The injecting energy at molecule/metal interfaces

Implications for conductance of molecular junctions from an ab initio molecular description

S. N. Yaliraki, A. E. Roitberg, C. Gonzalez, Vladimiro Mujica, Mark A Ratner

Research output: Contribution to journalArticle

274 Citations (Scopus)

Abstract

To study the electronic transport of molecular wire circuits, we present a time-independent scattering formalism which includes an ab initio description of the molecular electronic structure. This allows us to obtain the molecule-metal coupling description at the same level of theory. The conductance of junction α, α′ xylyl dithiol and benzene- 1,4-dithiol between gold electrodes is obtained and compared with available experimental data. The conductance depends dramatically on the relative position of the Fermi energy of the metal with respect to the molecular levels. We obtain an estimate for the injecting energy of the electron onto the molecule by varying the distance between the molecule and the attached gold clusters. Contrary to the standard assumption, we find that the injecting energy lies close to the molecular highest occupied molecular orbital, rather than in the middle of the gap; it is just the work function of the bulk metal. Finally, the adequacy of the widely used extended Hückel method for conductance calculations is discussed.

Original languageEnglish
Pages (from-to)6997-7002
Number of pages6
JournalJournal of Chemical Physics
Volume111
Issue number15
Publication statusPublished - Oct 15 1999

Fingerprint

Metals
thiols
Gold
Molecules
metals
gold
Molecular electronics
molecules
adequacy
molecular electronics
Molecular orbitals
Benzene
Fermi level
Molecular structure
Electronic structure
energy
molecular orbitals
benzene
wire
Wire

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

The injecting energy at molecule/metal interfaces : Implications for conductance of molecular junctions from an ab initio molecular description. / Yaliraki, S. N.; Roitberg, A. E.; Gonzalez, C.; Mujica, Vladimiro; Ratner, Mark A.

In: Journal of Chemical Physics, Vol. 111, No. 15, 15.10.1999, p. 6997-7002.

Research output: Contribution to journalArticle

@article{962028729a9c4d8bb563a68572acfa5c,
title = "The injecting energy at molecule/metal interfaces: Implications for conductance of molecular junctions from an ab initio molecular description",
abstract = "To study the electronic transport of molecular wire circuits, we present a time-independent scattering formalism which includes an ab initio description of the molecular electronic structure. This allows us to obtain the molecule-metal coupling description at the same level of theory. The conductance of junction α, α′ xylyl dithiol and benzene- 1,4-dithiol between gold electrodes is obtained and compared with available experimental data. The conductance depends dramatically on the relative position of the Fermi energy of the metal with respect to the molecular levels. We obtain an estimate for the injecting energy of the electron onto the molecule by varying the distance between the molecule and the attached gold clusters. Contrary to the standard assumption, we find that the injecting energy lies close to the molecular highest occupied molecular orbital, rather than in the middle of the gap; it is just the work function of the bulk metal. Finally, the adequacy of the widely used extended H{\"u}ckel method for conductance calculations is discussed.",
author = "Yaliraki, {S. N.} and Roitberg, {A. E.} and C. Gonzalez and Vladimiro Mujica and Ratner, {Mark A}",
year = "1999",
month = "10",
day = "15",
language = "English",
volume = "111",
pages = "6997--7002",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "15",

}

TY - JOUR

T1 - The injecting energy at molecule/metal interfaces

T2 - Implications for conductance of molecular junctions from an ab initio molecular description

AU - Yaliraki, S. N.

AU - Roitberg, A. E.

AU - Gonzalez, C.

AU - Mujica, Vladimiro

AU - Ratner, Mark A

PY - 1999/10/15

Y1 - 1999/10/15

N2 - To study the electronic transport of molecular wire circuits, we present a time-independent scattering formalism which includes an ab initio description of the molecular electronic structure. This allows us to obtain the molecule-metal coupling description at the same level of theory. The conductance of junction α, α′ xylyl dithiol and benzene- 1,4-dithiol between gold electrodes is obtained and compared with available experimental data. The conductance depends dramatically on the relative position of the Fermi energy of the metal with respect to the molecular levels. We obtain an estimate for the injecting energy of the electron onto the molecule by varying the distance between the molecule and the attached gold clusters. Contrary to the standard assumption, we find that the injecting energy lies close to the molecular highest occupied molecular orbital, rather than in the middle of the gap; it is just the work function of the bulk metal. Finally, the adequacy of the widely used extended Hückel method for conductance calculations is discussed.

AB - To study the electronic transport of molecular wire circuits, we present a time-independent scattering formalism which includes an ab initio description of the molecular electronic structure. This allows us to obtain the molecule-metal coupling description at the same level of theory. The conductance of junction α, α′ xylyl dithiol and benzene- 1,4-dithiol between gold electrodes is obtained and compared with available experimental data. The conductance depends dramatically on the relative position of the Fermi energy of the metal with respect to the molecular levels. We obtain an estimate for the injecting energy of the electron onto the molecule by varying the distance between the molecule and the attached gold clusters. Contrary to the standard assumption, we find that the injecting energy lies close to the molecular highest occupied molecular orbital, rather than in the middle of the gap; it is just the work function of the bulk metal. Finally, the adequacy of the widely used extended Hückel method for conductance calculations is discussed.

UR - http://www.scopus.com/inward/record.url?scp=0042042118&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0042042118&partnerID=8YFLogxK

M3 - Article

VL - 111

SP - 6997

EP - 7002

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 15

ER -