen chloride complex
dc.contributor.author | Sanz, M. Eugenia | en_US |
dc.contributor.author | Antolínez, Sonia | en_US |
dc.contributor.author | Alonso, José L. | en_US |
dc.contributor.author | López, Juan C. | en_US |
dc.contributor.author | Kuczkowski, Robert L. | en_US |
dc.contributor.author | Peebles, Sean A. | en_US |
dc.contributor.author | Peebles, Rebecca A. | en_US |
dc.contributor.author | Boman, Faith C. | en_US |
dc.contributor.author | Kraka, Elfi | en_US |
dc.contributor.author | Cremer, Dieter | en_US |
dc.date.accessioned | 2010-05-06T23:35:25Z | |
dc.date.available | 2010-05-06T23:35:25Z | |
dc.date.issued | 2003-05-22 | en_US |
dc.identifier.citation | Sanz, M. Eugenia; Antolínez, Sonia; Alonso, José L.; López, Juan C.; Kuczkowski, Robert L.; Peebles, Sean A.; Peebles, Rebecca A.; Boman, Faith C.; Kraka, Elfi; Cremer, Dieter (2003). "The microwave spectrum, ab initio analysis, and structure of the fluorobenzene–hydrogen chloride complex." The Journal of Chemical Physics 118(20): 9278-9290. <http://hdl.handle.net/2027.42/71342> | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/71342 | |
dc.description.abstract | The fluorobenzene–hydrogen chloride π-hydrogen-bonded complex has been studied by high resolution microwave spectroscopy and ab initio calculations. Rotational spectra of the C6H5F–H35Cl,C6H5F–H35Cl, C6H5F–H37Cl,C6H5F–H37Cl, and C6D5F–H35ClC6D5F–H35Cl isotopomers were assigned using pulsed molecular beam techniques in a Fourier-transform microwave spectrometer. The spectra are consistent with a structure of the complex in which the HCl is above the fluorobenzene ring near the ring center, similar to the benzene–HCl prototype dimer. An analysis of the inertial data and the chlorine quadrupole coupling tensor results in two mathematically possible locations for the HCl subunit with respect to the fluorobenzene arising from sign ambiguities in interpreting the spectral constants. One structure has the HCl nearly perpendicular to the aromatic ring; the other has the HCl pointing toward the fluorine end of the ring. Spectral intensities for the μaμa and μbμb transitions favor the former configuration. Ab initio calculations (MP2/6-311++G(2df,2pd)+BSSE corrections) indicate that the position of the HCl is driven by electrostatic interactions with the π electrons of the benzene ring. HCl is shifted by 0.16 Å from the center of the ring toward the para-C atom, where the π density is significantly higher. In the equilibrium form, HCl is tilted by δ=14° from perpendicular to the ring with the hydrogen end toward the para-C atom. The H atom can perform an internal rotation or at least a half-circular libration (barriers smaller than 100 cm−1). An average δ value of 0.7° is estimated in reasonable agreement with the derived vibrationally averaged value of 3.8°. The complex binding energy ΔEΔE calculated at the CCSD(T)/6-311++G(2df,2pd)+CP(BSSE) level of theory is 2.8 kcal/mol, suggesting a lower ΔEΔE value for benzene–HCl than previously reported. Fluorobenzene–HCl possesses some charge transfer character; however, just 5.5 melectron are transferred from the benzene ring to HCl. In view of this, π–H bonding in fluorobenzene–HCl is predominantly electrostatic rather than covalent in character contrary to claims made in connection with benzene–HCl. © 2003 American Institute of Physics. | en_US |
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dc.format.extent | 357390 bytes | |
dc.format.mimetype | text/plain | |
dc.format.mimetype | application/pdf | |
dc.publisher | The American Institute of Physics | en_US |
dc.rights | © The American Institute of Physics | en_US |
dc.title | The microwave spectrum, ab initio analysis, and structure of the fluorobenzene–hydrogen chloride complex | en_US |
dc.type | Article | en_US |
dc.subject.hlbsecondlevel | Physics | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109-1055 | en_US |
