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Current Physical Chemistry

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ISSN (Print): 1877-9468
ISSN (Online): 1877-9476

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Simple Models of Charge-Transfer Reactivity

Author(s): Roman F. Nalewajski*

Volume 12, Issue 1, 2022

Published on: 10 May, 2022

Page: [11 - 23] Pages: 13

DOI: 10.2174/1877946812666220302150715

Abstract

Finite-difference expressions for the chemical potential (negative electronegativity) and hardness (inverse softness) descriptors of molecular and donor-acceptor systems are summarized and chemically “biased” (informed) and “unbiased” (uninformed) estimates of charge-transfer (CT) descriptors in A(acid)-B(base) systems are reexamined. The former recognizes the chemical characteristics of reactants and the chemical-potential discontinuity, while in the latter no prior knowledge of such kind is used. The biased chemical potential and fragment hardness descriptors are interpreted in terms of the frontier-electron orbitals, and the equivalence of predictions in both treatments is demonstrated using the electronegativity- equalization principle. Two-state description of CT involves a statistical mixture of initial state |NCT = 0〉 = |A0, B0〉 of the polarized (mutually closed) reactants in R+ = (A+|B+), and one of admissible final states for the full electron transfer, |NCT| = 1, in the forward B0→A0 or reverse A0→B0 directions, leading to ion-pairs |B0→A0〉 = |NCT = 1〉 = |A−1, B+1〉 and |A0→B0〉 = |NCT = −1〉 = |A+1, B−1〉. Parabolic interpolation between energies of the integral-N states identifies the process activation and reaction energies predicts the equilibrium amount of CT and stabilization energy it generates.

Keywords: Charge-transfer reactivity, simple models, chemical potential, donor-acceptor systems, electronegativity- equalization principle, molecular-orbital.

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