Atomic Resolution for the Energy Derivatives on the Reaction Path

Area of Science:

• Computational chemistry
• Theoretical chemistry
• Quantum chemistry

Background:

• Understanding reaction mechanisms requires analyzing forces and energy changes along reaction paths.
• Identifying key molecular fragments involved in reactions is crucial for mechanism elucidation.

Purpose of the Study:

• To develop and present definite algorithms for calculating atomic contributions to reaction forces (Fξ) and reaction force constants (kξ).
• To separate the electronic component of atomic and group contributions to understand reactivity.
• To apply these methods to analyze the reaction pathways of CO + HF → HCOF and HONS → ONSH.

Main Methods:

• Calculation of atomic contributions to energy derivatives (first and second) along the reaction path.
• Separation of electronic contributions within atomic and group properties.
• Application of developed algorithms to canonical test reactions.

Main Results:

• Established algorithms for computing atomic contributions to reaction force and force constant.
• Enabled identification of reactive molecular fragments at different stages of a reaction.
• Demonstrated the utility of the methods on CO + HF and HONS reactions.

Conclusions:

• The developed algorithms provide a robust framework for analyzing reaction dynamics.
• The electronic component separation facilitates a deeper understanding of molecular reactivity.
• The study offers insights into the reaction mechanisms of the tested systems.