The ORP basis set designed for optical rotation calculations

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Spectroscopy

Background:

• Accurate calculation of optical rotation (OR) is crucial in stereochemistry.
• Existing basis sets can be computationally expensive for routine calculations.

Purpose of the Study:

• To develop and validate a new, efficient basis set for optical rotation prediction (ORP).
• To assess the performance of the ORP basis set against established larger basis sets.

Main Methods:

• Density functional theory (DFT) calculations were employed.
• The newly developed ORP basis set was tested on various chiral molecules.
• Results were compared with calculations using aug-cc-pVTZ and aug-pc-2 basis sets.

Main Results:

• The ORP basis set demonstrated superior performance compared to larger basis sets for small and large chiral systems.
• ORP calculations showed excellent agreement with high-level theoretical results (aug-cc-pVTZ).
• The ORP set provides accurate specific rotation values at a reduced computational cost.

Conclusions:

• The ORP basis set is a cost-effective and accurate tool for routine DFT-based optical rotation calculations.
• It is suitable for a wide range of molecules, including large and conformationally flexible systems.