Time-dependent density functional theory for resonant properties: resonance enhanced Raman scattering from the complex electric-dipole polarizability. 2009

Abdelsalam Mohammed, and Hans Agren, and Patrick Norman
Theoretical Chemistry, Royal Institute of Technology, SE-100 44, Stockholm, Sweden.

Based on resonant-convergent-and thereby complex-electric-dipole polarizabilities, formulae for differential cross sections in resonant Raman spectroscopy are presented. In absorptive regions of the spectrum, there are phase delays in the induced polarization that enter the expressions for the cross sections. The theory is exemplified by calculations employing the adiabatic time-dependent density functional theory approximation, with applications on the low-lying, dipole-allowed, electronic states of a sample of molecules, including hydrogen peroxide, pyridine, and trinitrotoluene. Results obtained with the Coulomb attenuated B3LYP exchange-correlation functional are found to be more accurate than those obtained with the conventional B3LYP functional-an observation that holds not only for trinitrotoluene with its transitions of charge-transfer character but also for the other cases. The qualitative features of the resonant Raman spectra for a given molecule vary strongly from one resonance wavelength to another, which is a fact that could further facilitate the use of this spectroscopy in applications of stand-off detection of gaseous samples in ultra-low concentrations.

UI MeSH Term Description Entries
D011725 Pyridines Compounds with a six membered aromatic ring containing NITROGEN. The saturated version is PIPERIDINES.
D011789 Quantum Theory The theory that the radiation and absorption of energy take place in definite quantities called quanta (E) which vary in size and are defined by the equation E Quantum Theories,Theories, Quantum,Theory, Quantum
D006861 Hydrogen Peroxide A strong oxidizing agent used in aqueous solution as a ripening agent, bleach, and topical anti-infective. It is relatively unstable and solutions deteriorate over time unless stabilized by the addition of acetanilide or similar organic materials. Hydrogen Peroxide (H2O2),Hydroperoxide,Oxydol,Perhydrol,Superoxol,Peroxide, Hydrogen
D013059 Spectrum Analysis, Raman Analysis of the intensity of Raman scattering of monochromatic light as a function of frequency of the scattered light. Raman Spectroscopy,Analysis, Raman Spectrum,Raman Optical Activity Spectroscopy,Raman Scattering,Raman Spectrum Analysis,Scattering, Raman,Spectroscopy, Raman
D013997 Time Factors Elements of limited time intervals, contributing to particular results or situations. Time Series,Factor, Time,Time Factor
D014303 Trinitrotoluene A 2,4,6-trinitrotoluene, which is an explosive chemical that can cause skin irritation and other toxic consequences. TNT,2,4,6-Trinitrotoluene

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