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

Research output: Contribution to journalArticle

43 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

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Porphyrins
porphyrins
Transition metals
Metals
transition metals
functionals
Molecules
metals
molecules
trends
Ionization potential
energy conversion
Energy conversion
Green's function
Gold
Electronic structure
Density functional theory
Cations
Charge transfer
counters

All Science Journal Classification (ASJC) codes

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

Cite this

Liu, Z. F., Wei, S., Yoon, H., Adak, O., Ponce, I., Jiang, Y., ... 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
Liu, Zhen Fei ; Wei, Sujun ; Yoon, Hongsik ; Adak, Olgun ; Ponce, Ingrid ; Jiang, Yivan ; Jang, Woo Dong ; Campos, Luis M. ; Venkataraman, Latha ; Neaton, Jeffrey B. / Control of single-molecule junction conductance of porphyrins via a transition-metal center. In: Nano letters. 2014 ; Vol. 14, No. 9. pp. 5365-5370.
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Liu, ZF, Wei, S, Yoon, H, Adak, O, Ponce, I, Jiang, Y, Jang, WD, Campos, LM, Venkataraman, L & Neaton, JB 2014, 'Control of single-molecule junction conductance of porphyrins via a transition-metal center', Nano letters, vol. 14, no. 9, pp. 5365-5370. https://doi.org/10.1021/nl5025062

Control of single-molecule junction conductance of porphyrins via a transition-metal center. / Liu, Zhen Fei; Wei, Sujun; Yoon, Hongsik; Adak, Olgun; Ponce, Ingrid; Jiang, Yivan; Jang, Woo Dong; Campos, Luis M.; Venkataraman, Latha; Neaton, Jeffrey B.

In: Nano letters, Vol. 14, No. 9, 10.09.2014, p. 5365-5370.

Research output: Contribution to journalArticle

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AU - Jiang, Yivan

AU - Jang, Woo Dong

AU - Campos, Luis M.

AU - Venkataraman, Latha

AU - Neaton, Jeffrey B.

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