Orbital control of single-molecule conductance perturbed by π-accepting anchor groups: Cyanide and isocyanide

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Electron transport properties through benzene molecules disubstituted with π-accepting cyanide and isocyanide anchor groups at their para and meta positions are investigated on the basis of a qualitative orbital analysis at the Hückel molecular orbital level of theory. The applicability of a previously derived orbital symmetry rule for electron transport is extended to the systems perturbed by the π-accepting anchor groups, where the HOMO-LUMO symmetry in the molecular orbital energies relative to the Fermi level is removed. The conservation of the HOMO-LUMO symmetry in the spatial distribution of the molecular orbitals between the unperturbed benzene molecule and the perturbed molecules with the anchor groups rationalizes symmetry-allowed electron transport through the para isomers. On the other hand, destructive interferences between the nearly 2-fold degenerate frontier orbitals constructed from the 2-fold degenerate orbitals of the unperturbed benzene molecule and the anchor groups lead to symmetry-forbidden electron transport through the meta isomers. The qualitative orbital thinking is supported by more quantitative density functional theory (DFT) calculations combined with the nonequilibrium Green's function (NEGF) method. The orbital analysis is a powerful tool for the understanding and rational design of molecular devices composed of π-conjugated hydrocarbons and those perturbed by the π-accepting anchor groups.

Original languageEnglish
Pages (from-to)20607-20616
Number of pages10
JournalJournal of Physical Chemistry C
Volume116
Issue number38
DOIs
Publication statusPublished - Sep 27 2012

Fingerprint

Cyanides
cyanides
Anchors
Molecular orbitals
orbitals
Benzene
Molecules
symmetry
molecules
molecular orbitals
Isomers
benzene
electrons
Electron transport properties
isomers
Hydrocarbons
Fermi level
Green's function
Spatial distribution
Density functional theory

All Science Journal Classification (ASJC) codes

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

Cite this

Orbital control of single-molecule conductance perturbed by π-accepting anchor groups : Cyanide and isocyanide. / Koga, Junya; Tsuji, Yuta; Yoshizawa, Kazunari.

In: Journal of Physical Chemistry C, Vol. 116, No. 38, 27.09.2012, p. 20607-20616.

Research output: Contribution to journalArticle

@article{c226f1cefe224da3a54c22f413a79a5b,
title = "Orbital control of single-molecule conductance perturbed by π-accepting anchor groups: Cyanide and isocyanide",
abstract = "Electron transport properties through benzene molecules disubstituted with π-accepting cyanide and isocyanide anchor groups at their para and meta positions are investigated on the basis of a qualitative orbital analysis at the H{\"u}ckel molecular orbital level of theory. The applicability of a previously derived orbital symmetry rule for electron transport is extended to the systems perturbed by the π-accepting anchor groups, where the HOMO-LUMO symmetry in the molecular orbital energies relative to the Fermi level is removed. The conservation of the HOMO-LUMO symmetry in the spatial distribution of the molecular orbitals between the unperturbed benzene molecule and the perturbed molecules with the anchor groups rationalizes symmetry-allowed electron transport through the para isomers. On the other hand, destructive interferences between the nearly 2-fold degenerate frontier orbitals constructed from the 2-fold degenerate orbitals of the unperturbed benzene molecule and the anchor groups lead to symmetry-forbidden electron transport through the meta isomers. The qualitative orbital thinking is supported by more quantitative density functional theory (DFT) calculations combined with the nonequilibrium Green's function (NEGF) method. The orbital analysis is a powerful tool for the understanding and rational design of molecular devices composed of π-conjugated hydrocarbons and those perturbed by the π-accepting anchor groups.",
author = "Junya Koga and Yuta Tsuji and Kazunari Yoshizawa",
year = "2012",
month = "9",
day = "27",
doi = "10.1021/jp3068156",
language = "English",
volume = "116",
pages = "20607--20616",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "38",

}

TY - JOUR

T1 - Orbital control of single-molecule conductance perturbed by π-accepting anchor groups

T2 - Cyanide and isocyanide

AU - Koga, Junya

AU - Tsuji, Yuta

AU - Yoshizawa, Kazunari

PY - 2012/9/27

Y1 - 2012/9/27

N2 - Electron transport properties through benzene molecules disubstituted with π-accepting cyanide and isocyanide anchor groups at their para and meta positions are investigated on the basis of a qualitative orbital analysis at the Hückel molecular orbital level of theory. The applicability of a previously derived orbital symmetry rule for electron transport is extended to the systems perturbed by the π-accepting anchor groups, where the HOMO-LUMO symmetry in the molecular orbital energies relative to the Fermi level is removed. The conservation of the HOMO-LUMO symmetry in the spatial distribution of the molecular orbitals between the unperturbed benzene molecule and the perturbed molecules with the anchor groups rationalizes symmetry-allowed electron transport through the para isomers. On the other hand, destructive interferences between the nearly 2-fold degenerate frontier orbitals constructed from the 2-fold degenerate orbitals of the unperturbed benzene molecule and the anchor groups lead to symmetry-forbidden electron transport through the meta isomers. The qualitative orbital thinking is supported by more quantitative density functional theory (DFT) calculations combined with the nonequilibrium Green's function (NEGF) method. The orbital analysis is a powerful tool for the understanding and rational design of molecular devices composed of π-conjugated hydrocarbons and those perturbed by the π-accepting anchor groups.

AB - Electron transport properties through benzene molecules disubstituted with π-accepting cyanide and isocyanide anchor groups at their para and meta positions are investigated on the basis of a qualitative orbital analysis at the Hückel molecular orbital level of theory. The applicability of a previously derived orbital symmetry rule for electron transport is extended to the systems perturbed by the π-accepting anchor groups, where the HOMO-LUMO symmetry in the molecular orbital energies relative to the Fermi level is removed. The conservation of the HOMO-LUMO symmetry in the spatial distribution of the molecular orbitals between the unperturbed benzene molecule and the perturbed molecules with the anchor groups rationalizes symmetry-allowed electron transport through the para isomers. On the other hand, destructive interferences between the nearly 2-fold degenerate frontier orbitals constructed from the 2-fold degenerate orbitals of the unperturbed benzene molecule and the anchor groups lead to symmetry-forbidden electron transport through the meta isomers. The qualitative orbital thinking is supported by more quantitative density functional theory (DFT) calculations combined with the nonequilibrium Green's function (NEGF) method. The orbital analysis is a powerful tool for the understanding and rational design of molecular devices composed of π-conjugated hydrocarbons and those perturbed by the π-accepting anchor groups.

UR - http://www.scopus.com/inward/record.url?scp=84866858947&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84866858947&partnerID=8YFLogxK

U2 - 10.1021/jp3068156

DO - 10.1021/jp3068156

M3 - Article

AN - SCOPUS:84866858947

VL - 116

SP - 20607

EP - 20616

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 38

ER -