Maximum bonding fragment orbitals for deciphering complex chemical interactions

Literature Information

Publication Date 2018-05-01
DOI 10.1039/C8CP01808A
Impact Factor 3.676
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Abstract

An optimal set of fragment orbitals is proposed that offers a simple and general way to describe complex bonding situations. The idea is based on the unique decomposition of the total bond order between fragments. Each resulting component corresponds to the bonding between a pair of optimal fragment orbitals. These pairs further form a set of exactly doubly occupied bond orbitals, which fully describes the chemical bonding between two fragments. Thereby, complex bonding interactions can be separated into a few well-defined pairwise orbital interactions. A remarkable feature of the theory is that one can build up a quantitative and clearly correlated orbital interaction diagram. Explicit analytical expressions are also presented for bond orders, bond polarities, occupancies, and orbital interaction energies, providing new insights into the bond order concept and the fundamental principles of molecular orbital theory. Through illustrative examples, this new approach is shown to be a simple and powerful tool for analyzing different kinds of chemical interactions, including covalent, ionic and noncovalent bonding.

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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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