Phenomenological description of a three-center insertion reaction: an information-theoretic study.
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.
Esquivel
Rodolfo O
RO
Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, 09340, México D.F. esquivel@xanum.uam.mx
Flores-Gallegos
Nelson
N
Dehesa
Jesús S
JS
Angulo
Juan Carlos
JC
Antolín
Juan
J
López-Rosa
Sheila
S
Sen
K D
KD