Accurate calculation of optically induced birefringences in chiral systems using efficient polarized basis sets

Area of Science:

• Theoretical Chemistry
• Quantum Chemistry
• Chirality Studies

Background:

• Optically induced birefringences are crucial properties of chiral fluids.
• Accurate evaluation of molecular parameters is essential for understanding these phenomena.
• Existing methods may not provide sufficient accuracy for chiral systems.

Purpose of the Study:

• To evaluate universal molecular parameters for optically induced birefringences in chiral fluids.
• To assess the accuracy of coupled cluster (CCSD) theory for these calculations.
• To compare CCSD results with Density Functional Theory (DFT) and various basis sets.

Main Methods:

• Utilized single and double excitation coupled cluster (CCSD) theory.
• Employed Dunning's augmented correlation consistent polarized basis sets.
• Tested on small chiral molecules: asymmetric methane and (R)-fluoro-oxirane.

Main Results:

• CCSD calculations provide accurate molecular parameters for chiral fluids.
• DFT calculations yielded significantly different results compared to CCSD.
• The LPol-ds basis set demonstrated efficient convergence for molecular parameters.

Conclusions:

• CCSD theory is recommended for accurate evaluation of optically induced birefringences in chiral systems.
• DFT is not suitable for precise calculations of these properties.
• The LPol-ds basis set is an efficient choice for studying larger chiral systems.