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Fermi Level Pinning And Orbital Polarization Effects In Molecular Junctions: The Role Of Metal Induced Gap States
C. Dyck, V. Geskin, J. Cornil
Published 2014 · Materials Science
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Understanding the alignment of molecular orbitals and corresponding transmission peaks with respect to the Fermi level of the electrodes is a major challenge in the field of molecular electronics. In order to design functional devices, it is of utmost importance to assess whether controlled changes in the electronic structure of isolated compounds are preserved once they are inserted in the molecular junctions. Here, light is shed on this central issue by performing density functional theory calculations on junctions including diarylethene-based molecules. It is demonstrated that the chemical potential equalization principle allows to rationalize the existence or not of a Fermi level pinning (i.e., same alignment in spite of a varying ionization potential in the isolated compounds), pointing to the essential role played by metal induced gap states (MIGS). It is further evidenced that the degree of level pinning is intimately linked to the degree of orbital polarization when a bias is applied between the two electrodes.
This paper references
Rotational Isomerization of Dithienylethenes: A Study on the Mechanism Determining Quantum Yield of Cyclization Reaction
Alexander F. G. Goldberg (2003)
Forty years of molecular electronics: Non-equilibrium heat and charge transport at the nanoscale
J. Bergfield (2013)
Adsorption of thiolates to singly coordinated sites on Au111 evidenced by photoelectron diffraction.
H. Kondoh (2003)
The Kohn-Sham gap, the fundamental gap and the optical gap: the physical meaning of occupied and virtual Kohn-Sham orbital energies.
E. J. Baerends (2013)
Electronegativity Equalization Method for the Calculation of Atomic Charges in Molecules.
W. J. Mortier (1986)
Microscopic study of electrical transport through individual molecules with metallic contacts. I. Band lineup, voltage drop, and high-field transport
Yongqiang Xue (2003)
Ab initio calculation of the biasdependent transport properties of Mn12 molecules
S. Sanvito (2009)
Interface states, negative differential resistance, and rectification in molecular junctions with transition-metal contacts
H. Dalgleish (2006)
Light-controlled conductance switching of ordered metal-molecule-metal devices.
S. J. van der Molen (2009)
Photo-modulable molecular transport junctions based on organometallic molecular wires
Fanben Meng (2012)
Molecular Electronic Junctions
R. McCreery (2004)
Resistance of alkanethiol molecular wires
C. Kaun (2003)
What can a scanning tunneling microscope image do for the insulating alkanethiol molecules on Au(111) substrates
Changgan Zeng (2002)
Doping molecular wires.
G. Heimel (2009)
Electrostatic potential profiles of molecular conductors
G. Liang (2004)
Introducing molecular electronics
M. Ratner (2002)
Electronics and chemistry: varying single-molecule junction conductance using chemical substituents.
L. Venkataraman (2007)
Nonlinear conductance in molecular devices: Molecular length dependence
Ž. Crljen (2005)
Role of the exchange-correlation potential in ab initio electron transport calculations.
S. Ke (2007)
Formation of an electric dipole at metal-semiconductor interfaces
R. Tung (2001)
Photoswitching of Conductivity through a Diarylperfluorocyclopentene Nanowire
Aleksandar Staykov (2007)
Electronegativity: The density functional viewpoint
R. Parr (1978)
Electronic structure of hybrid interfaces for polymer-based electronics.
M. Fahlman (2007)
Impact of derivatization on electron transmission through dithienylethene-based photoswitches in molecular junctions.
Colin Van Dyck (2013)
Electrical transmission of molecular bridges
F. Remacle (2004)
Ab-initio Non-Equilibrium Green’s Function Formalism for Calculating Electron Transport in Molecular Devices
K. Stokbro (2006)
Density-functional thermochemistry. III. The role of exact exchange
Axel D. Becke (1993)
Ab initio modeling of quantum transport properties of molecular electronic devices
J. Taylor (2001)
Generalized Gradient Approximation Made Simple.
What Do the Kohn−Sham Orbitals and Eigenvalues Mean?
R. Stowasser (1999)
Energetics of metal–organic interfaces: New experiments and assessment of the field
Jaehyung Hwang (2009)
SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS
H. J. Monkhorst (1976)
Renormalization of molecular electronic levels at metal-molecule interfaces.
J. Neaton (2006)
Tuning the Energy Levels of Photochromic Diarylethene Compounds for Opto-electronic Switch Devices
Fredrik Jakobsson (2009)
Energy‐Level Alignment at Organic/Metal and Organic/Organic Interfaces
S. Braun (2009)
Characterization of the interface dipole at organic/ metal interfaces.
