Mechanism for Si-Si Bond Rupture in Single Molecule Junctions

Haixing Li; Nathaniel T. Kim; Timothy A. Su; Michael L. Steigerwald; Colin Nuckolls; Pierre Darancet; James L. Leighton; Latha Venkataraman

doi:10.1021/jacs.6b10700

Mechanism for Si-Si Bond Rupture in Single Molecule Junctions

Haixing Li, Nathaniel T. Kim, Timothy A. Su, Michael L. Steigerwald^*, Colin Nuckolls, Pierre Darancet, James L. Leighton, Latha Venkataraman

^*Corresponding author for this work

MRC - Materials Research Center

Research output: Contribution to journal › Article › peer-review

33 Scopus citations

Abstract

The stability of chemical bonds can be studied experimentally by rupturing single molecule junctions under applied voltage. Here, we compare voltage-induced bond rupture in two Si-Si backbones: one has no alternate conductive pathway whereas the other contains an additional naphthyl pathway in parallel to the Si-Si bond. We show that in contrast to the first system, the second can conduct through the naphthyl group when the Si-Si bond is ruptured using an applied voltage. We investigate this voltage induced Si-Si bond rupture by ab initio density functional theory calculations and molecular dynamics simulations that ultimately demonstrate that the excitation of molecular vibrational modes by tunneling electrons leads to homolytic Si-Si bond rupture.

Original language	English (US)
Pages (from-to)	16159-16164
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	138
Issue number	49
DOIs	https://doi.org/10.1021/jacs.6b10700
State	Published - Dec 14 2016

Funding

We thank the National Science Foundation for the primary support of this work under Grant CHE-1404922. H.L. is supported in part by the Semiconductor Research Corporation and New York Center for Advanced Interconnect Science and Technology Program. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. P.D. thanks Badri Narayanan for helpful discussions

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.6b10700

Cite this

@article{a60acfbe88d14ce4a882808a5cf4f759,

title = "Mechanism for Si-Si Bond Rupture in Single Molecule Junctions",

abstract = "The stability of chemical bonds can be studied experimentally by rupturing single molecule junctions under applied voltage. Here, we compare voltage-induced bond rupture in two Si-Si backbones: one has no alternate conductive pathway whereas the other contains an additional naphthyl pathway in parallel to the Si-Si bond. We show that in contrast to the first system, the second can conduct through the naphthyl group when the Si-Si bond is ruptured using an applied voltage. We investigate this voltage induced Si-Si bond rupture by ab initio density functional theory calculations and molecular dynamics simulations that ultimately demonstrate that the excitation of molecular vibrational modes by tunneling electrons leads to homolytic Si-Si bond rupture.",

author = "Haixing Li and Kim, {Nathaniel T.} and Su, {Timothy A.} and Steigerwald, {Michael L.} and Colin Nuckolls and Pierre Darancet and Leighton, {James L.} and Latha Venkataraman",

note = "Funding Information: We thank the National Science Foundation for the primary support of this work under Grant CHE-1404922. H.L. is supported in part by the Semiconductor Research Corporation and New York Center for Advanced Interconnect Science and Technology Program. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. P.D. thanks Badri Narayanan for helpful discussions Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = dec,

day = "14",

doi = "10.1021/jacs.6b10700",

language = "English (US)",

volume = "138",

pages = "16159--16164",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "49",

}

TY - JOUR

T1 - Mechanism for Si-Si Bond Rupture in Single Molecule Junctions

AU - Li, Haixing

AU - Kim, Nathaniel T.

AU - Su, Timothy A.

AU - Steigerwald, Michael L.

AU - Nuckolls, Colin

AU - Darancet, Pierre

AU - Leighton, James L.

AU - Venkataraman, Latha

N1 - Funding Information: We thank the National Science Foundation for the primary support of this work under Grant CHE-1404922. H.L. is supported in part by the Semiconductor Research Corporation and New York Center for Advanced Interconnect Science and Technology Program. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. P.D. thanks Badri Narayanan for helpful discussions Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/12/14

Y1 - 2016/12/14

N2 - The stability of chemical bonds can be studied experimentally by rupturing single molecule junctions under applied voltage. Here, we compare voltage-induced bond rupture in two Si-Si backbones: one has no alternate conductive pathway whereas the other contains an additional naphthyl pathway in parallel to the Si-Si bond. We show that in contrast to the first system, the second can conduct through the naphthyl group when the Si-Si bond is ruptured using an applied voltage. We investigate this voltage induced Si-Si bond rupture by ab initio density functional theory calculations and molecular dynamics simulations that ultimately demonstrate that the excitation of molecular vibrational modes by tunneling electrons leads to homolytic Si-Si bond rupture.

AB - The stability of chemical bonds can be studied experimentally by rupturing single molecule junctions under applied voltage. Here, we compare voltage-induced bond rupture in two Si-Si backbones: one has no alternate conductive pathway whereas the other contains an additional naphthyl pathway in parallel to the Si-Si bond. We show that in contrast to the first system, the second can conduct through the naphthyl group when the Si-Si bond is ruptured using an applied voltage. We investigate this voltage induced Si-Si bond rupture by ab initio density functional theory calculations and molecular dynamics simulations that ultimately demonstrate that the excitation of molecular vibrational modes by tunneling electrons leads to homolytic Si-Si bond rupture.

UR - http://www.scopus.com/inward/record.url?scp=85006324376&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85006324376&partnerID=8YFLogxK

U2 - 10.1021/jacs.6b10700

DO - 10.1021/jacs.6b10700

M3 - Article

C2 - 27960303

AN - SCOPUS:85006324376

SN - 0002-7863

VL - 138

SP - 16159

EP - 16164

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 49

ER -

Mechanism for Si-Si Bond Rupture in Single Molecule Junctions

Abstract

Funding

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this