Strong electronic consequences of intercalation in cuprate
superconductors: The case of a trigonal planar AuI3 complex
stabilized in the Bi2Sr2CaCu2Oy lattice

J 2002

Strong electronic consequences of intercalation in cuprate superconductors: The case of a trigonal planar AuI3 complex stabilized in the Bi2Sr2CaCu2Oy lattice

MUNZAROVÁ, Markéta and Roald HOFFMANN

Basic information

Original name

Strong electronic consequences of intercalation in cuprate superconductors: The case of a trigonal planar AuI3 complex stabilized in the Bi2Sr2CaCu2Oy lattice

Authors

MUNZAROVÁ, Markéta (203 Czech Republic, guarantor) and Roald HOFFMANN (840 United States of America)

Edition

J. Am. Chem. Soc. Washington, American Chemical Society, 2002, 0002-7863

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10403 Physical chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

Impact factor

Impact factor: 6.201

RIV identification code

RIV/00216224:14310/02:00006522

Organization unit

Faculty of Science

Keywords in English

T-C SUPERCONDUCTORS; MOLECULAR-STRUCTURE; SINGLE-CRYSTAL; BAND-STRUCTURE; AB-INITIO; ENERGY; DIFFRACTION; MODULATION; PSEUDOPOTENTIALS; APPROXIMATION

Abstract

V originále

Recently, a molecular Aul(3) complex was stabilized in the interlayer space of the Bi2Sr2CaCu2Oy (Bi2212) high-T-c superconducting phase, adopting an exceptional D-3h structure (Choy, J.-H.; et al. J. Phys. Chem. B 2000, 104, 7273). If the gold were formally Au(III), a strong Jahn-Teller distortion to T- and Y-shaped structures would be expected. In this work, we try to understand the structural preferences of Aul(3) in both the gas phase and the Bi2212 lattice, as well as the influence of the Aul(3) intercalation on the superconductor lattice. What we think actually happens is that there is an effective electron transfer from the s-type Bi lone pair to the gold, increasing the formal oxidation state of Bi from +3 to +5 and decreasing that of Au from +3 to +1. A trigonal Au(I) trihalide is just fine. The DFT results confirm in the Bi-rich regions the same kind of electron transfer as encountered on the EHT level of theory, but they reveal additional complexities of the problem. The effect of the Bi to intercalating molecule electron transfer on the cuprate layer may be important, quite apart from this specific example, in tuning superconductivity in the cuprates.

Links

MSM 143100011, plan (intention)

Name: Struktura a vazebné poměry, vlastnosti a analýza syntetických a přírodních molekulových ansamblů

Investor: Ministry of Education, Youth and Sports of the CR, Structure and character of bonding, properties and analysis of synthetic and natural molecular ensembles

Citovat

MUNZAROVÁ, Markéta and Roald HOFFMANN. Strong electronic consequences of intercalation in cuprate superconductors: The case of a trigonal planar AuI3 complex stabilized in the Bi2Sr2CaCu2Oy lattice. J. Am. Chem. Soc. Washington: American Chemical Society, 2002, vol. 124, No 19, p. 5542-5549. ISSN 0002-7863.

@article{405828,
   author = {Munzarová, Markéta and Hoffmann, Roald},
   article_location = {Washington},
   article_number = {19},
   keywords = {T-C SUPERCONDUCTORS; MOLECULAR-STRUCTURE; SINGLE-CRYSTAL; BAND-STRUCTURE; AB-INITIO; ENERGY; DIFFRACTION; MODULATION; PSEUDOPOTENTIALS; APPROXIMATION},
   language = {eng},
   issn = {0002-7863},
   journal = {J. Am. Chem. Soc.},
   title = {Strong electronic consequences of intercalation in cuprate superconductors: The case of a trigonal planar AuI3 complex stabilized in the Bi2Sr2CaCu2Oy lattice},
   volume = {124},
   year = {2002}
}

TY  - JOUR
ID  - 405828
AU  - Munzarová, Markéta - Hoffmann, Roald
PY  - 2002
TI  - Strong electronic consequences of intercalation in cuprate superconductors: The case of a trigonal planar AuI3 complex stabilized in the Bi2Sr2CaCu2Oy lattice
JF  - J. Am. Chem. Soc.
VL  - 124
IS  - 19
SP  - 5542
EP  - 5542
PB  - American Chemical Society
SN  - 00027863
KW  - T-C SUPERCONDUCTORS
KW  - MOLECULAR-STRUCTURE
KW  - SINGLE-CRYSTAL
KW  - BAND-STRUCTURE
KW  - AB-INITIO
KW  - ENERGY
KW  - DIFFRACTION
KW  - MODULATION
KW  - PSEUDOPOTENTIALS
KW  - APPROXIMATION
N2  - Recently, a molecular Aul(3) complex was stabilized in the interlayer space of the Bi2Sr2CaCu2Oy (Bi2212) high-T-c superconducting phase, adopting an exceptional D-3h structure (Choy, J.-H.; et al. J. Phys. Chem. B 2000, 104, 7273). If the gold were formally Au(III), a strong Jahn-Teller distortion to T- and Y-shaped structures would be expected. In this work, we try to understand the structural preferences of Aul(3) in both the gas phase and the Bi2212 lattice, as well as the influence of the Aul(3) intercalation on the superconductor lattice. What we think actually happens is that there is an effective electron transfer from the s-type Bi lone pair to the gold, increasing the formal oxidation state of Bi from +3 to +5 and decreasing that of Au from +3 to +1. A trigonal Au(I) trihalide is just fine. The DFT results confirm in the Bi-rich regions the same kind of electron transfer as encountered on the EHT level of theory, but they reveal additional complexities of the problem. The effect of the Bi to intercalating molecule electron transfer on the cuprate layer may be important, quite apart from this specific example, in tuning superconductivity in the cuprates.
ER  -

MUNZAROVÁ, Markéta and Roald HOFFMANN. Strong electronic consequences of intercalation in cuprate superconductors: The case of a trigonal planar AuI3 complex stabilized in the Bi2Sr2CaCu2Oy lattice. \textit{J. Am. Chem. Soc.}. Washington: American Chemical Society, 2002, vol.~124, No~19, p.~5542-5549. ISSN~0002-7863.

Detailed Information on Publication Record