Theories of Optical Rotatory Power

As part of a general study of the time-dependent local density approximation (TDLDA), we here report calculations of optical activity of chiral molecules.The theory automatically satisfies sum rules and the Kramers-Kronig relation between circular dichroism and optical rotatory power. We find that the theory describes the measured circular dichroism of the lowest states in methyloxirane with an accuracy of about a factor of two. In the chiral fullerene C 76 the TDLDA provides a consistent description of the optical absorption spectrum, the circular dichroism spectrum, and the optical rotatory power, except for an overall shift of the theoretical spectrum. *

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“…Polarization of chiral molecule in applied electromagnetic field is expressed using two coefficients α and β as [21] …”

Section: Formalism a Some Definitionsmentioning

confidence: 99%

Application of the time-dependent local density approximation to optical activity

1999

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“…Theoretical methods that are able to assist the experimental research in this field are therefore of high importance. [5][6][7][8] The currently most applied method in first-principles quantum chemical calculations is density functional theory ͑DFT͒ because it combines computational efficiency with often reliable accuracy of the results. Not surprisingly therefore, there has been recently an increasing interest in the computation of optical activity related observables by timedependent density functional theory [9][10][11] ͑TDDFT͒.…”

Section: Introductionmentioning

confidence: 99%

Chiroptical properties from time-dependent density functional theory. II. Optical rotations of small to medium sized organic molecules

Autschbach

Patchkovskii

Ziegler

et al. 2002

The Journal of Chemical Physics

194

162

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We report an implementation for the computation of optical rotations within the Amsterdam Density Functional program package. The code is based on time-dependent density functional response theory. Optical rotations have been calculated for a test set of 36 organic molecules with various density functionals, and employing basis sets of different quality. The results obtained in this work with nonhybrid functionals are comparable in quality to those recently reported by other authors for the B3LYP hybrid functional, but show a somewhat larger tendency to produce outlyers. The median error is approximately 20°/(dm g/cm 3 ) for specific rotations ͓␣͔ D as compared to experimental data ͑approximately 30% median deviation from experimental values͒. Thereby it is demonstrated that density functional computations can be employed to assist with the solution of stereochemical problems in case the specific rotations of the species involved are not small and their structures are rigid. Recent newly developed functionals are investigated with respect to their applicability in computations of optical rotations.

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“…the models of Born, Oseen [1], Kuhn [2] and Kirkwood [3] based on a spatial distribution of coupled oscillators, and single-oscillator models, e.g. the Drude helix model [4] and the Condon, Altar and Eyring theory [5] (for a comprehensive review, consult [6]). The first consistent quantum mechanical theoretical formalism was put forward by Rosenfeld without invoking the couple oscillator model [7].…”

Section: Introductionmentioning

confidence: 99%

Nonlinear coherent magneto-optical response of a single chiral carbon nanotube

Slavcheva

Roussignol

2010

New J. Phys.

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View the article online for updates and enhancements. Abstract. We propose a theoretical framework and dynamical model for the description of the natural optical activity and Faraday rotation in an individual chiral single-wall carbon nanotube (CNT) in the highly nonlinear coherent regime. The model is based on a discrete-level representation of the optically active states near the band edge. Chirality is modelled by a system Hamiltonian in a four-level basis corresponding to energy-level configurations, specific for each handedness, that are mirror reflections of each other. The axial magnetic field is introduced through the Aharonov-Bohm and Zeeman energylevel shifts. The time evolution of the quantum system, describing a single nanotube with defined chirality, under an ultrashort polarized pulse excitation is studied using the coupled coherent vector Maxwell-pseudospin equations (Slavcheva 2008 Phys. Rev. B 77 115347). We provide an estimate for the effective dielectric constant and the optical dipole matrix element for transitions excited by circularly polarized light in a single nanotube and calculate the magnitude of the circular dichroism and the specific rotatory power in the absence and in the presence of an axial magnetic field. Giant natural gyrotropy (polarization rotatory power ∼3000 • mm −1 (B = 0 T)), superior to that of the crystal birefringent materials, liquid crystals and comparable or exceeding that of the artificially made helical photonic structures, is numerically demonstrated for the specific case of a (5, 4) nanotube. A quantitative estimate of the coherent nonlinear magneto-chiral optical effect in an axial magnetic field is given 3 Authors to whom any correspondence should be addressed. . The model provides a framework for the investigation of the chirality and magnetic field dependence of the ultrafast nonlinear optical response of a single CNT.

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Theories of Optical Rotatory Power

Cited by 833 publications

References 49 publications

Application of the time-dependent local density approximation to optical activity

Application of the time-dependent local density approximation to optical activity

Chiroptical properties from time-dependent density functional theory. II. Optical rotations of small to medium sized organic molecules

Nonlinear coherent magneto-optical response of a single chiral carbon nanotube

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