Coupled nuclear and electron dynamics in the vicinity of a conical intersection

Area of Science:

• Quantum dynamics
• Molecular spectroscopy
• Theoretical chemistry

Background:

• Ultrafast optical techniques enable the study of molecular dynamics involving nuclear and electronic motion.
• Interpreting these dynamics requires theoretical methods capable of describing both nuclear and electron behavior.
• Conical intersections are critical regions where non-adiabatic transitions occur, significantly influencing molecular dynamics.

Purpose of the Study:

• To revisit and expand the NEMol (Nuclear and Electron dynamics in Molecules) ansatz for a coupled quantum mechanical description of nuclear and electron dynamics.
• To simulate the coupled dynamics of nitrogen dioxide (NO2) near a conical intersection (CoIn).
• To investigate the control of molecular dynamics through tailored laser pulses, specifically focusing on carrier-envelope phase manipulation.

Main Methods:

• The NEMol ansatz combines quantum-dynamical description of nuclear motion with electron dynamics calculated in the eigenfunction basis.
• Simulations focus on the molecule NO2 in the vicinity of a conical intersection.
• A control scheme using the carrier envelope phase of a few-cycle infrared (IR) pulse is employed.

Main Results:

• The NEMol ansatz successfully simulates the coupled nuclear and electron dynamics of NO2 near a CoIn.
• Coherent electron dynamics induced by non-adiabatic coupling were investigated.
• The study demonstrates the potential to control molecular dynamics during passage through a CoIn using IR laser pulses.

Conclusions:

• The enhanced NEMol ansatz provides a robust framework for studying coupled nuclear-electron dynamics in molecular systems.
• Tailoring laser pulse properties, such as carrier-envelope phase, offers a viable strategy for controlling ultrafast molecular dynamics.
• This research advances the understanding and control of non-adiabatic processes in molecules.