2022
DOI: 10.1021/acs.jpca.2c07134
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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 c… Show more

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Cited by 34 publications
(51 citation statements)
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References 60 publications
(98 reference statements)
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“…First, for electronic degrees of freedom, some of these approaches represent the electronic density in real space, 27,31,36,65,66 whereas others use atom-centered Gaussian basis functions. 19,29,30,45 Second, photon degrees of freedom can be represented directly in real-space 20,24,67 or in Fock space 19,[29][30][31]45 (in a basis of photon-number states). Third, as with standard TDDFT, both real-time 24,31 and linearresponse 19,27,29,30,66 formulations have been put forward.…”
Section: B Cavity Qed Density Functional Theorymentioning
confidence: 99%
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“…First, for electronic degrees of freedom, some of these approaches represent the electronic density in real space, 27,31,36,65,66 whereas others use atom-centered Gaussian basis functions. 19,29,30,45 Second, photon degrees of freedom can be represented directly in real-space 20,24,67 or in Fock space 19,[29][30][31]45 (in a basis of photon-number states). Third, as with standard TDDFT, both real-time 24,31 and linearresponse 19,27,29,30,66 formulations have been put forward.…”
Section: B Cavity Qed Density Functional Theorymentioning
confidence: 99%
“…13 Moreover, a large number of computational studies have predicted a range of phenomena that are relevant to chemistry. 2,4,[14][15][16][17][18][19] Predictive electronic/polaritonic structure methods will be crucial for discovering general design principles for cavity-mediated chemistry; as a result, substantial effort has been dedicated to the generalization of familiar tools in quantum chemistry for the polaritonic problem.…”
Section: Introductionmentioning
confidence: 99%
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“…9, In recent works, traditional electronic structure methods have been generalized to include the effects of light-matter interactions and used to solve the polaritonic states of the moleculecavity hybrid systems. To name a few, these efforts include the cavity QED density functional theory (QED-DFT), 29,32,37,38 time-dependent DFT (QED-TD-DFT), 29,31,[39][40][41] coupled cluster (QED-CC) and its equation-of-motion extension (QED-EOM-CC), 33,33,37,42 or full configuration interaction (FCI) methods. 37,43 In this way, the light and matter description are calculated on the same footing in their respective methodologies, where the to-tal polariton wavefunction is expressed as the linear combination of different configurations (e.g., Slater determinants of single-particle states), with each configuration composed as a tensor product of the electronic configuration and the photonic configuration.…”
Section: Introductionmentioning
confidence: 99%
“…This is in stark contrast to many recent works focusing on the development of electronic-photonic structure methods. 31,40,41,43,70,71 There is strong merit to formulating such an approach as it allows a variational solution to the mixed electron-photon problem -meaning that the electronic and photonic bases are optimized to give the correct eigenstates of the QED Hamiltonian given only a few original adiabtic-Fock states as a starting point. However, there are two main issues at the present time: (I) These electronicphotonic structure methods are not widely available/tested in commercially available software.…”
Section: Introductionmentioning
confidence: 99%