Phenomenological description of a three-center insertion reaction: an information-theoretic study

Esquivel, Rodolfo O. ; Flores-Gallegos, Nelson ; Dehes, Jess S. ; Angulo, Juan Carlos ; Antoln, Juan ; Lpez-Rosa, Sheila ; Sen, K. D. (2010) Phenomenological description of a three-center insertion reaction: an information-theoretic study The Journal of Physical Chemistry A, 114 (4). pp. 1906-1916. ISSN 1089-5639

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jp908898w

Related URL: http://dx.doi.org/10.1021/jp908898w

Abstract

Information-theoretic measures are employed to describe the course of a three-center chemical reaction in terms of detecting the transition state and the stationary points unfolding the bond-forming and bond-breaking regions which are not revealed in the energy profile. The information entropy profiles for the selected reactions are generated by following the intrinsic-reaction-coordinate (IRC) path calculated at the MP2 level of theory from which Shannon entropies in position and momentum spaces at the QCISD(T)/6-311++G(3df,2p) level are determined. Several complementary reactivity descriptors are also determined, such as the dipole moment, the molecular electrostatic potential (MEP) obtained through a multipole expansion (DMA), the atomic charges and electric potentials fitted to the MEP, the hardness and softness DFT descriptors, and several geometrical parameters which support the information-theoretic analysis. New density-based structures related to the bond-forming and bond-breaking regions are proposed. Our results support the concept of a continuum of transient of Zewail and Polanyi for the transition state rather than a single state, which is also in agreement with reaction-force analyses.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:45053
Deposited On:24 Jun 2011 13:57
Last Modified:24 Jun 2011 13:57

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