Abstract
To reveal the reasons for the previously found absence of end radicals upon γ-radiolysis ofn-heptane polycrystals, we performed quantum-chemical calculations (SCF-MO, RHF, 6-31G* basis set) of then-heptane molecule and its four radicals. The energies of the crystal lattice were calculated by the atom-atom potential method. Comparison of the experimental and calculated data showed that the absence of the end radicals is not related to the intermolecular interaction in the crystals. The most probable reason for the selective radical formation upon radiolysis can be a transfer of the excitation energy within then-heptane molecule occurring before the radical formation.
Similar content being viewed by others
References
S. R. Allayarov and I. M. Barkalov,Izv. Akad. Nauk, Ser. Khim., 2000, 1034 [Russ. Chem. Bull., Int. Ed., 2000,49, 1028 (Engl. Transl.)].
A. M. Merle, M. Lamotte, S. Risemberg, C. Hauw, J. Gaultier, and J. Ph. Crivet,Chem. Phys., 1977,22, 207.
G. Filippini and A. Gavezzotti,Acta Crystallogr., 1993,B49, 868.
V. G. Dashevskii,Konformatsionnyi analiz organicheskikh molekul [Conformational Analysis of Organic Molecules], Khimiya, Moscow, 1982, 396 pp. (in Russian).
M. Dole and C. D. Keeling,J. Am. Chem. Soc., 1953,75, 6082.
P. Yu. Butyagin,Dokl. Akad. Nauk SSSR [Reports Acad. Sci. USSR], 1965,165, 103 (in Russian).
J. Kircher,J. Phys. Chem., 1965,69, 189.
M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. J. Su, T. L. Windus, M. Dupuis, and J. A. Montgomery,J. Comput. Chem., 1993,14, 1347.
T. Clark,A Handbook of Computational Chemistry, Wiley, New York, 1985, 384 pp.
A. Horsfield, J. R. Moton, and D. H. Whiffen,Mol. Phys., 1961,4, 425.
C. Heller and H. M. McConnell,J. Chem. Phys., 1960,32, 1535.
V. A. Radtsig, Ph. D. (Chem.) Thesis, Institute of Chemical Physics, Academy of Sciences of the USSR, Moscow, 1969, 7 (in Russian).
J. J. P. Stewart,QCPE, No. 455.
A. I. Dzyabchenko,Kristallografiya, 1983,28, 788 [Sov. Phys.-Crystallogr., 1983,28 (Engl. Transl.)].
A. J. Pertsin and A. J. Kitaigorodskii,The Atom-Atom Potential Method, Springer-Verlag, Berlin, 1987, 69.
V. A. Zakrevskii, V. V. Baptizmanskii, and E. Yu. Tomashevskii,Fizika Tverdogo Tela, 1967,9, 1434 [Sov. Phys. Sol. State, 1967,9 (Engl. Transl.)].
V. A. Zakrevskii, V. V. Baptizmanskii, and E. Yu. Tomashevskii,Fizika Tverdogo Tela, 1968,10, 1699 [Sov. Phys. Sol. State, 1968,10 (Engl. Transl.)].
V. A. Radtsig and P. Yu. Butyagin,Vysokomolekulyar. Soedin., 1967,9A, 2549 [Polym. Sci., Ser. A, 1967 (in Russian)].
P. Yu. Butyagin, A. M. Dubinskaya, and V. A. Radtsig,Usp. Khim., 1969,38, 593 [Russ. Chem. Rev., 1969,38 (Engl. Transl.)].
P. B. Ayscough and C. Thomson,Trans. Farad. Soc., 1962,58, 1477.
J. Henderson and J. E. Williard,J. Am. Chem. Soc., 1969,91, 3014.
P. B. Ayscough, R. G. Collins, and F. S. Dainton,Nature, 1965,205, 965.
Author information
Authors and Affiliations
Additional information
For Part 1, see Ref. 1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1038–1042, June, 2000.
Rights and permissions
About this article
Cite this article
Allayarov, S.R., Konovalikhin, S.V. A study of alkyl radicals in the matrix of polycrystallinen-alkane irradiated at 77 K. Russ Chem Bull 49, 1032–1036 (2000). https://doi.org/10.1007/BF02494890
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF02494890