BUILDING BLOCKS FOR MOLECULAR AND MACROMOLECULAR 'METALS'. ELECTRONIC STRUCTURE OF GROUP IVA PHTHALOCYANINE MONOMERS AND COFACIALLY-JOINED DIMERS.

William J. Pietro, Donald E. Ellis, Tobin J Marks, Mark A Ratner

Research output: Contribution to journalArticle

34 Citations (Scopus)

Abstract

The first-principles discrete variational method local exchange (DV-X alpha ) technique has been employed to study electronic structure in the conductive polymer building blocks Si(Pc)(OH)//2 and HOSi(Pc)-OSi(Pc)OH (Pc equals phthalocyaninato). For the monomer, a 'four orbital' porphyrin-like pi electron structure is obtained, and excellent agreement between experimental and calculated optical spectral features is observed. The HOMO-HOMO splitting in the cofacial dimer (2t) can be related to the tight-binding conduction bandwidth in the corresponding polymer (4t). Favorable agreement is obtained between the DV-X alpha calculated splitting and that observed in dimer UPS measurements and polymer optical analyses.

Original languageEnglish
Pages (from-to)273-287
Number of pages15
JournalMolecular Crystals and Liquid Crystals
Volume105
Issue number1-4
Publication statusPublished - Mar 1983

Fingerprint

Dimers
Electronic structure
Polymers
monomers
Monomers
Metals
dimers
electronic structure
polymers
metals
Porphyrins
pi-electrons
porphyrins
bandwidth
Bandwidth
conduction
orbitals
Electrons
phthalocyanine

ASJC Scopus subject areas

  • Engineering(all)

Cite this

@article{286a105ad23c4ae1940cf6cde092a6c1,
title = "BUILDING BLOCKS FOR MOLECULAR AND MACROMOLECULAR 'METALS'. ELECTRONIC STRUCTURE OF GROUP IVA PHTHALOCYANINE MONOMERS AND COFACIALLY-JOINED DIMERS.",
abstract = "The first-principles discrete variational method local exchange (DV-X alpha ) technique has been employed to study electronic structure in the conductive polymer building blocks Si(Pc)(OH)//2 and HOSi(Pc)-OSi(Pc)OH (Pc equals phthalocyaninato). For the monomer, a 'four orbital' porphyrin-like pi electron structure is obtained, and excellent agreement between experimental and calculated optical spectral features is observed. The HOMO-HOMO splitting in the cofacial dimer (2t) can be related to the tight-binding conduction bandwidth in the corresponding polymer (4t). Favorable agreement is obtained between the DV-X alpha calculated splitting and that observed in dimer UPS measurements and polymer optical analyses.",
author = "Pietro, {William J.} and Ellis, {Donald E.} and Marks, {Tobin J} and Ratner, {Mark A}",
year = "1983",
month = "3",
language = "English",
volume = "105",
pages = "273--287",
journal = "Molecular Crystals and Liquid Crystals",
issn = "1542-1406",
publisher = "Taylor and Francis Ltd.",
number = "1-4",

}

TY - JOUR

T1 - BUILDING BLOCKS FOR MOLECULAR AND MACROMOLECULAR 'METALS'. ELECTRONIC STRUCTURE OF GROUP IVA PHTHALOCYANINE MONOMERS AND COFACIALLY-JOINED DIMERS.

AU - Pietro, William J.

AU - Ellis, Donald E.

AU - Marks, Tobin J

AU - Ratner, Mark A

PY - 1983/3

Y1 - 1983/3

N2 - The first-principles discrete variational method local exchange (DV-X alpha ) technique has been employed to study electronic structure in the conductive polymer building blocks Si(Pc)(OH)//2 and HOSi(Pc)-OSi(Pc)OH (Pc equals phthalocyaninato). For the monomer, a 'four orbital' porphyrin-like pi electron structure is obtained, and excellent agreement between experimental and calculated optical spectral features is observed. The HOMO-HOMO splitting in the cofacial dimer (2t) can be related to the tight-binding conduction bandwidth in the corresponding polymer (4t). Favorable agreement is obtained between the DV-X alpha calculated splitting and that observed in dimer UPS measurements and polymer optical analyses.

AB - The first-principles discrete variational method local exchange (DV-X alpha ) technique has been employed to study electronic structure in the conductive polymer building blocks Si(Pc)(OH)//2 and HOSi(Pc)-OSi(Pc)OH (Pc equals phthalocyaninato). For the monomer, a 'four orbital' porphyrin-like pi electron structure is obtained, and excellent agreement between experimental and calculated optical spectral features is observed. The HOMO-HOMO splitting in the cofacial dimer (2t) can be related to the tight-binding conduction bandwidth in the corresponding polymer (4t). Favorable agreement is obtained between the DV-X alpha calculated splitting and that observed in dimer UPS measurements and polymer optical analyses.

UR - http://www.scopus.com/inward/record.url?scp=0020715585&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0020715585&partnerID=8YFLogxK

M3 - Article

VL - 105

SP - 273

EP - 287

JO - Molecular Crystals and Liquid Crystals

JF - Molecular Crystals and Liquid Crystals

SN - 1542-1406

IS - 1-4

ER -