Charge Transfer Is Promoted by Electronic Heat Exchange in Atoms and Molecules

Area of Science:

• Theoretical Chemistry
• Chemical Physics
• Materials Science

Background:

• Understanding chemical reactivity traditionally focuses on ground-state properties.
• Finite-temperature effects on electron transfer dynamics remain a significant theoretical challenge.
• Existing models often struggle to capture the nuances of charge transfer under non-isothermal conditions.

Purpose of the Study:

• To develop the first theoretical model for charge transfer at finite temperatures.
• To elucidate the role of electronic heat and thermal fluctuations in chemical reactivity.
• To provide a framework for predicting fractional electron transfers in chemical interactions.

Main Methods:

• Compilation of a decade of theoretical progress in temperature-dependent chemical reactivity.
• Development of a finite-temperature charge transfer model incorporating thermodynamic parameters.
• Analysis of electronic heat capacity, softness, and chemical potential.
• Investigation of thermal fluctuation effects on molecular response functions.

Main Results:

• The model predicts fractional electron transfers driven by electronic heat.
• Identified transition from inert to reactive states based on electronic decorrelation.
• Demonstrated the role of thermal fluctuations in simultaneous energy and charge exchange.
• Reduced the model to a linear equation in reservoir chemical potential, supporting and refining the electrophilicity index.

Conclusions:

• Finite-temperature effects are crucial for understanding chemical reactivity and charge transfer.
• Electronic heat is a key driver of charge transfer processes.
• The developed model offers new predictive capabilities for chemical interactions under varying temperatures.
• The findings provide a more comprehensive understanding of electron transfer mechanisms in chemical reactions.