A Phase-Space Electronic Hamiltonian For Vibrational Circular Dichroism.

Area of Science:

• Quantum Chemistry
• Spectroscopy
• Theoretical Physics

Background:

• The Born-Oppenheimer approximation is a cornerstone of quantum chemistry, separating nuclear and electronic motion.
• Limitations of the Born-Oppenheimer approximation in describing certain quantum phenomena are increasingly recognized.
• Vibrational circular dichroism (VCD) spectroscopy is a powerful tool for analyzing molecular chirality.

Purpose of the Study:

• To investigate the efficacy of a phase-space non-Born-Oppenheimer electronic Hamiltonian approach for calculating VCD spectra.
• To explore the potential of this phase-space method for uncovering new dynamical physics beyond VCD.
• To examine the implications for understanding chiral induced spin selectivity (CISS).

Main Methods:

• Empirical demonstration of a phase-space electronic Hamiltonian approach.
• Parametrization of the electronic Hamiltonian by both nuclear position and momentum.
• Calculation and recovery of vibrational circular dichroism spectra.

Main Results:

• The phase-space non-Born-Oppenheimer method is shown to be both practical and accurate for VCD spectral recovery.
• The approach successfully reproduces empirical VCD spectra.
• A hypothesis is proposed regarding new dynamical physics potentially revealed by this method.

Conclusions:

• The phase-space non-Born-Oppenheimer electronic Hamiltonian is a viable and accurate method for VCD spectroscopy.
• This theoretical framework offers a promising avenue for exploring novel quantum dynamics.
• The method's conservation properties may be key to understanding phenomena like CISS.