Ab initio molecular optical rotations and absolute configurations

Polavarapu, Prasad L.

doi:10.1080/00268979709482744

Cited by 204 publications

(87 citation statements)

References 2 publications

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“…A review of the literature indicates that significant progress has been made in recent years on computing the chiroptical characteristics, such as optical rotatory dispersion (ORD) and electronic circular dichroism spectra (ECD) (29–45). The reliability of these methods for determining the absolute configurations of chiral organic molecules has increased substantially (46–48).…”

Section: Introductionmentioning

confidence: 99%

Absolute configurations of DNA lesions determined by comparisons of experimental ECD and ORD spectra with DFT calculations

et al. 2009

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The usefulness of modern DFT methods is considered for establishing the absolute configurations of DNA lesions by comparisons of computed and experimentally measured optical rotatory dispersion (ORD) and electronic circular dichroism (ECD) spectra. Two rigid, structurally different DNA lesions (two spiroiminodihydantoin stereoisomers and four equine estrogen 4-hydoxyequilenin – DNA stereoisomeric adducts) have been investigated. In all cases, the signs and shapes of the computed ORD spectra reproduced the experimentally measured ORD spectra, although the magnitudes of the computed ORD values are different. The computed ECD spectra also reproduced the shapes of the experimental ECD spectra rather well, but are blue-shifted by 10 – 20 nm. The assignments of the absolute configurations of the DNA lesions studied based on computed and experimental ORD and ECD spectra are fully consistent with one another. The computational DFT method shows significant promise for determining the absolute configurations of DNA lesions. Establishing the stereochemistry of DNA lesions is highly useful for understanding their biological impact, especially when sufficient amounts of material are not available for other methods of structural characterization.

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Section: Introductionmentioning

confidence: 99%

Absolute configurations of DNA lesions determined by comparisons of experimental ECD and ORD spectra with DFT calculations

et al. 2009

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“…23 Stephens and co-workers have demonstrated how the gauge-origin independent DFT calculation of optical rotation is achieved by the use of London atomic orbitals 7,10 combined with time-dependent DFT. We recently implemented 19 this formalism in the Dalton program system.…”

Section: Theorymentioning

confidence: 99%

Gauge-Origin Independent Density-Functional Theory Calculations of Vibrational Raman Optical Activity

2002

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We present density-functional theory calculations of vibrational Raman optical activity. Gauge-origin independence of the results is ensured by using London atomic orbitals, and the frequency dependence is included by using analytical response theory. The Raman optical activity circular intensity differences are obtained by combining analytical calculations of linear response functions with numerical differentiation with respect to nuclear distortions. The results are compared with experiment, previous Hartree-Fock calculations, and a more recent approximate sum-over-states approach.

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“…Similar observations have also been reported for other nonlinear birefringences. [62][63][64][65][66] In contrast, the inclusion of diffuse polarizing functions can be seen to be very important for all the molecular parameters, increasing the different contributions by about an order of magnitude. Interestingly, the smallest effect of augmentation is for the contribution involving the magnetic dipole operator, M i (ω), which is surprising as diffuse polarizing functions have been shown to be important for magnetic and chiroptical properties.…”

Section: Resultsmentioning

confidence: 99%

Gauge-origin independent calculations of electric-field-induced second-harmonic generation circular intensity difference using London atomic orbitals

2016

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We present the first gauge-origin independent calculations of the circular intensity difference (CID) in electric-field-induced second-harmonic generation (EFISHG), including all contributions up to the electric-quadrupole-magnetic-dipole level.A recursive, open-ended response theory framework in combination with the use of London atomic orbitals allows us to ensure gauge-origin independent results. We apply this approach to study EFISHG-CID in a collection of chiral amino acids. We demonstrate that diffuse polarizing basis functions are critical in order to obtain accurate CIDs, and that a basis set of at least aug-cc-pVTZ quality is needed in order to obtain results close to the basis-set limit. The use of London orbitals does not lead to significantly faster basis set convergence, although the improved basis set convergence allows the aug-cc-pVDZ basis set to be used with some confidence for larger molecules.

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Ab initio molecular optical rotations and absolute configurations

Cited by 204 publications

References 2 publications

Absolute configurations of DNA lesions determined by comparisons of experimental ECD and ORD spectra with DFT calculations

Absolute configurations of DNA lesions determined by comparisons of experimental ECD and ORD spectra with DFT calculations

Gauge-Origin Independent Density-Functional Theory Calculations of Vibrational Raman Optical Activity

Gauge-origin independent calculations of electric-field-induced second-harmonic generation circular intensity difference using London atomic orbitals

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