dc.contributor.affiliationother | Departamento de Química Física, Facultad de Ciencias, Universidad de Valladolid, 47005, Valladolid, Spain | en_US |
dc.contributor.affiliationother | Department of Theoretical Chemistry, Göteborg University, S-41320 Göteborg, Reutersgatan 2, Sweden | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/71342/2/JCPSA6-118-20-9278-1.pdf | |
dc.identifier.doi | 10.1063/1.1567714 | en_US |
dc.identifier.source | The Journal of Chemical Physics | en_US |
dc.identifier.citedreference | P. Tarakeshwar, S. J. Lee, J. Y. Lee, and K. S. Kim, J. Chem. Phys. JCPSA6108, 7217 (1998). | en_US |
dc.identifier.citedreference | H. S. Gutowsky, E. Arunan, T. Emilsson, S. L. Tschopp, and C. E. Dykstra, J. Chem. Phys. JCPSA6103, 3917 (1995). | en_US |
dc.identifier.citedreference | S. A. Cooke, G. K. Corlett, C. M. Evans, and A. C. Legon, Chem. Phys. Lett. CHPLBC272, 61 (1997). | en_US |
dc.identifier.citedreference | W. G. Read, E. J. Campbell, G. Henderson, and W. H. Flygare, J. Am. Chem. Soc. JACSAT103, 7670 (1981); W. G. Read, E. J. Campbell, and G. Henderson, J. Chem. Phys. JCPSA678, 3501 (1983). | en_US |
dc.identifier.citedreference | A. J. Gotch and T. S. Zwier, J. Chem. Phys. JCPSA693, 6977 (1990). | en_US |
dc.identifier.citedreference | F. A. Baiocchi, J. H. Williams, and W. Klemperer, J. Phys. Chem. JPCHAX87, 2079 (1983). | en_US |
dc.identifier.citedreference | E. A. Walters, J. R. Grover, M. G. White, and E. T. Hui, J. Phys. Chem. JPCHAX89, 3814 (1985). | en_US |
dc.identifier.citedreference | Y-H. Zhang, J-K. Hao, X. Wang, W. Zhou, and T-H. Tang, J. Mol. Struct.: THEOCHEM THEODJ455, 85 (1998). | en_US |
dc.identifier.citedreference | (a) B. V. Cheney and M. W. Schulz, J. Phys. Chem. JPCHAX94, 6268 (1990); (b) B. V. Cheney, M. W. Schulz, J. Cheney, and W. G. Richards, J. Am. Chem. Soc. JACSAT110, 4195 (1988). | en_US |
dc.identifier.citedreference | A. M. Sapse and D. C. Jain, J. Phys. Chem. JPCHAX88, 4970 (1984). | en_US |
dc.identifier.citedreference | W. O. George, Rh. Lewis, G. Hussain, and G. J. Rees, J. Mol. Struct. JMOSB4189, 211 (1988). | en_US |
dc.identifier.citedreference | M. P. Henry and A. N. Hambly, Aust. J. Chem. AJCHAS20, 1887 (1967). | en_US |
dc.identifier.citedreference | D. M. Upadhyay, M. K. Shukla, and P. C. Mishra, J. Mol. Struct.: THEOCHEM THEODJ531, 249 (2000). | en_US |
dc.identifier.citedreference | C. Petrongolo and J. Tomasi, Int. J. Quantum Chem., Quantum Biol. Symp. IJQBDZ2, 181 (1975). | en_US |
dc.identifier.citedreference | R. A. Appleman, S. A. Peebles, and R. L. Kuczkowski, J. Mol. Struct. JMOSB4446, 55 (1998). | en_US |
dc.identifier.citedreference | R. J. Wilson, S. A. Peebles, S. Antolínez, M. E. Sanz, and R. L. Kuczkowski, J. Phys. Chem. A JPCAFH102, 10630 (1998). | en_US |
dc.identifier.citedreference | T. J. Balle and W. H. Flygare, Rev. Sci. Instrum. RSINAK52, 33 (1981). | en_US |
dc.identifier.citedreference | (a) R. J. McMahon, R. J. Halter, R. L. Fimmen, R. J. Wilson, S. A. Peebles, R. L. Kuczkowski, and J. F. Stanton, J. Am. Chem. Soc. JACSAT122, 939 (2000); (b) J. L. Alonso, F. J. Lorenzo, J. L. López, A. Lesarri, S. Mata, and H. Dreizler, Chem. Phys. CMPHC2218, 267 (1997). | en_US |
dc.identifier.citedreference | (a) W. Gordy and R. L. Cook, Microwave Molecular Spectra, 3rd ed. (Wiley-Interscience, New York, 1984); (b) H. M. Pickett, J. Mol. Spectrosc. JMOSA3148, 371 (1991). | en_US |
dc.identifier.citedreference | See EPAPS Document No. E-JCPSA6-118-003320for Tables S1, S2 (measured transitions) and Table S3 (coordinates). A direct link to this document may be found in the online article’s HTML reference section. The document may also be reached via the EPAPS homepage (http://www.aip.org/pubservs/epaps.html) or from ftp.aip.org in the directory /epaps/. See the EPAPS homepage for more information. | en_US |