X. Crispin (2002)
First-principles study of length dependence of conductance in alkanedithiols.
Y. Zhou (2008)
Polarization-induced renormalization of molecular levels at metallic and semiconducting surfaces
J. M. García-Lastra (2009)
Photoinduced work function changes by isomerization of a densely packed azobenzene-based SAM on Au: a joint experimental and theoretical study.
N. Crivillers (2011)
Numerical atomic orbitals for linear-scaling calculations
J. Junquera (2001)
Self-consistent GW calculations of electronic transport in thiol- and amine-linked molecular junctions
M. Strange (2011)
Schottky Barrier Heights and the Continuum of Gap States
J. Tersoff (1984)
Energy level alignment and quantum conductance of functionalized metal-molecule junctions: density functional theory versus GW calculations.
Chengjun Jin (2013)
Understanding the Electronic Structure of Metal/SAM/Organic−Semiconductor Heterojunctions
Ferdinand Rissner (2009)
Density functional calculations of nanoscale conductance
M. Koentopp (2008)
Conduction switching of photochromic molecules.
J. Li (2004)
Modeling the electronic properties of pi-conjugated self-assembled monolayers.
G. Heimel (2010)
Molecular tunnel junctions based on π-conjugated oligoacene thiols and dithiols between Ag, Au, and Pt contacts: effect of surface linking group and metal work function.
B. Kim (2011)
A critical perspective on molecular electronic junctions: there is plenty of room in the middle.
R. McCreery (2013)
Contact configuration dependence of conductance of 1,4-phenylene diisocyanide molecular junction
X. Yan (2006)
Exact differential equation for the density and ionization energy of a many-particle system
M. Levy (1984)
Charge Transfer on the Nanoscale: Current Status
D. Adams (2003)
Switching of a photochromic molecule on gold electrodes: single-molecule measurements
J. He (2005)
Recent advances in Schottky barrier concepts
R. Tung (2001)
Are Kohn-Sham conductances accurate?
Hector Mera (2010)
Molecular Transport Junctions: Clearing Mists
S. Lindsay (2007)
First-principles based matrix Green's function approach to molecular electronic devices: general formalism
Yongqiang Xue (2002)
Comment on “Generalized Gradient Approximation Made Simple”
Y. Zhang (1998)
Constrained-DFT method for accurate energy-level alignment of metal/molecule interfaces
A. M. Souza (2013)
Diarylethenes for Memories and Switches.
M. Irie (2000)
Extracting electron transfer coupling elements from constrained density functional theory.
Qin Wu (2006)
One-way optoelectronic switching of photochromic molecules on gold.
D. Dulić (2003)
Comparison of Electronic Transport Measurements on Organic Molecules
Adi Salomon (2003)
Density-functional exchange-energy approximation with correct asymptotic behavior.
Molecular electronics—science and technology
A. Aviram (1989)
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density.
Determination of performance on tunnel conduction through molecular wire using a conductive atomic force microscope
H. Sakaguchi (2001)
Investigation of the conducting properties of a photoswitching dithienylethene molecule.
A. Odell (2010)
Revealing the role of anchoring groups in the electrical conduction through single-molecule junctions.
L. Zotti (2010)
Electron transport in molecular junctions
N. Tao (2006)
Density-functional method for nonequilibrium electron transport
M. Brandbyge (2002)
Moletronics: future electronics
K. Kwok (2002)
Exact results for the charge and spin densities, exchange-correlation potentials, and density-functional eigenvalues.
An Interpretation of Bond Lengths and a Classification of Bonds.
R. Sanderson (1951)
Quantum Physics Under Control
I. A. Walmsley (2003)
Theoretical study of the electronic and optical properties of photochromic dithienylethene derivatives connected to small gold clusters.
A. Perrier (2007)
Reversible Conductance Switching in Molecular Devices
A. Kronemeijer (2008)
Identifying the length dependence of orbital alignment and contact coupling in molecular heterojunctions.
J. Malen (2009)
Single molecule electron transport junctions: charging and geometric effects on conductance.
D. Q. Andrews (2006)
A New Electroaffinity Scale; Together with Data on Valence States and on Valence Ionization Potentials and Electron Affinities
R. S. Mulliken (1934)
Role of the virtual orbitals and HOMO-LUMO gap in mean-field approximations to the conductance of molecular junctions
A. Cehovin (2008)
This paper is referenced by
Large Negative Differential Resistance and Rectification from a Donor-σ-Acceptor Molecule in the Presence of Dissimilar Electrodes.
