Local molecular properties and their use in predicting reactivity

Area of Science:

• Theoretical Chemistry
• Computational Chemistry
• Quantum Chemistry

Background:

• Local electronic properties are crucial for understanding chemical reactivity.
• Existing methods for local ionization energy provide a foundation for further development.
• The need for comprehensive local descriptors of molecular electronic structure is recognized.

Purpose of the Study:

• To derive and define expressions for local electron affinity, electronegativity, and hardness.
• To introduce a definition for local polarizability using an additive atomic orbital model.
• To investigate the characteristics and chemical relevance of these local properties at molecular surfaces.

Main Methods:

• Derivation of local electronic property expressions by analogy to local ionization energy.
• Definition of local polarizability using Rivail's variational technique and an additive atomic orbital model.
• Analysis of local properties in the context of molecular surfaces and chemical reactions.

Main Results:

• Novel expressions for local electron affinity, electronegativity, and hardness were successfully derived.
• A new definition for local polarizability was established.
• The study explored the behavior and significance of these local properties on molecular surfaces.

Conclusions:

• The derived local electronic properties offer valuable insights into molecular behavior.
• These local properties are relevant for predicting and understanding various chemical reactions, including electrophilic aromatic substitution, S(N)2 reactions, and enolate nucleophilicity.
• The findings contribute to the development of more accurate computational chemistry tools for reactivity prediction.