Local Temperature as a Chemical Reactivity Descriptor.
Chunna Guo1, Xin He1, Chunying Rong1
1Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan Normal University, Changsha, Hunan 410081, China.
The Journal of Physical Chemistry Letters
|June 10, 2021
Summary
Local temperature, derived from kinetic energy density, effectively quantifies molecular reactivity in density functional theory. This approach aids in predicting reaction pathways and regioselectivity for various chemical transformations.
Area of Science:
- Computational chemistry
- Quantum chemistry
- Chemical reactivity theory
Background:
- Electron density is crucial for quantifying molecular properties in density functional theory (DFT).
- Local temperature, based on kinetic energy density, presents a novel intrinsic property for reactivity assessment.
Purpose of the Study:
- To explore the utility of local temperature as a descriptor for chemical reactivity.
- To evaluate the performance of local temperature in predicting regioselectivity and reaction pathways.
Main Methods:
- Investigated the behavior of local temperature using different kinetic energy density functionals.
- Applied local temperature to determine regioselectivity in nucleophilic and electrophilic reactions.
- Analyzed local temperature's performance along intrinsic reaction pathways for diverse reaction types.
Main Results:
- Local temperature exhibits predictable behavior with various kinetic energy density approximations.
- Local temperature successfully predicts regioselectivity for nucleophilic and electrophilic additions.
- The descriptor accurately reflects reaction energetics along intrinsic reaction pathways.
Conclusions:
- Local temperature is a robust and effective descriptor for molecular reactivity within DFT.
- This method offers a promising avenue for understanding and predicting chemical reaction outcomes.
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