Sayantanu Koley (2018)
Strong Fermi level pinning induces a high rectification ratio and negative differential resistance in hydrogen bonding bridged single cytidine pair junctions.
H. Ren (2016)
Effect of the substitution of F on the photoswitching behavior in single molecular device
Baoan Bian (2017)
Novel electron-deficient oligo(phenyleneethynylene) derivatives for molecular electronics
Rachid Kitouni (2018)
HOMO-LUMO coupling: the fourth rule for highly effective molecular rectifiers.
Aaron Zhenghui Thong (2017)
Impact of Anchoring Groups on Ballistic Transport: Single Molecule vs Monolayer Junctions
V. Obersteiner (2015)
Molecular Junctions: Control of the Energy Gap Achieved by a Pinning Effect
Colin Van Dyck (2017)
Experimental and Theoretical Analysis of Nanotransport in Oligophenylene Dithiol Junctions as a Function of Molecular Length and Contact Work Function.
Z. Xie (2015)
Energy Level Alignment at Interfaces Between Au (111) and Thiolated Oligophenylenes of Increasing Chain Size: Theoretical Evidence of Pinning Effects
Valentín Diez-Cabanes (2018)
Paving the way to single-molecule chemistry through molecular electronics.
Masateru Taniguchi (2019)
Heterospin biradicals provide insight into molecular conductance and rectification† †Electronic supplementary information (ESI) available. CCDC 1526005 and 1526006. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc00073a
Martin L. Kirk (2017)
Large-Area, Ensemble Molecular Electronics: Motivation and Challenges.
A. Vilan (2017)
Influence of the donor unit on the rectification ratio in tunnel junctions based on donor-acceptor SAMs using PTM units as acceptors.
M. Souto (2018)
Electronic transport regimes through an alkoxythiolated diphenyl-2,2'-bithiophene-based molecular junction diodes: critical assessment of the thermal dependence.
G. Pace (2015)
Electronic transport induced by asymmetric adsorption site of sulfur in molecular device
Baoan Bian (2019)
Understanding the Properties of Tailor-Made Self-Assembled Monolayers with Embedded Dipole Moments for Interface Engineering
Michael Gärtner (2018)
Effect of the lateral linking groups on the switching behavior in single molecular device
Jingjuan Yang (2018)
Energy Level Alignment at Titanium Oxide−Dye Interfaces: Implications for Electron Injection and Light Harvesting
Laurent Lasser (2015)
Chain Length Dependence of the Dielectric Constant and Polarizability in Conjugated Organic Thin Films.
C. Van Dyck (2017)
Effects of electronic coupling and electrostatic potential on charge transport in carbon-based molecular electronic junctions
Richard L McCreery (2016)
Influence of anchoring groups on single-molecular junction conductance: Theoretical comparative study of thiol and amine
Fang Xie (2017)
Large Built‐In Fields Control the Electronic Properties of Nanoscale Molecular Devices with Dipolar Structures
Colin Van Dyck (2018)
Electronic Communication as a Transferable Property of Molecular Bridges?
C. Herrmann (2019)
Electron transport through phenylene sandwiched between zigzag graphene nanoribbons
A-Long Yao (2018)
Harnessing Quantum Interference in Molecular Dielectric Materials.
Justin P. Bergfield (2015)
A surprising way to control the charge transport in molecular electronics: the subtle impact of the coverage of self-assembled monolayers of floppy molecules adsorbed on metallic electrodes.
Ioan Bâldea (2017)
Protonation tuning of quantum interference in azulene-type single-molecule junctions† †Electronic supplementary information (ESI) available: Synthesis and characterization of compounds, details of single-molecule conductance measurement and the calculation. See DOI: 10.1039/c7sc01014a Click here for
G. Yang (2017)
Switching behavior induced by different substituents of group in single molecular device
Baoan Bian (2018)
Enhancement of magnetoresistance and current spin polarization in single-molecule junctions by manipulating the hybrid interface states via anchoring groups
S. Qiu (2019)
Molecular rectifiers: a new design based on asymmetric anchoring moieties.
C. Van Dyck (2015)
Light‐Stimulated Charge Transport in Bilayer Molecular Junctions for Photodetection
Shailendra K Saxena (2019)
Tuning electronic transport via hepta-alanine peptides junction by tryptophan doping
Cunlan Guo (2016)See more