Reaction pathway of the [4 + 2] diels-alder adduct formation on Si(100)-2x1

Peter Minary, Mark Tuckerman

Research output: Contribution to journalArticle

Abstract

Despite a long history of experimental and theoretical investigation, the mechanism of the Diels-Alder (DA) reaction has been controversial since its discovery 80 years ago. From these investigations, two schools of thought have emerged, namely that the reaction can proceed via a concerted, symmetric or asymmetric mechanism or via a nonconcerted mechanism involving a zwitterion or diradical as an intermediate. Here, we employ finite temperature ab initio molecular dynamics simulations, employing forces computed "on the fly" from electronic structure calculations, to investigate the microscopic mechanism of DA adduct formation between 1,3-butadiene and the Si(100)-2×1 surface. Free energy profiles and nonequilibrium trajectories strongly suggest a nonconcerted mechanism that forms a zwitterionic intermediate state. This mechanism, which begins with a nucleophilic attack of the C=C double bond on the positive member of a charge-asymmetric buckled Si-Si dimer, was previously shown to be common to the formation of a wide range of adducts that can form on the surface.

Original languageEnglish (US)
Pages (from-to)13920-13921
Number of pages2
JournalJournal of the American Chemical Society
Volume126
Issue number43
DOIs
StatePublished - Nov 3 2004

Fingerprint

Alnus
Cycloaddition Reaction
Molecular Dynamics Simulation
Diptera
Temperature
Butadiene
Dimers
Free energy
Electronic structure
Molecular dynamics
Trajectories
Computer simulation
1,3-butadiene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Reaction pathway of the [4 + 2] diels-alder adduct formation on Si(100)-2x1. / Minary, Peter; Tuckerman, Mark.

In: Journal of the American Chemical Society, Vol. 126, No. 43, 03.11.2004, p. 13920-13921.

Research output: Contribution to journalArticle

@article{27361a68e4064c349cc2ea45edebad37,
title = "Reaction pathway of the [4 + 2] diels-alder adduct formation on Si(100)-2x1",
abstract = "Despite a long history of experimental and theoretical investigation, the mechanism of the Diels-Alder (DA) reaction has been controversial since its discovery 80 years ago. From these investigations, two schools of thought have emerged, namely that the reaction can proceed via a concerted, symmetric or asymmetric mechanism or via a nonconcerted mechanism involving a zwitterion or diradical as an intermediate. Here, we employ finite temperature ab initio molecular dynamics simulations, employing forces computed {"}on the fly{"} from electronic structure calculations, to investigate the microscopic mechanism of DA adduct formation between 1,3-butadiene and the Si(100)-2×1 surface. Free energy profiles and nonequilibrium trajectories strongly suggest a nonconcerted mechanism that forms a zwitterionic intermediate state. This mechanism, which begins with a nucleophilic attack of the C=C double bond on the positive member of a charge-asymmetric buckled Si-Si dimer, was previously shown to be common to the formation of a wide range of adducts that can form on the surface.",
author = "Peter Minary and Mark Tuckerman",
year = "2004",
month = "11",
day = "3",
doi = "10.1021/ja046522m",
language = "English (US)",
volume = "126",
pages = "13920--13921",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "43",

}

TY - JOUR

T1 - Reaction pathway of the [4 + 2] diels-alder adduct formation on Si(100)-2x1

AU - Minary, Peter

AU - Tuckerman, Mark

PY - 2004/11/3

Y1 - 2004/11/3

N2 - Despite a long history of experimental and theoretical investigation, the mechanism of the Diels-Alder (DA) reaction has been controversial since its discovery 80 years ago. From these investigations, two schools of thought have emerged, namely that the reaction can proceed via a concerted, symmetric or asymmetric mechanism or via a nonconcerted mechanism involving a zwitterion or diradical as an intermediate. Here, we employ finite temperature ab initio molecular dynamics simulations, employing forces computed "on the fly" from electronic structure calculations, to investigate the microscopic mechanism of DA adduct formation between 1,3-butadiene and the Si(100)-2×1 surface. Free energy profiles and nonequilibrium trajectories strongly suggest a nonconcerted mechanism that forms a zwitterionic intermediate state. This mechanism, which begins with a nucleophilic attack of the C=C double bond on the positive member of a charge-asymmetric buckled Si-Si dimer, was previously shown to be common to the formation of a wide range of adducts that can form on the surface.

AB - Despite a long history of experimental and theoretical investigation, the mechanism of the Diels-Alder (DA) reaction has been controversial since its discovery 80 years ago. From these investigations, two schools of thought have emerged, namely that the reaction can proceed via a concerted, symmetric or asymmetric mechanism or via a nonconcerted mechanism involving a zwitterion or diradical as an intermediate. Here, we employ finite temperature ab initio molecular dynamics simulations, employing forces computed "on the fly" from electronic structure calculations, to investigate the microscopic mechanism of DA adduct formation between 1,3-butadiene and the Si(100)-2×1 surface. Free energy profiles and nonequilibrium trajectories strongly suggest a nonconcerted mechanism that forms a zwitterionic intermediate state. This mechanism, which begins with a nucleophilic attack of the C=C double bond on the positive member of a charge-asymmetric buckled Si-Si dimer, was previously shown to be common to the formation of a wide range of adducts that can form on the surface.

UR - http://www.scopus.com/inward/record.url?scp=7544228947&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=7544228947&partnerID=8YFLogxK

U2 - 10.1021/ja046522m

DO - 10.1021/ja046522m

M3 - Article

C2 - 15506742

AN - SCOPUS:7544228947

VL - 126

SP - 13920

EP - 13921

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 43

ER -