Towards an accurate description of anharmonic infrared spectra in solution within the polarizable continuum model: Reaction field, cavity field and nonequilibrium effects

Cappelli, Chiara; Lipparini, Filippo; Bloino, Julien; Barone, Vincenzo

doi:10.1063/1.3630920

Cited by 48 publications

(53 citation statements)

References 62 publications

(85 reference statements)

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“…It is known that the original formulation of the PCM approach, which is used to model the effect of the solvent on OR, neglects the local field and nonequilibrium effects. In 2012, a new methodology to calculate harmonic and anharmonic vibrational corrections to the OR of solvated systems within the PCM framework was proposed by Egidi et al Besides, these authors call attention to the importance of taking into account the local field and nonequilibrium effects on OR calculations of solvated molecules to have an appropriate comparison between theory and experiment.…”

Section: Resultsmentioning

confidence: 99%

CAM‐B3LYP optical rotations at different wavelengths: Comparison with CCSD results

Jorge

Oliveira

Silva

2015

Int J of Quantum Chemistry

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A hierarchical sequence of basis sets along with one long‐range corrected functional (CAM‐B3LYP) were used to calculate electronic optical rotations (OR) at three wavelengths (355.0, 589.3, and 633.0 nm) of 14 rigid chiral molecules whose experimental values are available in the literature. As the results showed to be sensitive to the basis set quality, complete basis set limits were estimated. Special attention was given to five particularly difficult compounds. In these cases, one verifies that vibrational corrections (taken from the literature) must be added to the CAM‐B3LYP equilibrium OR to correct signs. In general, the complete basis set limits reported in this work are in good agreement with the experimental data and with those obtained at a higher level of theory. For some compounds, solvent effects are taken into account by means of the polarizable continuum model. For the solvated systems, the dependence between OR and cavity size is also examined. © 2015 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 99%

CAM‐B3LYP optical rotations at different wavelengths: Comparison with CCSD results

Jorge

Oliveira

Silva

2015

Int J of Quantum Chemistry

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“…Solvation is surely a complex phenomenon, involving interactions and effects of different nature, which are difficult to be modeled by means of a single theory. In many cases, continuum solvation models are efficient and reliable especially in their refined formulations including nonequilibrium and local field effects . However, they may fail, even dramatically, whenever specific solute–solvent interactions (or solute–solute aggregation effects) dominate the solute environment interaction, and especially when a chiral imprinting in the solvation shell can occur .…”

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

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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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“…The vibrational nonequilibrium solvation regime also affects the calculation of IR and VCD spectra, both at the level of the vibrational analysis (normal modes and normal mode frequencies) and the spectroscopic IR and VCD intensities. It is therefore crucial to include nonequilibrium effects while performing the harmonic vibrational analysis and the subsequent calculation of the anharmonic contributions, in order to compute all terms constituting the observables in a consistent manner …”

Section: Methodsmentioning

confidence: 99%

“…The IR and VCD spectra were computed for the molecule in chloroform solution. Solvent effects were included in the calculations by means of the PCM, with local field effects and within the electronic and vibrational nonequilibrium regimes. The PCM cavity was built using a set of interlocking spheres centered on the atoms and with the following radii (in angstroms): 1.443 for hydrogen, 1.926 for carbon, and 1.830 for nitrogen, each multiplied by a factor of 1.1.…”

Section: Computational Detailsmentioning

confidence: 99%

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Development of a Virtual Spectrometer for Chiroptical Spectroscopies: The Case of Nicotine

et al. 2013

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The impressive advances of computational spectroscopy in most recent years are providing robust and user-friendly multifrequency virtual spectrometers, which can also be used by nonspecialists to complement experimental studies. At the heart of these developments there are latest-generation models based on Density Functional Theory for the proper treatment of stereo-electronic effects, coupled to the polarizable continuum model to deal with bulk solvent effects, and low-order perturbative treatments of anharmonic effects. Continuing our efforts to increase the range of application of virtual spectrometers, we report here about chiroptical spectroscopies with special reference to optical rotation and vibrational circular dichroism. The capabilities and possible limitations of our latest tool will be analyzed for the specific case of (S)-nicotine in vacuo and in different solvents.

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Towards an accurate description of anharmonic infrared spectra in solution within the polarizable continuum model: Reaction field, cavity field and nonequilibrium effects

Cited by 48 publications

References 62 publications

CAM‐B3LYP optical rotations at different wavelengths: Comparison with CCSD results

CAM‐B3LYP optical rotations at different wavelengths: Comparison with CCSD results

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

Development of a Virtual Spectrometer for Chiroptical Spectroscopies: The Case of Nicotine

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