A vibrational circular dichroism implementation within a Slater-type-orbital based density functional framework and its application to hexa- and hepta-helicenes

Artemisinin and two of its derivatives, dihydroartemisinin and artesunate, front line drugs against malaria, were studied using Raman optical activity (ROA), vibrational circular dichroism (VCD) experiments and density functional theory (DFT) calculations.

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Determination of the Absolute Configurations of Pharmacological Natural Products via Density Functional Theory Calculations of Vibrational Circular Dichroism: The New Cytotoxic Iridoid Prismatomerin

The Journal of Organic Chemistry ◽

10.1021/jo071183b ◽

2007 ◽

Vol 72 (20) ◽

pp. 7641-7649 ◽

Cited By ~ 68

Author(s):

Philip J. Stephens ◽

Jian-Jung Pan ◽

Karsten Krohn

Keyword(s):

Density Functional Theory ◽

Natural Products ◽

Circular Dichroism ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Vibrational Circular Dichroism ◽

Functional Theory ◽

The Absolute ◽

Circular Dichroïsm

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Evaluation of Molecular Polarizability and of Intensity Carrying Modes Contributions in Circular Dichroism Spectroscopies

Applied Sciences ◽

10.3390/app9214691 ◽

2019 ◽

Vol 9 (21) ◽

pp. 4691 ◽

Cited By ~ 1

Author(s):

Chiara Zanchi ◽

Giovanna Longhi ◽

Sergio Abbate ◽

Giovanni Pellegrini ◽

Paolo Biagioni ◽

...

Keyword(s):

Circular Dichroism ◽

Density Functional ◽

Vibrational Circular Dichroism ◽

Molecular Polarizability ◽

Metal Nanostructures ◽

Dipole Polarizability ◽

Dft Methods ◽

Visible Absorption ◽

Long Run ◽

Circular Dichroïsm

We re-examine the theory of electronic and vibrational circular dichroism spectroscopy in terms of the formalism of frequency-dependent molecular polarizabilities. We show the link between Fermi’s gold rule in circular dichroism and the trace of the complex electric dipole–magnetic dipole polarizability. We introduce the C++ code polar to compute the molecular polarizability complex tensors from quantum chemistry outputs, thus simulating straightforwardly UV-visible absorption (UV-Vis)/electronic circular dichroism (ECD) spectra, and infrared (IR)/vibrational circular dichroism (VCD) spectra. We validate the theory and the code by referring to literature data of a large group of chiral molecules, showing the remarkable accuracy of density functional theory (DFT) methods. We anticipate the application of this methodology to the interpretation of vibrational spectra in various measurement conditions, even in presence of metal surfaces with plasmonic properties. Our theoretical developments aim, in the long run, at embedding the quantum-mechanical details of the chiroptical spectroscopic response of a molecule into the simulation of the electromagnetic field distribution at the surface of plasmonic devices. Such simulations are also instrumental to the interpretation of the experimental spectra measured from devices designed to enhance chiroptical interactions by the surface plasmon resonance of metal nanostructures.

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Prediction of Vibrational Circular Dichroism Spectra Using Density Functional Theory: Camphor and Fenchone

Journal of the American Chemical Society ◽

10.1021/ja961219+ ◽

1996 ◽

Vol 118 (26) ◽

pp. 6327-6328 ◽

Cited By ~ 50

Author(s):

F. J. Devlin ◽

P. J. Stephens ◽

J. R. Cheeseman ◽

M. J. Frisch

Keyword(s):

Density Functional Theory ◽

Circular Dichroism ◽

Density Functional ◽

Vibrational Circular Dichroism ◽

Circular Dichroism Spectra ◽

Functional Theory ◽

Circular Dichroïsm

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Conformational Analysis in Solution of a Chiral Bisoxazoline Molecule: Vibrational Circular Dichroism Spectroscopy and Density Functional Theory Study

International Journal of Spectroscopy ◽

10.1155/2011/905045 ◽

2011 ◽

Vol 2011 ◽

pp. 1-11

Author(s):

A. Aamouche ◽

P. J. Stephens

Keyword(s):

Density Functional Theory ◽

Circular Dichroism ◽

Conformational Analysis ◽

Density Functional ◽

Circular Dichroism Spectroscopy ◽

Vibrational Circular Dichroism ◽

Kcal Mole ◽

Functional Theory ◽

High Degree ◽

Circular Dichroïsm

The conformations of the chiral bisoxazoline: 2,2′-methylenebis[3a,8a-dihydro-8H-indeno[1,2-d]oxazole] (also named IndaBOX), have been studied. Density functional theory (DFT) calculations identify four inequivalent stable conformations. Two, I and II have, C2 symmetry; two, III and IV, have C1 symmetry. The electronic energies of I–IV are ordered: I<II<III<IV. The span in energy is <1.0 kcal/mole. Vibrational unpolarised absorption and circular dichroism spectra have been predicted for the four conformations using DFT. Comparison of population-weighted spectra to experimental spectra of CHCl3 and CDCl3 solutions in mid-IR region strongly supports the DFT predictions of the number, structures, and relative energies of the conformations of IndaBOX. This shows that DFT predicts spectra with a high degree of reliability. We will undoubtedly illustrate the advantage added by vibrational circular dichroism spectroscopy in conformational analysis and in the absolute configuration determination.

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