The reactive flux method applied to complex isomerization reactions: Using the unstable normal mode as a reaction coordinate

Otter den, W.K. and Briels, W.J. (1997) The reactive flux method applied to complex isomerization reactions: Using the unstable normal mode as a reaction coordinate. Journal of Chemical Physics, 106 (13). pp. 5494-5508. ISSN 0021-9606

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Abstract:	A basic problem when calculating reaction rates using the reactive flux method is the introduction of a reaction coordinate. In this paper we show that it is advantageous to define a reaction coordinate by means of the unstable normal mode of the saddle point of the potential energy surface. This particular choice is made since it yields a high transmission function. Moreover, the reaction coordinate is calculated via a rapidly converging algorithm, and its derivative, which is needed in constrained runs, is calculated analytically. Calculations on the transmission coefficient of the isomerization of n-butane are in good agreement with results published by others. Runs with an isomerizing calix[4]arene in vacuo produce a very high transmission coefficient, as is the purpose of the reaction coordinate. The same molecule is also studied in chloroform.
Item Type:	Article
Copyright:	© 1997 American Institute of Physics
Faculty:	Science and Technology (TNW)
Research Group:	Computational Biophysics (CBP)
Link to this item:	http://purl.utwente.nl/publications/59946
Official URL:	http://dx.doi.org/10.1063/1.473573
Publisher URL:	http://link.aip.org/link/?JCPSA6/106/5494/1
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