Propensity rules for inelastic electron tunneling spectroscopy of single-molecule transport junctions

Alessandro Troisi, Mark A Ratner

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

Using a perturbative approach to simple model systems, we derive useful propensity rules for inelastic electron tunneling spectroscopy (IETS) of molecular wire junctions. We examine the circumstances under which this spectroscopy (that has no rigorous selection rules) obeys well defined propensity rules based on the molecular symmetry and on the topology of the molecule in the junction. Focusing on conjugated molecules of C2h symmetry, semiquantitative arguments suggest that the IETS is dominated by ag vibrations in the high energy region and by out of plane modes (au and bg) in the low energy region. Realistic computations verify that the proposed propensity rules are strictly obeyed by medium to large-sized conjugated molecules but are subject to some exceptions when small molecules are considered. The propensity rules facilitate the use of IETS to help characterize the molecular geometry within the junction.

Original languageEnglish
Article number214709
JournalJournal of Chemical Physics
Volume125
Issue number21
DOIs
Publication statusPublished - 2006

Fingerprint

Electron tunneling
electron tunneling
Spectroscopy
Molecules
spectroscopy
molecules
symmetry
topology
Topology
wire
Wire
vibration
Geometry
energy
geometry

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Propensity rules for inelastic electron tunneling spectroscopy of single-molecule transport junctions. / Troisi, Alessandro; Ratner, Mark A.

In: Journal of Chemical Physics, Vol. 125, No. 21, 214709, 2006.

Research output: Contribution to journalArticle

@article{c22244fa53084f6da5091322d14aa2a5,
title = "Propensity rules for inelastic electron tunneling spectroscopy of single-molecule transport junctions",
abstract = "Using a perturbative approach to simple model systems, we derive useful propensity rules for inelastic electron tunneling spectroscopy (IETS) of molecular wire junctions. We examine the circumstances under which this spectroscopy (that has no rigorous selection rules) obeys well defined propensity rules based on the molecular symmetry and on the topology of the molecule in the junction. Focusing on conjugated molecules of C2h symmetry, semiquantitative arguments suggest that the IETS is dominated by ag vibrations in the high energy region and by out of plane modes (au and bg) in the low energy region. Realistic computations verify that the proposed propensity rules are strictly obeyed by medium to large-sized conjugated molecules but are subject to some exceptions when small molecules are considered. The propensity rules facilitate the use of IETS to help characterize the molecular geometry within the junction.",
author = "Alessandro Troisi and Ratner, {Mark A}",
year = "2006",
doi = "10.1063/1.2390698",
language = "English",
volume = "125",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "21",

}

TY - JOUR

T1 - Propensity rules for inelastic electron tunneling spectroscopy of single-molecule transport junctions

AU - Troisi, Alessandro

AU - Ratner, Mark A

PY - 2006

Y1 - 2006

N2 - Using a perturbative approach to simple model systems, we derive useful propensity rules for inelastic electron tunneling spectroscopy (IETS) of molecular wire junctions. We examine the circumstances under which this spectroscopy (that has no rigorous selection rules) obeys well defined propensity rules based on the molecular symmetry and on the topology of the molecule in the junction. Focusing on conjugated molecules of C2h symmetry, semiquantitative arguments suggest that the IETS is dominated by ag vibrations in the high energy region and by out of plane modes (au and bg) in the low energy region. Realistic computations verify that the proposed propensity rules are strictly obeyed by medium to large-sized conjugated molecules but are subject to some exceptions when small molecules are considered. The propensity rules facilitate the use of IETS to help characterize the molecular geometry within the junction.

AB - Using a perturbative approach to simple model systems, we derive useful propensity rules for inelastic electron tunneling spectroscopy (IETS) of molecular wire junctions. We examine the circumstances under which this spectroscopy (that has no rigorous selection rules) obeys well defined propensity rules based on the molecular symmetry and on the topology of the molecule in the junction. Focusing on conjugated molecules of C2h symmetry, semiquantitative arguments suggest that the IETS is dominated by ag vibrations in the high energy region and by out of plane modes (au and bg) in the low energy region. Realistic computations verify that the proposed propensity rules are strictly obeyed by medium to large-sized conjugated molecules but are subject to some exceptions when small molecules are considered. The propensity rules facilitate the use of IETS to help characterize the molecular geometry within the junction.

UR - http://www.scopus.com/inward/record.url?scp=33845432476&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33845432476&partnerID=8YFLogxK

U2 - 10.1063/1.2390698

DO - 10.1063/1.2390698

M3 - Article

VL - 125

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 21

M1 - 214709

ER -