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Impact of Vibrations and Electronic Coherence on Electron Transfer in Flat Molecular Wires

Published online by Cambridge University Press:  07 February 2017

Oscar Grånäs ,
Grigory Kolesov  and
Efthimios Kaxiras
Oscar Grånäs*
Affiliation:
School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, USA Department of Physics and Astronomy, Division of Materials Theory, Uppsala University, Box 516, SE-75120 Uppsala, Sweden
Grigory Kolesov
Affiliation:
School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, USA
Efthimios Kaxiras
Affiliation:
School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, USA
*
*(Email: oscar.granas@physics.uu.se)
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Abstract

Electron transfer in molecular wires are of fundamental importance for a range of optoelectronic applications. The impact of electronic coherence and ionic vibrations on transmittance are of great importance to determine the mechanisms, and subsequently the type of wires that are most promising for applications. In this work, we use the real-time formulation of time-dependent density functional theory to study electron transfer through oligo-p-phenylenevinylene (OPV) and the recently synthesized carbon bridged counterpart (COPV). A system prototypical of organic photovoltaics is setup by bridging a porphyrin-fullerene dyad, allowing a photo-excited electron to flow between the Zn-porphyrin (ZnP) chromophore and the C60 electron acceptor through the molecular wire. The excited state is described using the fully self-consistent ∆-SCF method. The state is then propagated in time using the real-time TD-DFT scheme, while describing ionic vibrations with classical nuclei. The charge transferred between porphyrin and C60 is calculated and correlated with the velocity autocorrelation functions of the ions. This provides a microscopic insight to vibrational and tunneling contributions to electron transport in linked porphyrin-fullerene dyads. We elaborate on important details in describing the excited state and trajectory sampling.

Keywords

photovoltaicoptoelectronicelectronic structure
Type
Articles
Information
MRS Advances , Volume 2 , Issue 14: Nanomaterials , 2017 , pp. 811 - 816
Copyright
Copyright © Materials Research Society 2017 

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References

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