Abstract
The supermolecule method was used to describe the mechanism of liquid-phase processes taking the reaction of ethylene carbonate with methylamine as an example. Specific features of the approach are considered. The problem of choosing the reference point for calculating the relative energies of individual reaction steps was solved by introducing the idea of the structure of noninteracting solvated reactants. In this case, no basis set superposition error (BSSE) correction is required because the solvated reactants, the pre-reaction complex, and the transition state have the same atomic composition and are calculated in the same basis set. To calculate the title reaction in dioxane by the supermolecule method with acceptable accuracy, it is sufficient to consider one solvent molecule.
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B. Ya. Simkin, I. I. Sheichet, Kvantovo-Khimicheskaya i statisticheskaya teoriya rastvorov. Vychislitelnye metody i ikh primenenie [Quantum Chemical and Statistical Theory of Solutions. Computational Methods and Their Applications], Khimiya, Moscow, 1989, 256 pp. (in Russian).
M. V. Bazilevskii, V. I. Faustov, Russ. Chem. Rev., 1992, 61, 651.
Quantum Theory of Chemical Reactions, Eds R. Daudel, A. Pullman, L. Salem, A. Veillard, D. Reidel Publishing Company, Dordrecht—Boston—London, 1980, Vol. II, p. 1—24.
S. Glasstone, K. J. Laidler, H. Eyring, The Theory of Rate Processes. The Kinetics of Chemical Reactions, Viscosity, Diffusion and Electrochemical Phenomena, McGraw-Hill, New York—London, 1941, 611 pp.
K. J. Laidler, Reaction Kinetics, Homogeneous Gas Reactions, Pergamon Press, Oxford—London—New York—Paris, 1963, Vol. I, 242 pp.
A. M. North, The Collision Theory of Chemical Reactions in Liquids, Methuen, London—New York, 1964, 145 pp.
S. G. Entelis, R. P. Tiger, Reaction Kinetics in the Liquid Phase, J. Wiley and Sons, New York—Toronto, 1976, 362 pp.
J. Frenkel, Kinetic Theory of Liquids, Clarendon Press, Oxford, 1946, 488 pp.
M. V. Zabalov, R. P. Tiger, A. A. Berlin, Dokl. Phys. Chem. (Engl. Transl.), 2011, 441, 355 [Dokl. Akad. Nauk, 2011, 441, 480].
M. V. Zabalov, R. P. Tiger, A. A. Berlin, Russ. Chem. Bull. (Int. Ed.), 2012, 61, 518 [Izv. Akad. Nauk, Ser. Khim., 2012, 518].
M. V. Zabalov, M. A. Levina, V. G. Krasheninnikov, R. P. Tiger, Russ. Chem. Bull. (Int. Ed.), 2014, 63, 1740 [Izv. Akad. Nauk, Ser. Khim., 2014, 1740].
M. A. Levina, V. G. Krasheninnikov, M. V. Zabalov, R. P. Tiger, Polym. Sci., Ser. B (Engl. Transl.), 2014, 56, 139 [Vysokomolekular. Soedineniya, Ser. B, 2014, 56, 152].
J. P. Perdew, K. Burke, M. Ernzerhoff, Phys. Rev. Lett., 1996, 77, 3865.
M. Ernzerhoff, G. E. Scuseria, J. Chem. Phys., 1999, 110, 5029.
D. N. Laikov, Chem. Phys. Lett., 1997, 281, 151.
D. N. Laikov, Yu. A. Ustynuk, Russ. Chem. Bull. (Int. Ed.), 2005, 54, 820 [Izv. Akad. Nauk, Ser. Khim., 2005, 804].
A. D. Becke, J. Chem. Phys., 1993, 98, 5648.
A. A. Granovsky, Firefly version 8.0.0, wwwhttp://classic. chem.msu.su/gran/firefly/index.html.
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. Su, T. L. Windus, M. Dupuis, J. A. Montgomery, J. Comput. Chem., 1993, 14, 1347.
S. F. Boys, F. Bernardi, Mol. Phys., 1970, 19, 553.
C. J. Cramer, Essentials of Computational Chemistry. Theories and Models, 2nd ed., John Wiley and Sons, Chichester, 2004, p. 196.
F. B. van Duijneveldt, J. G. C. M. van Duijneveldt-van de Rijdt, J. H. van Lenthe, Chem. Rev., 1994, 94, 1873.
S. Simon, M. Duran, J. J. Dannenberg, J. Chem. Phys., 1996, 105, 11024.
N. Kobko, J. J. Dannenberg, J. Phys. Chem. A, 2001, 105, 1944.
A. Kaczmarek, A. J. Sadley, J. Leszczynski, J. Chem. Phys., 2004, 120, 7837.
A. J. C. Varandas, Theor. Chem. Acc., 2008, 119, 544.
R. M. Balabin, J. Chem. Phys., 2008, 129, 164101.
E. Papajak, H. R. Leverentz, J. Zheng, D. G. Truhlar, J. Chem. Theory Comput., 2009, 5, 1197.
J. R. Alvarez-Idaboy, A. Galano, Theor. Chem. Acc., 2010, 126, 75.
H. Kruse, S. Grimme, J. Chem. Phys., 2012, 136, 154101.
T. Schwabe, J. Phys. Chem. A, 2013, 117, 2879.
L. M. Mentel, E. J. Baerends, J. Chem. Theory Comput., 2014, 10, 252.
I. H. Williams, D. Spangler, D. A. Femec, G. M. Maggiora, R. L. Schowen, J. Am. Chem. Soc., 1980, 102, 6619.
I. H. Williams, D. Spangler, D. A. Femec, G. M. Maggiora, R. L. Schowen, J. Am. Chem. Soc., 1983, 105, 31.
E. A. Moelwyn-Hughes, The Chemical Statics and Kinetics of Solutions, Academic Press, London—New York, 1971, 530 pp.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0631—0639, March, 2016.
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Zabalov, M.V., Tiger, R.P. The supermolecule method, as applied to studies of liquid-phase reaction mechanisms taking cyclocarbonate aminolysis in dioxane as an example: specific features. Russ Chem Bull 65, 631–639 (2016). https://doi.org/10.1007/s11172-016-1347-6
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DOI: https://doi.org/10.1007/s11172-016-1347-6