Enhanced diastereocontrol via strong light-matter interactions in an optical cavity

Abstract

The enantiopurification of racemic mixtures of chiral molecules is important for a range of applications. Recent work has shown that chiral group-directed photoisomerization is a promising approach to enantioenrich racemic mixtures of BINOL, but increased control of the diasteriomeric excess (de) is necessary for its broad utility. Here we develop a cavity quantum electrodynamics (QED) generalization of time-dependent density functional theory and demonstrate computationally that strong light-matter coupling can alter the de of chiral group-directed photoisomerization of BINOL. The relative orientation of the cavity mode polarization and the molecules in the cavity dictates the nature of the cavity interactions, which either enhance the de of the (R)-BINOL diasteriomer (from 17% to $\approx$ 40%) or invert the favorability to the (S)-BINOL derivative (to $\approx$ 34% de). The latter outcome is particularly remarkable because it indicates that the preference in diasteriomer can be influenced via orientational control, without changing the chirality of the directing group. We demonstrate that the observed effect stems from cavity-induced changes to the Kohn-Sham orbitals of the ground state.

References in corpus (10)

• Quantum Electrodynamical Density-Functional Theory: Bridging Quantum Optics and Electronic-Structure Theory
• Intermolecular interactions in optical cavities: an ab initio QED study
• Cavity-modulated ionization potentials and electron affinities from quantum electrodynamics coupled-cluster theory
• Quantum-Electrodynamical Time-Dependent Density Functional Theory. I. A Gaussian Atomic Basis Implementation
• Equation-of-motion cavity quantum electrodynamics coupled-cluster theory for electron attachment
• Simple Exchange-Correlation Energy Functionals for Strongly Coupled Light-Matter Systems based on the Fluctuation-Dissipation Theorem
• On the characteristic features of ionization in QED environments
• Reduced-density-matrix-based ab initio cavity quantum electrodynamics
• Exact functionals for correlated electron-photon systems
• Catalysis in Click Chemistry Reactions Controlled by Cavity Quantum Vacuum Fluctuations: The Case of endo/exo Diels-Alder Reaction

Cited by in corpus (9)

• Cavity-Born-Oppenheimer Hartree-Fock Ansatz: Light-matter Properties of Strongly Coupled Molecular Ensembles
• Strong coupling in chiral cavities: nonperturbative framework for enantiomer discrimination
• Assessing the Effects of Orbital Relaxation and the Coherent-State Transformation in Quantum Electrodynamics Density Functional and Coupled-Cluster Theories
• Variational Lang-Firsov approach plus Møller-Plesset perturbation theory with applications to ab initio polariton chemistry
• Engineering flat bands in twisted-bilayer graphene away from the magic angle with chiral optical cavities
• Do Molecular Geometries Change Under Vibrational Strong Coupling?
• Vacuum-Induced Symmetry Breaking of Chiral Enantiomer Formation in Chemical Reactions
• Simulating polaritonic ground states on noisy quantum devices
• Scalable Quantum Monte Carlo Method for Polariton Chemistry via Mixed Block Sparsity and Tensor Hypercontraction Method