Analyzing Kullback–Leibler information profiles: an indication of their chemical relevance

Literature Information

Publication Date 2008-11-18
DOI 10.1039/B814533D
Impact Factor 3.676
Authors

Alex Borgoo, Pablo Jaque, Alejandro Toro-Labbé, Christian Van Alsenoy, Paul Geerlings


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Abstract

The Kullback–Leibler information deficiency is evaluated along molecular internal rotational or vibrational coordinates and along the intrinsic reaction coordinate for several reactions (intra- and intermolecular proton transfer and SN2 reaction). For the first time an in depth analysis of the information deficiency along the reaction path is reported. The results are consistent with the Hammond postulate, indicating that the information profiles contain relevant chemical information. A local version of the information deficiency is defined by considering Hirshfeld’s partitioning of atoms in molecules. The analysis of the local information profiles permits the identification of the atoms taking part in the electron reorganization processes.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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