A combined experimental and theoretical study of optical rotatory dispersion for (<i>R</i>)-glycidyl methyl ether in aqueous solution

Egidi, Franco; Giovannini, Tommaso; Frate, Gianluca Del; Lemler, Paul M.; Vaccaro, Patrick H.; Cappelli, Chiara

doi:10.1039/c8cp04445g

Cited by 34 publications

(33 citation statements)

References 60 publications

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“…This observation should not be interpreted as discouraging the general use of MD simulations, because the analyses of solution-phase spectra using MD geometries have certainly helped in many situations. 22−24…”

Section: Results and Discussionmentioning

confidence: 99%

“…This approach has facilitated probing not only the AC but also the molecular conformational space, in a variety of systems, containing both small and large molecules. The availability of faster computer processors with larger memory and storage space has led to the use of molecular dynamics (MD) for generating the geometries of solute–solvent clusters and simulating the QC-predicted spectra for solvated species. − Attempts to analyze the experimental chiroptical spectra using corresponding QC-predicted spectra have now become a routine practice . Recent works have also emphasized on quantitative comparisons between experimental and calculated spectra using the similarity index and spectral similarity overlap (SSO) plots. − …”

Section: Introductionmentioning

confidence: 99%

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Chiral Molecular Structures of Substituted Indans: Ring Puckering, Rotatable Substituents, and Vibrational Circular Dichroism

Johnson

Polavarapu

2019

ACS Omega

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The chiral molecular structures of four different substituted indans, namely, ( S )-1-methylindan, ( R )-1-methylindan-1-d, ( R )-1-aminoindan, and ( S )-1-indanol, were investigated using experimental vibrational absorption and vibrational circular dichroism spectra and corresponding spectra predicted using quantum chemical (QC) calculations. All of these molecules possess two ring puckering conformations, with ring puckering leading to the pseudoequatorial substituent being approximately four times more abundant over that leading to the pseudoaxial substituent. The amino group in 1-aminoindan has three conformations arising from the rotation of NH 2 group, for each ring puckering conformation, resulting in a total of six conformations. Whereas 1-indanol in the nonhydrogen-bonding solvent CCl 4 also has six conformations similar to those of 1-aminoindan, 1-indanol in the hydrogen-bonding solvent DMSO- d 6 adopts numerous conformations, of which 30 conformers are considered to have at least ∼1% or more population. In DMSO solution, ring puckering leading to pseudoequatorial substituent accounts for 77% population and 23% for pseudoaxial substituent. The QC spectra predicted for the geometry optimized conformers are found to be in excellent quantitative agreement with corresponding experimental spectra in all of the molecules considered. The procedures suggested in this work are hoped to provide successful pathways for future chiral molecular structural analyses.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Chiral Molecular Structures of Substituted Indans: Ring Puckering, Rotatable Substituents, and Vibrational Circular Dichroism

Johnson

Polavarapu

2019

ACS Omega

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“…In fact, the consequences can be seen directly in the spectra, with shifts of a few nanometers in UV-Vis spectra and substantial broadening of IR/Raman bands, or even sign inversion in computed chiral properties. 11,40,41 For this reason, neglecting a proper treatment of hydrogen bonding in the computation of spectral properties of aqueous systems is generally unsafe, can lead to relevant artifacts in the computed spectra and should therefore be avoided. 14,21,40,41…”

Section: Hydrogen Bondingmentioning

confidence: 99%

Molecular spectroscopy of aqueous solutions: a theoretical perspective

2020

Self Cite

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“…Another problem is that a direct comparison with experimental data is difficult for this sensitive molecular property. On the one hand, simulations are not yet able to reliably account for solvation effects, [41][42][43][44][45][46][47][48][49][50] vibrational effects are typically introduced only through approximate perturbative treatments, [51][52][53][54][55][56] and proper averaging of multiple conformers of the same enantiomer with opposite OR sign requires very accurate relative energy calculations. 57,58 On the other hand, experimental measurements of rigid chiral molecules in the gas phase (which would sidestep some of the above simulation limitations, i.e., conformational averaging and solvation effects) are very limited due to the low volatility of these compounds and the overall small signal.…”

Section: Introductionmentioning

confidence: 99%

Basis Set Dependence of Optical Rotation Calculations with Different Choices of Gauge

Parsons

Balduf

Cheeseman³

et al. 2022

Preprint

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In this work, the basis set dependence of optical rotation (OR) calculations is examined for various choices of gauge/level of theory. The OR is calculated for a set of 50 molecules using B3LYP and CAM-B3LYP, and 17 molecules using coupled cluster with single and double ex- citations (CCSD). The calculations employ the correlation-consistent basis sets, aug-cc-pVζZ with ζ = D, T, Q. An inverse-power extrapolation formula is then utilized to obtain OR values at the complete basis set (CBS) limit. We investigate the basis set convergence for these methods and three choices of gauge: length gauge (with gauge-including atomic orbitals, LG(GIAOs), for DFT), the origin-invariant length gauge [LG(OI)], and the modified velocity gauge (MVG). The results show that all methods converge smoothly to the CBS limit and that the LG(OI) approach has a slightly faster convergence rate than the other choices of gauge. While the DFT methods reach gauge invariance at the CBS limit, CCSD does not. The significant difference between the MVG and LG(OI) results at the CBS limit, 26%, indicates that CCSD is not quite at convergence in the description of electron correlation for this property. On the other hand, gauge invariance at the CBS limit for DFT does not lead to the same OR values for the two density functionals, which is also due to electron correlation incompleteness. A limited comparison to gas-phase experimental OR values for the DFT methods shows that CAM-B3LYP seems more accurate than B3LYP. Overall, this study shows that the LG(OI) approach with the aug-cc-pVTZ basis set for DFT, and with the CBS(DT) extrapolation for CCSD, provides a good cost/accuracy balance.

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A combined experimental and theoretical study of optical rotatory dispersion for (R)-glycidyl methyl ether in aqueous solution

Abstract: We present a theoretical-experimental study of the optical rotation of (R)-glycidylmethylether using a mixed quantum-classical model for solvent effects.

Cited by 34 publications

References 60 publications

Chiral Molecular Structures of Substituted Indans: Ring Puckering, Rotatable Substituents, and Vibrational Circular Dichroism

Chiral Molecular Structures of Substituted Indans: Ring Puckering, Rotatable Substituents, and Vibrational Circular Dichroism

Molecular spectroscopy of aqueous solutions: a theoretical perspective

Basis Set Dependence of Optical Rotation Calculations with Different Choices of Gauge

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