Contribution of a Solute's Chiral Solvent Imprint to Optical Rotation

Mukhopadhyay, Parag; Zuber, Gérard; Wipf, Peter; Beratan, David N.

doi:10.1002/anie.200702273

Cited by 107 publications

(89 citation statements)

References 32 publications

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“…In particular for couplings at short range, this may provide significant new insights, since assumptions concerning the cavity in implicit solvation models can be tested. But also quite unusual phenomena may be investigated, as for example the recently reported optical rotation due to chiral imprinting and related effects [407] (see also Ref. [408]).…”

Section: Discussionmentioning

confidence: 98%

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Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy

2010

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Section: Discussionmentioning

confidence: 98%

“…To give an example, it has recently been argued that the optical rotatory dispersion of methyloxirane in benzene is caused mainly by the response of the benzene molecules due to a chiral imprinting effect [407] (see also Ref. [408]).…”

Section: General Response Properties From Subsystem Tddftmentioning

confidence: 99%

Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy

2010

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“…Refinements of continuum models by means of an extension of the definition of the solute have been proposed, 32 but they cause an increase in both the computational cost and the complexity of the calculation that is often not accompanied by a definite improvement in the reliability of the calculations, especially whenever chiral imprinting in the solvation shell can be invoked. 23,33 In this case, standard QM/molecular mechanics (MM) or supermolecular approaches can also be inadequate because the imprinting is in fact a dynamic and local effect that requires the coupling of accurate electronic methods to evaluate the property with equally accurate dynamic simulations to obtain a reliable description of the fluctuations in the solute− solvent interactions, which in this case do not average out to result in an isotropic effect but instead sustain the chiral response in the solvent cage around the chiral solute.…”

Section: Introductionmentioning

confidence: 97%

The Electronic Circular Dichroism of Nicotine in Aqueous Solution: A Test Case for Continuum and Mixed Explicit-Continuum Solvation Approaches

et al. 2015

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In this paper, we extend an integrated QM/MM/polarizable continuum model (PCM) method, which combines a fluctuating charge (FQ) approach to the MM polarization with the PCM, to describe electronic circular dichroism (ECD) spectra of systems in aqueous solution. The main features of the approach are presented, and then applications to the UV and ECD spectra of neutral (S)-nicotine in aqueous solution are reported. The performance of the QM/FQ/PCM is compared with that of the PCM against newly measured UV ECD spectra, which are in agreement with previous findings. The inclusion of specific solvation effects via the QM/FQ/PCM method leads to an improvement in the calculated spectra compared to the experimental findings, though the pure PCM results are still qualitatively correct and are a useful tool for the characterization of the states.

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“…Therefore, the question of what is the best way to model solvent effects on chiroptical properties of systems in strongly interacting media is far from being finally assessed, especially because implicit solvation model, and the polarizable continuum model (PCM) in particular, have been tested thoroughly, whereas only few attempts have been performed so far by exploiting explicit or combined explicit/implicit models, that mainly due to the few hybrid QM/classical molecular mechanics (MM) approaches currently able to calculate chiroptical responses . In this review, the latter methodologies are discussed, with particular focus on a recently developed fully polarizable QM/MM/PCM approach, which has shown to be extremely powerful at overtaking the limitations of continuum solvation approaches.…”

Section: Introductionmentioning

confidence: 99%

Integrated QM/polarizable MM/continuum approaches to model chiroptical properties of strongly interacting solute–solvent systems

Cappelli

2016

Int J of Quantum Chemistry

140

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Solvent effects on chiroptical properties and spectroscopies can be huge, and affect not only the absolute value but the sign of molecular chiroptical responses. Therefore, the definition of reliable theoretical models and computational protocols to calculate chiroptical responses and assist the assignment of the chiral absolute configuration cannot overlook the effects of the surrounding environment. Continuum solvation methodologies are successful in case of weakly interacting solute-solvent couples, whereas in case of strongly interacting systems, such as those dominated by explicit hydrogen bonding interaction, a change of strategy is required to gain a reliable modeling.In this review, a recently developed integrated Quantum-Mechanical/Polarizable molecular mechanics (MM)/polarizable continuum model (PCM) method is discussed, which combines a fluctuating charge approach to the MM polarization with the PCM. Its theoretical fundamentals, and issues related to the calculation of chiroptical responses are summarized, and the application to few representative test cases in aqueous solution is discussed.aqueous solutions, chirality, polarizable embedding, solvent effects, quantum mechanical/molecular mechanics | I N T R O D U C T I O NThe calculation of chiroptical properties and chiral spectra by means of Quantum-Mechanical (QM) methods [1][2][3][4][5] is a mature research field.Many theoretical developments have been reported in the literature, focusing on the different aspects (accuracy in the description of the molecular Hamiltonian, choice of the basis set, inclusion of environmental effects) [3,[6][7][8][9] which may contribute to reach an accurate description of chirality. The definition of accurate protocols is nowadays accompanied by several applications, which demonstrate that a significant level of accuracy is accessible, so that QM calculations are universally accepted as a powerful methodology to assist the determination of the molecular absolute configuration.[10]In case of standard (non-chiral) spectroscopies, the most relevant information which is extracted from spectra is mainly related to peak positions (energies), whereas peak intensities play a secondary role. This is reflected in the computational methodologies which have been developed so far, which are mainly interested in getting an accurate reproduction of peak positions (infrared/Raman wavenumbers, UV-Vis transition energies, NMR chemical shieldings, etc.), reserving instead much less attention to spectral intensities. [11][12][13] In case of chiroptical properties/spectroscopies, an opposite situation occurs, in fact not only the absolute value but also especially the sign of the spectroscopic response is the most relevant information taken from the spectra. This feature makes chiroptical properties among the most challenging for theoretical models, and the difficulties in their accurate modeling are further increased by that fact that they are formally mixed electricmagnetic properties, where the effects of both the fields are ...

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Contribution of a Solute's Chiral Solvent Imprint to Optical Rotation

Abstract: Solvent or solute dissymmetry? The dissymmetric ordering of solvent molecules around the chiral solute (see picture) contributes to the chiroptical signature. Indeed, the solvent can dominate the chiroptical response, as shown for (S)‐methyloxirane in benzene.

Cited by 107 publications

References 32 publications

Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy

Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy

The Electronic Circular Dichroism of Nicotine in Aqueous Solution: A Test Case for Continuum and Mixed Explicit-Continuum Solvation Approaches

Integrated QM/polarizable MM/continuum approaches to model chiroptical properties of strongly interacting solute–solvent systems

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