Concurrent phenomena at the transition region of selected elementary chemical reactions: An information-theoretical complexity analysis

Authors

  • Rodolfo O. Esquivel,

    Corresponding author
    1. Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, 09340 - México D.F., México
    2. Departamento de Física Atómica, Molecular y Nuclear, Universidad de Granada, 18071-Granada, Spain
    3. Instituto Carlos I de Física Teórica y Computacional, Universidad de Granada, 18071-Granada, Spain
    • Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, 09340 - México D.F., México
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  • Moyocoyani Molina-Espíritu,

    1. Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, 09340 - México D.F., México
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  • Jesús S. Dehesa,

    1. Departamento de Física Atómica, Molecular y Nuclear, Universidad de Granada, 18071-Granada, Spain
    2. Instituto Carlos I de Física Teórica y Computacional, Universidad de Granada, 18071-Granada, Spain
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  • Juan Carlos Angulo,

    1. Departamento de Física Atómica, Molecular y Nuclear, Universidad de Granada, 18071-Granada, Spain
    2. Instituto Carlos I de Física Teórica y Computacional, Universidad de Granada, 18071-Granada, Spain
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  • Juan Antolín

    1. Instituto Carlos I de Física Teórica y Computacional, Universidad de Granada, 18071-Granada, Spain
    2. Departamento de Física Aplicada, EINA, Universidad de Zaragoza, 50018-Zaragoza, Spain
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Abstract

In this work, we have investigated in position (r) and momentum (p) spaces the concurrent phenomena occurring at the vicinity of the transition state (TS) (the so-called transition region) of selected chemical reactions (such as the hydrogenic abstraction and the exchange hydrogenic reactions) by means of a broad set of single information-theoretic functionals of the one-particle density (such as the disequilibrium (D), exponential entropy (L), Fisher information (I) and the power entropy (J)) and composite information-theoretic measures which includes various information planes (such as the I-D, D-L, and I-J planes) and complexities of the Fisher-Shannon and López-Mancini-Calbet (LMC) types. The analysis of the single functionals and the information planes revealed that these information-theoretical elements can identify all the chemically significant regions, not only the reactant/product regions (R/P) and the TS but also those that are not present in the energy profile, such as the bond cleavage energy region (BCER), the bond breaking/forming regions (B-B/F) and the charge transfer complex. Moreover, the analysis of the complexities shows that in position as well as in the joint (r-p) spaces, the energy profile of the abstraction reaction bears the same information-theoretical features of the LMC and FS measures. Finally, it is shown why most of the chemical features of interest (such as e.g., BCER and B-B/F) are lost in the energy profile, being only revealed when particular information-theoretical aspects of localizability (L or J), uniformity (D) and disorder (I) are considered. © 2012 Wiley Periodicals, Inc.

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