Control of single-molecule junction conductance of porphyrins via a transition-metal center

Zhen Fei Liu, Sujun Wei, Hongsik Yoon, Olgun Adak, Ingrid Ponce, Yivan Jiang, Woo Dong Jang, Luis M. Campos, Latha Venkataraman, Jeffrey B. Neaton

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48 Citations (Scopus)

Abstract

Using scanning tunneling microscope break-junction experiments and a new first-principles approach to conductance calculations, we report and explain low-bias charge transport behavior of four types of metal-porphyrin-gold molecular junctions. A nonequilibrium Green's function approach based on self-energy corrected density functional theory and optimally tuned range-separated hybrid functionals is developed and used to understand experimental trends quantitatively. Importantly, due to the localized d states of the porphyrin molecules, hybrid functionals are essential for explaining measurements; standard semilocal functionals yield qualitatively incorrect results. Comparing directly with experiments, we show that the conductance can change by nearly a factor of 2 when different metal cations are used, counter to trends expected from gas-phase ionization energies which are relatively unchanged with the metal center. Our work explains the sensitivity of the porphyrin conductance with the metal center via a detailed and quantitative portrait of the interface electronic structure and provides a new framework for understanding transport quantitatively in complex junctions involving molecules with localized d states of relevance to light harvesting and energy conversion.

Original languageEnglish
Pages (from-to)5365-5370
Number of pages6
JournalNano letters
Volume14
Issue number9
DOIs
Publication statusPublished - 2014 Sep 10

All Science Journal Classification (ASJC) codes

  • Bioengineering
  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanical Engineering

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    Liu, Z. F., Wei, S., Yoon, H., Adak, O., Ponce, I., Jiang, Y., Jang, W. D., Campos, L. M., Venkataraman, L., & Neaton, J. B. (2014). Control of single-molecule junction conductance of porphyrins via a transition-metal center. Nano letters, 14(9), 5365-5370. https://doi.org/10.1021/nl5025062