Polarizable continuum model study of solvent effects on electronic circular dichroism parameters

Pecul, Magdalena; Marchesan, Domenico; Ruud, Kenneth; Coriani, Sonia

doi:10.1063/1.1829046

Cited by 62 publications

(57 citation statements)

References 50 publications

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“…A computationally very efficient way to model solvent effects is via continuum models. [66,67] Applications to CD and optical rotations have been carried out previously, [68,69] in some cases with mixed success. Another issue is the large magnitude of vibrational effects on optical rotations.…”

Section: Discussionmentioning

confidence: 99%

Time‐Dependent Density Functional Theory for Calculating Origin‐Independent Optical Rotation and Rotatory Strength Tensors

Autschbach

2011

ChemPhysChem

124

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An approach to calculate origin-independent electronic chiroptical property tensors using time-dependent density functional theory (TDDFT) and gauge-including atomic orbital (GIAO) basis sets is evaluated. Computations of origin-dependent optical rotation tensors and of rotatory strengths needed to simulate circular dichroism spectra are presented. The optical rotation tensor computations employ solutions of coupled perturbed Kohn-Sham equations for a dynamic electric field and a static magnetic field. Because the magnetic field is time independent, the GIAO treatment is somewhat simplified compared to a previously reported method, at some added computational cost if hybrid functionals are employed. GIAO rotatory strengths are also calculated, using transition density matrices from a standard TDDFT excitation energy module. A new implementation in the NWChem quantum chemistry package is employed for representative computations of origin-invariant chiroptical response tensors for methyloxirane, norbornenone, and the ketosteroid androstadienone. For the steroid molecule the vibrational structure of the CD spectrum is modeled explicitly by using calculated Franck-Condon factors. The agreement with experiment is favorable.

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Section: Discussionmentioning

confidence: 99%

Time‐Dependent Density Functional Theory for Calculating Origin‐Independent Optical Rotation and Rotatory Strength Tensors

Autschbach

2011

ChemPhysChem

124

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“…Particularly, for the Raman signal, the broader relative widths of peaks corresponding to normal mode nos. [4][5][6]8, and 24-26 can be explained by the molecular flexibility (cf., Figures 5 and 6). Overall, the experimental line widths, however, are still slightly wider, which can be attributed to a dynamical influence of the solvent, not included in the static CPCM model.…”

Section: Table 3: Definitions Of Symmetry-adapted Internal Coordinatementioning

confidence: 99%

“…Advances of the computational techniques based on first principles 1 enabled better involvement of the molecular environment including the solvent [2][3][4][5][6] and allowed for modeling of finer structural details. This provides an important feedback into spectroscopic techniques, such as those exploring the Raman scattering, interpretation of which is to a large extent dependent on solid theoretical models.…”

Section: Introductionmentioning

confidence: 99%

Conformational Flexibility of l-Alanine Zwitterion Determines Shapes of Raman and Raman Optical Activity Spectral Bands

et al. 2006

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Detailed analysis of Raman and Raman optical activity (ROA) of L-alanine zwitterion (ALAZW) revealed that shapes of the spectral bands are to a large extent determined by the rotation of the NH 3 + , CO 2 -, and CH 3 groups. Aqueous solution ALAZW spectra were measured down to 100 cm -1 and compared to complex simulations based on ab initio (B3LYP/CPCM/6-31++G**) computations of molecular energies and spectral parameters. The bands exhibit different sensitivities to the motion of the rotating group; typically, for more susceptible bands the Raman signal becomes broader and the ROA intensity decreases. When these dynamical factors are taken into account in Boltzmann averaging of conformer contributions, simulated spectra not only better agree with the experiment, but shapes of the rotational potentials can be estimated. Effects of the molecular flexibility could be also demonstrated on differences in Raman spectra of the solution, crystalline, and glass (gellike) solid states of ALAZW. Experimental Raman and ROA spectra of four model dipeptides of different rigidities (Ala-Pro, Pro-Ala, Pro-Gly, and Gly-Pro) indicate that the broadening of spectral lines can be used as a general site-specific indicator of molecular rigidity or flexibility.

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“…The technical aspects related to the calculation of the OR using LAOs within the PCM are discussed in detail elsewhere. 30,31,41 To find the stable conformers, we follow a strategy similar to the one adopted in our previous investigations on the paraconic acid 32 and its a-methyl derivatives. 33 For each molecule, we select a certain number of initial conformations by varying the dihedral angles describing the five-membered ring puckering (two positions, up and down), the carboxylic group torsional motion (three positions), plus, for the ethylesters, the torsion of the ethyl group (three positions).…”

Section: Definitions and Computational Detailsmentioning

confidence: 99%

Solvent effects on the conformational distribution and optical rotation of γ‐methyl paraconic acids and esters

et al. 2006

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A computational investigation of the optical rotatory power of cis and trans 2-methyl-5-oxo-tetrahydro-3-furancarboxylic acids and the corresponding methyl and ethyl esters is presented. Solvent effects on both the conformational space and the rotatory power are analyzed by comparing results obtained in vacuo with those computed--using the Polarizable Continuum Model--in methanol. A comparison with experimental observations for the optical rotatory power of the title compounds in methanol is also carried out, in a few cases also for several wavelengths. Agreement between theory and experiment is in all cases excellent, in particular when solvent effects are included both in the geometry optimization and in the calculation of the OR, thus confirming the validity of the computational procedure adopted, even for this challenging family of floppy molecules.

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Polarizable continuum model study of solvent effects on electronic circular dichroism parameters

Cited by 62 publications

References 50 publications

Time‐Dependent Density Functional Theory for Calculating Origin‐Independent Optical Rotation and Rotatory Strength Tensors

Time‐Dependent Density Functional Theory for Calculating Origin‐Independent Optical Rotation and Rotatory Strength Tensors

Conformational Flexibility of l-Alanine Zwitterion Determines Shapes of Raman and Raman Optical Activity Spectral Bands

Solvent effects on the conformational distribution and optical rotation of γ‐methyl paraconic acids and esters

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