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http://dx.doi.org/10.5012/bkcs.2002.23.2.337

Theoretical Approach for the Equilibrium Structures and Relative Energies of C7H7+ Isomers and the Transition States between o-, m-, and p-Tolyl Cations  

Shin, Chang-Ho (Department of Chemistry, HanNam University)
Park, Kyung-Chun (Department of Chemistry, HanNam University)
Kim, Seung-Joon (Department of Chemistry, HanNam University)
Kim, Byung-Joo (Division of Chemical Metrology and Materials Evaluation, Korea Research Institute of Standards and Science)
Publication Information
Bulletin of the Korean Chemical Society / v.23, no.2, 2002 , pp. 337-345 More about this Journal
Abstract
The equilibrium structures for the ground and transition states of $C_7H_7^+$ isomers have been investigated using sophisticated ab initio quantum mechanical techniques with various basis sets. The structures of tropyrium and benzyl cations have been fully optimized at the DZP CCSD(T) levels of theory. And the structures of o-, m-and p-tolyl cations are optimized fully up to the DZ CCSD(T) levels of theory. The geometries for the transition states between three isomers of tolyl cations have been optimized up to DZP CISD level of theory. The SCF harmonic vibrational frequencies for tropylium, benzyl, and three isomers of tolyl cations are all real numbers, which confirm the potential minima and each unique imaginary vibrational frequencies for TS1 and TS2 confirm the true transition states. The relative energy of the benzyl cation with respect to the tropyrium cation is predicted to be 28.5 kJ/mol and is in good agreement with the previous theoretical predictions. The 0 K heats of formation, ${\Delta}H^{\circ}_{f0}$, have been predicted to be 890, 1095, 1101, and 1110 kJ/mol for tropylium, ortho-, meta-, and para-tolyl cations by taking the experimental value of 919 kJ/mol for the benzyl cation as the base level. The relative stability between tolyl cations is in the order of ortho
Keywords
Ab initio; $C_7H_7^+$; Tolyl; Benzyl; Tropylium;
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1 Morgenthaler, L. N.; Eyler, J. R. Int. J. Mass Spectrom. Ion Processes 1981, 31, 153
2 Traeger, J. C.; Kompe, B. M. Int. J. Mass Spectrom. Ion Processes 1990, 101, 111   DOI   ScienceOn
3 Houle, F. A.; Beauchamp, J. L. J. Am. Chem. Soc. 1978, 100, 3293
4 Mcmillen, D. F.; Golden, D. M. Annu. Rev. Phys. Chem. 1982, 33, 493   DOI   ScienceOn
5 Scheiner, A. C.; Scuseria, G. E.; Rice, J. E.; Lee, T. J.; Schaefer, H. F. J. Chem. Phys. 1987, 87, 5361   DOI
6 Saxe, P.; Yamaguchi, Y.; Schaefer, H. F. J. Chem. Phys. 1982, 77, 5647   DOI
7 Janssen, C. L.; Seidl, E. T.; Scuseria, G. E.; Hamilton, T. P.; Yamaguchi, Y.; Remington, R. B.; Xie, Y.; Vacek, G.; Sherrill, C. D.; Crawford, T. D.; Fermann, J. T.; Allen, W. D.; Brocks, B. R.; Fitzgerald, G. B.; Fox, D. J.; Gaw, J. F.; Handy, N. C.; Laidig, W. D.; Lee, T. J.; Pitzer, R. M.; Rice, J. E.; Saxe, P.; Scheiner, A. C.; Schaefer, H. F. PSI 2.0.8; PSITECH Inc.: Watkinssvills, GA. U.S.A., 1994
8 Kim, B.; Shin, S. K. J. Chem. Phys. 1997, 106, 1411   DOI   ScienceOn
9 Lifshitz, C.; Levin, I.; Kababia, S.; Dunbar, R. C. J. Phys. Chem. 1991, 95, 1667   DOI
10 Shin, S. K.; Han, S. J.; Kim, B. Int. J. Mass Spectrom. Ion Processes 1996, 158, 345   DOI   ScienceOn
11 Choe, J. C.; Kim, M. S. Int. J. Mass Spectrom. Ion Processes 1991, 107, 103   DOI   ScienceOn
12 McLafferty, F. W.; Bockhoff, F. M. Org. Mass Spectrom. 1979, 14, 181   DOI
13 Cho, Y. S.; Kim, M. S.; Choe, J. C. Int. J. Mass Spectrom. Ion Processes 1995, 145, 187   DOI   ScienceOn
14 Olesik, S.; Baer, T.; Morrow, J. C.; Ridal, J. J.; Buschek, J.; Holmes, J. L. Org. Mass Spectrom. 1989, 24, 1008   DOI
15 Jackson, J.-A.; Lias, S. G.; Ausloos, P. J. Am. Chem. Soc. 1977, 99, 7515   DOI
16 Lifshitz, C. Acc. Chem. Soc. 1994, 27, 138   DOI   ScienceOn
17 McLafferty, F. W.; Bockhoff, F. M. J. Am. Chem. Soc. 1979, 101, 1783   DOI
18 Baer, T.; Morrow, J. C.; Shao, J. D.; Olesik, S. J. Am. Chem. Soc. 1988, 110, 5633   DOI
19 Cone, C.; Dewar, J. S.; Landman, D. J. Am. Chem. Soc. 1977, 99, 372   DOI
20 Nicolaides, A.; Radom, L. J. Am. Chem. Soc. 1994, 116, 9769   DOI   ScienceOn
21 Shin, S. K. Chem, Phys. Lett. 1997, 280, 260   DOI   ScienceOn
22 Ignatyev, I. S.; Sundius, T. Chem. Phys. Lett. 2000, 326, 101   DOI   ScienceOn
23 Yamaguchi, Y.; Osamura, Y.; Goddard, J. D.; Schaefer, H. F. A New Dimension to Quantum Chemistry: Analytic Derivative Methods in Ab initio Molecular Electronic structure Theory; Oxford University Press: New York, 1994
24 Huzinaga, S. J. Chem. Phys. 1965, 42, 1293   DOI
25 Dunning, T. H. J. Chem. Phys. 1970, 53, 2823   DOI
26 Dunning, T. H. J. Chem. Phys. 1971, 55, 716   DOI
27 Brooks, B. R.; Laidig, W. D.; Sate, P.; Goddard, J. D.; Yamaguchi, Y.; Schaefer, H. F. J. Chem. Phys. 1980, 72, 4652   DOI
28 Lin, C. Y.; Dunbar, R. C. J. Phys. Chem. 1994, 98, 1369   DOI   ScienceOn
29 Eiden, G. C.; Lu, K.-T.; Badenhoop, J.; Weinhold, F.; Weisshaar, J. C. J. Chem. Phys. 1996, 104, 8886   DOI   ScienceOn
30 Dunbar, R. C. J. Am. Chem. Soc. 1973, 95, 472   DOI
31 Dunbar, R. C.; Honovich, J. P.; Asamoto, B. J. Phys. Chem. 1988, 92, 6935   DOI
32 Dunbar, R. C.; Lifshitz, C. J. Chem. Phys. 1991, 94, 3542   DOI
33 Cabana, A.; Bachand, J.; Giguere, J. Can. J. Phys. 1974, 52, 1949   DOI
34 Grev, R. S.; Janssen, C. L.; Schaefer, H. F. J. Chem. Phys. 1991, 95, 5128   DOI
35 Klots, C. J. Phys. Chem. 1992, 96, 1733   DOI