Electronic and optical properties of vertex-sharing homo- and hetero-biicosahedral gold clusters

Takeshi Iwasa, Katsuyuki Nobusada, Atsushi Nakajima

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

Electronic and optical properties of vertex sharing homo- and heterobiicosahedral gold clusters [M1M2Au 23(PH3)10(SCH3)5Cl 2]2+ (M1/M2 = Au/Au, Pt/Hg) are investigated by means of density functional computations, focusing on superatom assembly. In the homo clusters, the projected density of states onto the spherical harmonics reveals that each icosahedral unit behaves as a superatom with the Au(6s6p) electrons and electron shell closings of S and P orbitals followed by unoccupied D orbitals; each unit satisfies an 8-electron superatom condition. Because the Au(5d) band appears between the S and P orbitals, the electronic structure is characterized as S, Au(5d)-band, and P. The lowest electronic excitation in the homo cluster is the P to D transition. In the hetero biicosahedral cluster, the central Au atoms of each icosahedron are replaced by Pt and Hg. The HOMO and LUMO are well localized to the PtAu 12 and HgAu12 units, respectively, forming a cluster-assembled heterojunction in a single stable structure. The absorption spectrum of the heterobiicosahedral cluster is characterized by charge transfer from PtAu12 to HgAu12 in the visible region, accompanied by a weak charge transfer in the opposite direction. Despite low numbers of charge carriers, the heterobiicosahedral cluster shows a large dipole moment.

Original languageEnglish
Pages (from-to)24586-24591
Number of pages6
JournalJournal of Physical Chemistry C
Volume117
Issue number46
DOIs
Publication statusPublished - 2013 Nov 21

Fingerprint

Gold
Electronic properties
apexes
Optical properties
gold
optical properties
Electrons
Charge transfer
electronics
Dipole moment
Charge carriers
Electronic structure
Heterojunctions
Absorption spectra
orbitals
charge transfer
Atoms
electrons
spherical harmonics
closing

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Electronic and optical properties of vertex-sharing homo- and hetero-biicosahedral gold clusters. / Iwasa, Takeshi; Nobusada, Katsuyuki; Nakajima, Atsushi.

In: Journal of Physical Chemistry C, Vol. 117, No. 46, 21.11.2013, p. 24586-24591.

Research output: Contribution to journalArticle

@article{21d2b402a4fb47f0b129d44dbef76d95,
title = "Electronic and optical properties of vertex-sharing homo- and hetero-biicosahedral gold clusters",
abstract = "Electronic and optical properties of vertex sharing homo- and heterobiicosahedral gold clusters [M1M2Au 23(PH3)10(SCH3)5Cl 2]2+ (M1/M2 = Au/Au, Pt/Hg) are investigated by means of density functional computations, focusing on superatom assembly. In the homo clusters, the projected density of states onto the spherical harmonics reveals that each icosahedral unit behaves as a superatom with the Au(6s6p) electrons and electron shell closings of S and P orbitals followed by unoccupied D orbitals; each unit satisfies an 8-electron superatom condition. Because the Au(5d) band appears between the S and P orbitals, the electronic structure is characterized as S, Au(5d)-band, and P. The lowest electronic excitation in the homo cluster is the P to D transition. In the hetero biicosahedral cluster, the central Au atoms of each icosahedron are replaced by Pt and Hg. The HOMO and LUMO are well localized to the PtAu 12 and HgAu12 units, respectively, forming a cluster-assembled heterojunction in a single stable structure. The absorption spectrum of the heterobiicosahedral cluster is characterized by charge transfer from PtAu12 to HgAu12 in the visible region, accompanied by a weak charge transfer in the opposite direction. Despite low numbers of charge carriers, the heterobiicosahedral cluster shows a large dipole moment.",
author = "Takeshi Iwasa and Katsuyuki Nobusada and Atsushi Nakajima",
year = "2013",
month = "11",
day = "21",
doi = "10.1021/jp4081405",
language = "English",
volume = "117",
pages = "24586--24591",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "46",

}

TY - JOUR

T1 - Electronic and optical properties of vertex-sharing homo- and hetero-biicosahedral gold clusters

AU - Iwasa, Takeshi

AU - Nobusada, Katsuyuki

AU - Nakajima, Atsushi

PY - 2013/11/21

Y1 - 2013/11/21

N2 - Electronic and optical properties of vertex sharing homo- and heterobiicosahedral gold clusters [M1M2Au 23(PH3)10(SCH3)5Cl 2]2+ (M1/M2 = Au/Au, Pt/Hg) are investigated by means of density functional computations, focusing on superatom assembly. In the homo clusters, the projected density of states onto the spherical harmonics reveals that each icosahedral unit behaves as a superatom with the Au(6s6p) electrons and electron shell closings of S and P orbitals followed by unoccupied D orbitals; each unit satisfies an 8-electron superatom condition. Because the Au(5d) band appears between the S and P orbitals, the electronic structure is characterized as S, Au(5d)-band, and P. The lowest electronic excitation in the homo cluster is the P to D transition. In the hetero biicosahedral cluster, the central Au atoms of each icosahedron are replaced by Pt and Hg. The HOMO and LUMO are well localized to the PtAu 12 and HgAu12 units, respectively, forming a cluster-assembled heterojunction in a single stable structure. The absorption spectrum of the heterobiicosahedral cluster is characterized by charge transfer from PtAu12 to HgAu12 in the visible region, accompanied by a weak charge transfer in the opposite direction. Despite low numbers of charge carriers, the heterobiicosahedral cluster shows a large dipole moment.

AB - Electronic and optical properties of vertex sharing homo- and heterobiicosahedral gold clusters [M1M2Au 23(PH3)10(SCH3)5Cl 2]2+ (M1/M2 = Au/Au, Pt/Hg) are investigated by means of density functional computations, focusing on superatom assembly. In the homo clusters, the projected density of states onto the spherical harmonics reveals that each icosahedral unit behaves as a superatom with the Au(6s6p) electrons and electron shell closings of S and P orbitals followed by unoccupied D orbitals; each unit satisfies an 8-electron superatom condition. Because the Au(5d) band appears between the S and P orbitals, the electronic structure is characterized as S, Au(5d)-band, and P. The lowest electronic excitation in the homo cluster is the P to D transition. In the hetero biicosahedral cluster, the central Au atoms of each icosahedron are replaced by Pt and Hg. The HOMO and LUMO are well localized to the PtAu 12 and HgAu12 units, respectively, forming a cluster-assembled heterojunction in a single stable structure. The absorption spectrum of the heterobiicosahedral cluster is characterized by charge transfer from PtAu12 to HgAu12 in the visible region, accompanied by a weak charge transfer in the opposite direction. Despite low numbers of charge carriers, the heterobiicosahedral cluster shows a large dipole moment.

UR - http://www.scopus.com/inward/record.url?scp=84888596880&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84888596880&partnerID=8YFLogxK

U2 - 10.1021/jp4081405

DO - 10.1021/jp4081405

M3 - Article

VL - 117

SP - 24586

EP - 24591

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 46

ER -