Electronic Currents Induced by Optical Fields and Rotatory Power Density in Chiral Molecules

Area of Science:

• Theoretical Chemistry
• Computational Chemistry
• Spectroscopy

Background:

• Optical activity in chiral molecules is crucial for understanding molecular interactions.
• The electric dipole-magnetic dipole polarizability tensor (κ') is key to interpreting optical activity.
• Existing methods for evaluating polarizability components can be complex and origin-dependent.

Purpose of the Study:

• To develop a computational approach for evaluating the electric dipole-magnetic dipole polarizability tensor.
• To investigate the origin-dependence of polarizability density functions (kαβ').
• To identify invariant properties for determining molecular domains responsible for optical activity.

Main Methods:

• Expressing the polarizability tensor κ' using density functions kαβ'.
• Utilizing frequency-dependent electronic current densities induced by monochromatic light.
• Analyzing the invariance of kαβ' and its trace (kαα') with respect to the coordinate system origin.
• Performing computations on hydrogen peroxide with varying dihedral angles.

Main Results:

• A computational method for kαβ' based on induced electronic current densities was established.
• The origin-dependence of kαβ' components was analyzed.
• The trace of the density function (kαα') was found to be invariant to the origin when using continuous translation.
• The invariant kαα' was shown to be a useful tool for identifying key molecular domains for optical activity.

Conclusions:

• The invariant trace of the density function (kαα') is a reliable indicator of molecular domains governing optical activity.
• The proposed computational method provides a valuable tool for analyzing chiral molecules.
• The study offers pictorial documentation of the method using hydrogen peroxide as a model system.