Marcus, R. A. (1966) On the Analytical Mechanics of Chemical Reactions. Classical Mechanics of Linear Collisions. Journal of Chemical Physics, 45 (12). pp. 4500-4504. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120829-110842187
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The classical mechanics of chemically reactive linear collisions is investigated for vibrationally near‐adiabatic reactions. A coordinate system which passes smoothly from one suited to the reactants to one suited to the products is used. The Hamilton—Jacobi equation is then solved in the adiabatic approximation by introduction of an "adiabatic‐separable" method. Nonadiabatic corrections, which describe the probability of vibrational transitions, are also calculated. They involve the Fourier component of local internal centrifugal and vibration frequency‐change terms. The reaction coordinate for the adiabatic system is shown to be that curve on which local vibrational and internal centrifugal forces balance pointwise. Applications can be made to the role of translational—vibrational energy interchange in reactions, reaction‐cross‐section theory, bobsled effect, and other topics. The results may be compared with electronic computer calculations as they become available.
|Additional Information:||© 1966 American Institute of Physics. Received 3 June 1966. Supported by a grant from the National Science Foundation.|
|Official Citation:||On the Analytical Mechanics of Chemical Reactions. Classical Mechanics of Linear Collisions R. A. Marcus, J. Chem. Phys. 45, 4500 (1966), DOI:10.1063/1.1727529|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Jason Perez|
|Deposited On:||29 Aug 2012 18:24|
|Last Modified:||26 Dec 2012 16:04|
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