Jump to main content
Jump to site search

Issue 96, 2016, Issue in Progress
Previous Article Next Article

Fractional molecular charge studied via molecular vibrational properties. Specific aspects in Jahn–Teller active molecular species

Author affiliations

Abstract

In this paper, we report results obtained within the density functional theory (DFT) demonstrating that information on the fractional (non-integral) charge of a single molecule can be extracted from its vibrational properties. This is important because, unlike the former, the latter can be measured experimentally, e.g., via surface enhanced Raman spectroscopy (SERS). As a concrete example, we choose a benzene molecule and consider changes brought about by continuously varying the fractional charge from q = 0 to q = 1 corresponding to neutral and radical cation species. Molecular electronics or electrochemical platforms may offer experimental realizations of continuously tuning non-integral molecular charges. We found that changes in the vibrational frequencies ωv(q) can be substantially larger than those recently measured by varying applied bias in molecular junctions. Our results indicate important qualitative and quantitative differences between the dependence ωv = ωv(q) exhibited by vibrational modes that are JT active and those that are JT inactive; typically, the former is stronger and nonlinear, while the latter is weaker and linear.

Graphical abstract: Fractional molecular charge studied via molecular vibrational properties. Specific aspects in Jahn–Teller active molecular species

Back to tab navigation

Supplementary files

Publication details

The article was received on 26 Aug 2016, accepted on 22 Sep 2016 and first published on 22 Sep 2016


Article type: Paper
DOI: 10.1039/C6RA21476B
Citation: RSC Adv., 2016,6, 93715-93721
  • Open access: Creative Commons BY license
  •   Request permissions

    Fractional molecular charge studied via molecular vibrational properties. Specific aspects in Jahn–Teller active molecular species

    I. Bâldea, RSC Adv., 2016, 6, 93715
    DOI: 10.1039/C6RA21476B

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements