Abstract
A study of internal rotation in the radicals n-C n H2n+1C·H2, (2 ≤ n ≤ 7) was carried out for the case of rotation around the bonds not including the radical center. 21 potential functions of internal rotation V(φ) were calculated. The coefficients in V(φ) were shown to depend only on the immediate environment at the bond of rotation. Characteristics of internal rotation in n-alkyl radicals were compared with related parameters of the corresponding alkane molecules. The generalized function V av(φ) with the coefficients defined only by the position of the bond of rotation in the hydrocarbon chain and possessing the transposition property were proposed. The functions V av(φ) were recommended for the simulation of the structure and properties of large molecules containing hydrocarbon fragments. This work continues a systematic study on the characteristics of the internal rotation in the n-alkane molecules and the groups containing free valence in n-alkyl radicals.
Similar content being viewed by others
References
Turovtsev, V.V., Orlov, Yu.D., Kizin, A.N., and Lebedev, Yu.A., Zh. Obshch. Khim., 2007, vol. 77, no. 9, p. 1508.
Turovtsev, V.V. and Orlov, Yu.D., Zh. Obshch. Khim., 2010, vol. 80, no. 4, p. 588.
Helgaker, T., Jorgensen, P., and Olsen, J., Molecular Electronic-Structure Theory, Chichester: Wiley, 2000.
Orlov, M.Yu., Turovtsev, V.V., and Orlov, Yu.D., Vestnik Bashkirskogo Univ., 2008, vol. 13. no. 3(I), p. 758.
East, A.L. and Radom, L., J. Chem. Phys., 1997, vol. 106, no. 16, p. 6655.
Internal Rotation in Molecules, Orville-Thomas, W.Y., Ed., Moscow: Mir, 1977.
Chung-Phillips, A., J. Comput. Chem., 1992, vol. 13, p. 874
Chung-Phillips, A., J. Molecular Structure (Theochem.), 1992, vol. 257, p. 417.
Feller, D., J. Comput. Chem., 1996, vol. 17, no. 13, p. 1571.
Schuchardt, K.L., Didier, B.T., Elsethagen, T., Sun, L., Gurumoorthi, V., Chase, J., Li, J., and Windus, T.L., J. Chem. Inf. Model., 2007, vol. 47, no. 3, p. 1045.
Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, J.A., Jr., Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M., Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J.E., Hratchian, H.P., Cross, J.B., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Ayala, P.Y., Morokuma, K., Voth, G.A., Salva-dor, P., Dannenberg, J.J., Zakrzewski, V.G., Daniels, A.D., Farkas, O., Rabuck, A.D., Raghavachari, K., and Ortiz, J.V., Gaussian 03, Revision E0.1, Gaussian Inc., Pittsburgh PA, 2007.
Granovsky, A.A., PC GAMESS/Firefly version 7.1.F, http://classic.chem.msu.su/gran/gamess/index.html.
Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T., Gordon, M.S., Jensen, J.H., Koseki, S., Matsunaga, N., Nguyen, K.A., Su, S., Windus, T.L., Dupuis, M., and Montgomery, J.A., J. Comput. Chem., 1993, vol. 14, no. 11, p. 1347.
Peng, C. and Schlegel, H.B., Israel. J. of Chem., 1993, vol. 33, p. 449.
Peng, C., Ayala, P.Y., Schlegel, H.B., and Frisch, M.J., J. Comput. Chem., 1996, vol. 17, p. 49.
Vereshchagin, A.N., Induktivnyi effekt (Inductive Effect), Moscow: Nauka, 1987.
Höltje H-D., Sippl, W., Rognan, D., and Folkers, G., Molecular Modeling: Basic Principles and Applications, Moscow: Binom, Laboratoriya Znanii, 2010.
Turovtsev, V.V., and Orlov, Yu.D., Lebedev, Yu.A., Zh. Fiz. Khim., 2009, vol. 83, no. 2, p. 313.
Matta, C.F., Castillo, N., and Boyd, R., J. Chem. Phys., 2006, vol. 125, no. 20, p. 204103.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © V.V. Turovtsev, Yu.D. Orlov, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 9, pp. 1458–1464.
Rights and permissions
About this article
Cite this article
Turovtsev, V.V., Orlov, Y.D. Effect of free valence on the characteristics of internal rotation in n-alkyl radicals. Russ J Gen Chem 81, 1798 (2011). https://doi.org/10.1134/S1070363211090118
Received:
Published:
DOI: https://doi.org/10.1134/S1070363211090118