Skip to main content
eScholarship
Open Access Publications from the University of California

UC San Diego

UC San Diego Previously Published Works bannerUC San Diego

Raman scattering in molecular junctions: a pseudoparticle formulation.

  • Author(s): White, Alexander J;
  • Tretiak, Sergei;
  • Galperin, Michael
  • et al.

Published Web Location

https://doi.org/10.1021/nl4039532
Abstract

We present a formulation of Raman spectroscopy in molecular junctions based on a many-body state representation of the molecule. The approach goes beyond the previous effective single orbital formalism and provides a convenient way to incorporate computational methods and tools proven for equilibrium molecular spectroscopy into the realm of current carrying junctions. The presented framework is illustrated by first principle simulations of Raman response in a three-ring oligophenylene vinylene terminating in amine functional groups (OPV3) junction. The calculated shift in Stokes lines and estimate of vibrational heating by electric current agree with available experimental data. In particular, our results suggest that participation of the OPV3 cation in Raman scattering under bias may be responsible for the observed shift, and that the direction of the shift depends on renormalization of normal modes. This work is a step toward atomistic quantum ab initio modeling of the optical response of nonequilibrium electronic dynamics in molecular junctions.

Many UC-authored scholarly publications are freely available on this site because of the UC's open access policies. Let us know how this access is important for you.

Main Content
For improved accessibility of PDF content, download the file to your device.
Current View