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Modeling Complex Solvent Effects on the Optical Rotation of Chiral Molecules: A Combined Molecular Dynamics and Density Functional Theory Study
- Source :
- The journal of physical chemistry. A. 125(15)
- Publication Year :
- 2021
-
Abstract
- 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.
- Subjects :
- 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
Subjects
Details
- ISSN :
- 15205215
- Volume :
- 125
- Issue :
- 15
- Database :
- OpenAIRE
- Journal :
- The journal of physical chemistry. A
- Accession number :
- edsair.doi.dedup.....f08288d6e5e723dedc91f9c4ffe7b61c