Conical intersection-regulated intermediates in bimolecular reactions: Insights from C(¹D) + HD dynamics

Area of Science:

• Chemical Dynamics
• Quantum Chemistry
• Reaction Mechanisms

Background:

• Conical intersections (CIs) are crucial in nonadiabatic processes.
• Their role in adiabatic dynamics has been largely underestimated.

Purpose of the Study:

• To investigate the influence of CIs on adiabatic dynamics.
• To elucidate the role of CIs in the C(1D) + HD reaction.

Main Methods:

• Combined experimental and theoretical studies.
• Quantum dynamics calculations on ab initio potential energy surfaces.
• Quasi-classical trajectory calculations.

Main Results:

• CIs induce a barrier and regulate intermediate conversion.
• This leads to bond-selective activation in the C(1D) + HD reaction.
• Unusual reaction mechanisms, including C─H activation complex conversion and cyclic complex, were identified.

Conclusions:

• CI-induced barriers significantly impact adiabatic dynamics.
• The findings validate theoretical models with experimental data.
• The dynamical effects of CIs may have broad significance in reactive systems.