dc.identifier.citedreference | (a) S. Doraiswamy and S. D. Sharma, J. Mol. Struct. JMOSB4102, 81 (1983); (b) A. C. Legon and D. J. Millen, Proc. R. Soc. London, Ser. A PRLAAZ417, 21 (1988); (c) A. C. Legon, Faraday Discuss. ZZZZZZ97, 19 (1994); (d) R. H. Schwendeman, in Critical Evaluation of Chemical and Physical Structural Information, edited by D. R. Lide and M. A. Paul (National Academy of Sciences, Washington, DC, 1974). | en_US |
dc.identifier.citedreference | F. H. de Leeuw and A. Dymanus, J. Mol. Spectrosc. JMOSA348, 427 (1973). | en_US |
dc.identifier.citedreference | (a) C. Møller and M. S. Plesset, Phys. Rev. PHRVAO46, 618 (1934).(b) For a recent review, see D. Cremer, in Encyclopedia of Computational Chemistry, edited by P. V. R. Schleyer, N. L. Allinger, T. Clark, J. Gasteiger, P. A. Kollman, H. F. Schaefer, III, and P. R. Schreiner (Wiley, Chichester, UK, 1998), Vol. 3, p. 1706. | en_US |
dc.identifier.citedreference | K. Raghavachari, G. W. Trucks, J. A. Pople, and M. Head-Gordon, Chem. Phys. Lett. CHPLBC157, 479 (1989). | en_US |
dc.identifier.citedreference | M. A. Spackman, J. Phys. Chem. JPCHAX93, 7594 (1989). The 6-31G(+sd,+sp) basis was derived by Spackman by adding to Pople’s 6-31G basis (Ref. 27) diffuse polarization functions as well as a diffuse s-function. Spackman optimized the exponents of the d-type polarization functions for first- and second-row atoms as well as of the p-type polarization functions for hydrogen in the way that the mean polarizability of first- and second-row AHnAHn hydrides is maximized. | en_US |
dc.identifier.citedreference | Basis 6-31G(d,p): P. C. Hariharan and J. A. Pople, Chem. Phys. Lett. CHPLBC16, 217 (1972). | en_US |
dc.identifier.citedreference | Basis 6-311++G(2df,2pd): R. Krishnan, M. Frisch, and J. A. Pople, J. Chem. Phys. JCPSA672, 4244 (1980). | en_US |
dc.identifier.citedreference | For a review on the basis set superposition problem, see F. B. van Duijneveldt, J. G. C. M. van Duijneveldt-van de Rijdt, and J. H. van Lenthe, Chem. Rev. CHREAY94, 1873 (1994). | en_US |
dc.identifier.citedreference | J. J. Oh, I. Park, R. J. Wilson, S. A. Peebles, R. L. Kuczkowski, E. Kraka, and D. Cremer, J. Chem. Phys. JCPSA6113, 9051 (2000). | en_US |
dc.identifier.citedreference | (a) E. Kraka, D. Cremer, U. Spoerel, I. Merke, W. Stahl, and H. Dreizler, J. Phys. Chem. JPCHAX99, 12466 (1995); (b) U. Spoerel, H. Dreizler, W. Stahl, E. Kraka, and D. Cremer, 100, 14298 (1996). | en_US |
dc.identifier.citedreference | S. F. Boys and F. Bernardi, Mol. Phys. MOPHAM19, 553 (1970). | en_US |
dc.identifier.citedreference | (a) J. E. Carpenter and F. Weinhold, J. Mol. Struct.: THEOCHEM THEODJ169, 41 (1988); (b) A. E. Reed, R. B. Weinstock, and F. Weinhold, J. Chem. Phys. JCPSA683, 735 (1985).(c) A. E. Reed, L. A. Curtiss, and F. Weinhold, Chem. Rev. CHREAY88, 899 (1988). | en_US |
dc.identifier.citedreference | E. Kraka, J. Gräfenstein, J. Gauss, F. Reichel, L. Olsson, Z. Konkoli, Z. He, Y. He, and D. Cremer, COLOGNE2000, Göteborg University, Göteborg, 2000. | en_US |
dc.identifier.citedreference | (a) J. F. Stanton, J. Gauss, J. D. Watts, W. J. Lauderdale, and R. J. Bartlett, ACES II, Quantum Theory Project, University of Florida, 1992. (b) See also J. F. Stanton, J. Gauss, J. D. Watts, W. J. Lauderdale, and R. J. Bartlett, Int. J. Quantum Chem., Symp. ZZZZZZ26, 879 (1992). | en_US |
dc.identifier.citedreference | P. Salvador, S. Simon, M. Duran, and J. J. Dannenberg, J. Chem. Phys. JCPSA6113, 5666 (2000). | en_US |
dc.identifier.citedreference | P. Tarakeshwar, K. S. Kim, E. Kraka, and D. Cremer, J. Chem. Phys. JCPSA6115, 6018 (2001). | en_US |
dc.identifier.citedreference | E. Kraka, D. Cremer, and R. L. Kuczkowski, (unpublished). | en_US |
dc.owningcollname | Physics, Department of |
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