Phase space geometry of dynamics passing through saddle coupled with spatial rotation

Area of Science:

• Chemical Dynamics
• Theoretical Chemistry
• Physical Chemistry

Background:

• Nonlinear reaction dynamics are crucial for understanding complex chemical transformations.
• Phase space geometry in saddle regions provides insights into reaction pathways.
• Spatial rotation effects on many-particle systems are not fully understood.

Purpose of the Study:

• To develop a theoretical framework for incorporating spatial rotation into reaction dynamics.
• To investigate nonlinear reaction dynamics through a rank-one saddle in rotating systems.
• To analyze the impact of rovibrational couplings on reaction pathways.

Main Methods:

• Developed a theoretical framework based on phase space geometry.
• Incorporated spatial rotation dynamically coupled with internal vibrational motions.
• Applied the framework to the isomerization reaction of HCN with nonzero total angular momenta.

Main Results:

• Identified no-return transition states (TS) and impenetrable reaction boundaries analytically.
• Demonstrated the influence of rovibrational couplings and anharmonicities on TS and boundaries.
• Showcased distinct effects of angular momentum components on reaction dynamics.

Conclusions:

• The developed method provides new insights into the origin of reactions with nonzero angular momentum.
• Spatial rotation significantly impacts reaction dynamics and boundary identification.
• Analytical identification of TS and reaction boundaries is possible under rovibrational couplings.