Molecular Rectification Enhancement Based on Conformational and Chemical Modifications

Jesús Valdiviezo, Julio L. Palma Anda

Research output: Contribution to journalArticle

Abstract

Design principles for molecules with intrinsic directional charge transport will likely prove crucial for breakthroughs in nanotechnology and other emerging fields like biosensors and advanced photovoltaics. Here, we perform a systematic computational study to characterize the electronic rectification induced by conformational and chemical modifications at low bias potentials and elucidate design principles for intrinsic molecular rectifiers. We study donor-bridge-acceptor (D-B-A) systems that consist of phenylene units with geometrical rotation of the rings and representative electron-donating and -withdrawing substituent groups at the donor and acceptor sites. We calculate transport properties using the non-equilibrium Green's function technique and density functional theory (DFT-NEGF) and obtain I-V characteristics and rectification ratios. Our results indicate that efficient intrinsic rectification at low bias voltages can only be obtained by combining dihedral angles of 60° between phenyl rings and asymmetric chemical substitution. Together, these structural features cause rectification enhancement by localizing the molecular orbital closer to the Fermi level of the electrode in one end of the molecular device. Our designed systems present rectification ratios up to 20.08 at 0.3 V in their minimum-energy geometry and are predicted to be stable under thermal fluctuations.

Original languageEnglish (US)
Pages (from-to)2053-2063
Number of pages11
JournalJournal of Physical Chemistry C
Volume122
Issue number4
DOIs
StatePublished - Feb 1 2018

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Chemical modification
rectification
augmentation
Molecular orbitals
Dihedral angle
Bias voltage
Fermi level
Nanotechnology
Green's function
Biosensors
Discrete Fourier transforms
Transport properties
Density functional theory
Charge transfer
Substitution reactions
Electrodes
Molecules
Geometry
Electrons
rectifiers

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

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abstract = "Design principles for molecules with intrinsic directional charge transport will likely prove crucial for breakthroughs in nanotechnology and other emerging fields like biosensors and advanced photovoltaics. Here, we perform a systematic computational study to characterize the electronic rectification induced by conformational and chemical modifications at low bias potentials and elucidate design principles for intrinsic molecular rectifiers. We study donor-bridge-acceptor (D-B-A) systems that consist of phenylene units with geometrical rotation of the rings and representative electron-donating and -withdrawing substituent groups at the donor and acceptor sites. We calculate transport properties using the non-equilibrium Green's function technique and density functional theory (DFT-NEGF) and obtain I-V characteristics and rectification ratios. Our results indicate that efficient intrinsic rectification at low bias voltages can only be obtained by combining dihedral angles of 60° between phenyl rings and asymmetric chemical substitution. Together, these structural features cause rectification enhancement by localizing the molecular orbital closer to the Fermi level of the electrode in one end of the molecular device. Our designed systems present rectification ratios up to 20.08 at 0.3 V in their minimum-energy geometry and are predicted to be stable under thermal fluctuations.",
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Molecular Rectification Enhancement Based on Conformational and Chemical Modifications. / Valdiviezo, Jesús; Palma Anda, Julio L.

In: Journal of Physical Chemistry C, Vol. 122, No. 4, 01.02.2018, p. 2053-2063.

Research output: Contribution to journalArticle

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