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

Literature Information

Publication Date 2009-05-11
DOI 10.1039/B903250A
Impact Factor 3.676
Authors

Abdelsalam Mohammed, Hans Ågren, Patrick Norman


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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.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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