Issue 22, 2009

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

Abstract

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.

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

Article information

Article type
Paper
Submitted
16 Feb 2009
Accepted
24 Mar 2009
First published
11 May 2009

Phys. Chem. Chem. Phys., 2009,11, 4539-4548

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

A. Mohammed, H. Ågren and P. Norman, Phys. Chem. Chem. Phys., 2009, 11, 4539 DOI: 10.1039/B903250A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements