Circular dichroism: electronic

Abstract

AbstractFirst‐principles calculations of electronic circular dichroism (ECD) are widely used to determine absolute configurations of chiral molecules. In addition, ECD is a sensitive probe for the three‐dimensional molecular structure, making ECD calculations a useful tool to study conformational changes. In this review, we explain the origin of ECD and optical activity using response theory. While the quantum‐mechanical underpinnings of ECD have been known for a long time, efficient electronic structure methods for ECD calculations on molecules with more than 10–20 atoms have become widely available only in the past decade. We review the most popular methods for ECD calculation, focusing on time‐dependent density functional theory. Although single‐point vertical ECD calculations yield useful accuracy for conformationally rigid systems, inclusion of finite‐temperature effects is necessary for flexible molecules. The scope and limitations of modern ECD calculations are illustrated by applications to helicenes, fullerenes, iso‐schizozygane alkaloids, paracyclophanes, β‐lactams, and transition metal complexes. © 2011 John Wiley & Sons, Ltd. WIREs Comput Mol Sci 2011 00 1–17 DOI: 10.1002/wcms.55This article is categorized under: Electronic Structure Theory > Density Functional Theory