Modeling Complex Solvent Effects on the Optical Rotation of Chiral Molecules: A Combined Molecular Dynamics and Density Functional Theory Study
| Autor: | Ruhee D'Cunha, T. Daniel Crawford |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
Physics::Biological Physics
Quantitative Biology::Biomolecules 010304 chemical physics Chemistry Ab initio 010402 general chemistry 01 natural sciences 0104 chemical sciences Condensed Matter::Soft Condensed Matter Molecular dynamics Chemical physics Solvent models Molecular property 0103 physical sciences Density functional theory Physics::Chemical Physics Physical and Theoretical Chemistry Optical rotation Solvent effects Basis set |
| Zdroj: | The journal of physical chemistry. A. 125(15) |
| ISSN: | 1520-5215 |
| Popis: | The challenge of assigning the absolute stereochemical configuration to a chiral compound can be overcome via accurate ab initio predictions of optical rotation, a sensitive molecular property that is further complicated by solvent effects. The solvent's "chiral imprint"-the transfer of the chirality from the solute to the surrounding achiral solvent-is explored here using conformational averaging and time-dependent density-functional theory. These complex solvent effects are taken into account via simple averaging over a molecular dynamics trajectory together with the explicit quantum mechanical consideration of the solvent molecules within the solute's cybotactic region and implicit modeling of the bulk solvent. We consider several axes along which the system's optical rotation varies, including the sampling of the dynamical trajectory, the quality of the one-electron basis set, and the use of continuum solvent models to account for bulk effects. |
| Databáze: | OpenAIRE |
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