title: Short-range solvation effects on chiroptical properties: a time-dependent density functional theory and ab initio molecular dynamics computational case study on austdiol.
abstract: The description of solvation effects on the chiroptical properties of chiral molecules is still a difficult challenge in the field of computational spectroscopy; this issue is critical in stereochemical characterization, since a reliable assessment of absolute configuration requires high accuracy. The present case study reports the huge effect of solvation on the chiroptical properties of austdiol, a fungal metabolite of known stereochemistry. Standard protocols based on time-dependent density functional theory calculations failed to reproduce its experimental chiroptical properties in methanol. When short-range solvation effects are explicitly considered by means of ab initio molecular dynamics, the correlation between calculated and experimental data is greatly improved because of a better description of the chiral environment around the ketone chromophore, showing that the modeling of subtle solvent-induced perturbations may require the most accurate computational methods.
authors.affiliation: Department of Pharmacy and Biotechnology, University of Bologna , Via Belmeloro 6, I-40126 Bologna, Italy.
authors.forename: Daniele
authors.initials: D
authors.lastname: Tedesco
authors.forename: Riccardo
authors.initials: R
authors.lastname: Zanasi
authors.forename: Barbara
authors.initials: B
authors.lastname: Kirchner
authors.forename: Carlo
authors.initials: C
authors.lastname: Bertucci
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D001578:Benzopyrans / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D012995:Solubility; D013997:Time Factors
chemical_list: D000447:Aldehydes; D001578:Benzopyrans; C474729:austdiol