The Relation Between Vector and Bond Eigenfunction Methods for Spin Degeneracy
A method previously developed for the calculation of matrix components for problems in which spin degeneracy only is important is shown to be equivalent to an operator method derivable from the vector...
A method previously developed for the calculation of matrix components for problems in which spin degeneracy only is important is shown to be equivalent to an operator method derivable from the vector...
Thermodynamic Functions of Tetramethylmethane
The Q-sum corresponding to La Coste's eigenvalues for the rotational levels of tetramethylmethane has been expressed by the usual asymptotic expansion. The relatively large coupling terms between the ...
The Q-sum corresponding to La Coste's eigenvalues for the rotational levels of tetramethylmethane has been expressed by the usual asymptotic expansion. The relatively large coupling terms between the ...
The Activated Complex in Chemical Reactions
J. Chem. Phys. 3, 107 (1935); doi:10.1063/1.1749604
Issue Date: February 1935
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The calculation of absolute reaction rates is formulated in terms of quantities which are available from the potential surfaces which can be constructed at the present time. The probability of the activated state is calculated using ordinary statistical mechanics. This probability multiplied by the rate of decomposition gives the specific rate of reaction. The occurrence of quantized vibrations in the activated complex, in degrees of freedom which are unquantized in the original molecules, leads to relative reaction rates for isotopes quite different from the rates predicted using simple kinetic theory. The necessary conditions for the general statistical treatment to reduce to the usual kinetic treatment are given.
The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
| History: | Received November 8, 1934 |
| Permalink: |
http://link.aip.org/link/?JCPSA6/3/107/1 |
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REFERENCES (11)
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- Moelwyn-Hughes, Kinetics of Reactions in Solution, Oxford Press (1933).
- W. E. Vaughan, J. Am. Chem. Soc. 55, 4115 (1933).
- K. F. Herzfeld, Kinetische Theorie der Wärme (Müller-Pouillets Lehrbuch der Physik) 1925.
- R. C. Tolman, Statistical Mechanics, Chemical Catalog Co., 1927.
- R. H. Fowler, Statistical Mechanics, Cambridge Univ. Press, 1929.
- H. Pelzer and E. Wigner, Zeits. f. Physik. Chemie B15, 445 (1932).
- Volmer and Kummerow, Zeits. f. Physik. Chemie B9, 141 (1930).
- See, for example, Whittaker, Analytic Dynamics, Cambridge Univ. Press, 1927.
- J. H. Van Vleck and P. C. Cross, J. Chem. Phys. 1, 357 (1933).
- M. Polanyi and E. Wigner, Zeits. f. Physik. Chemie A (Haber Band), 439 (1928).
- L. S. Kassel,
J. Phys. Chem. 34, 1777 (1930) . - H. S. W. Massey and C. B. O. Mohr, Proc. Roy. Soc. A141, 434 (1933);
- W. H. Rodebush, J. Chem. Phys. 1, 440 (1933);
O. K. Rice and H. Gershinowitz, ibid. 2, 853 (1934).
