Superatomic Orbitals under Spin-Orbit Coupling

被引：124

作者：

Jiang, De-en ^{[1
]}

Kuehn, Michael ^{[2
]}

Tang, Qing ^{[1
]}

Weigend, Florian ^{[2
,3
]}

机构：

[1] Univ Calif Riverside, Dept Chem, Riverside, CA 92521 USA

[2] Karlsruher Inst Technol, Inst Phys Chem, D-76131 Karlsruhe, Germany

[3] Karlsruher Inst Technol, Inst Nanotechnol, D-76021 Karlsruhe, Germany

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2014年 / 5卷 / 19期

关键词：

PROTECTED GOLD CLUSTERS; CRYSTAL-STRUCTURE; ELECTRONIC-STRUCTURE; AU-25; NANOCLUSTERS; LIGAND-EXCHANGE; APPROXIMATION; STABILITY; ORIGIN;

D O I：

10.1021/jz501745z

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The Au-25(SR)18(-) cluster has been the poster child of success in applying the superatom complex concept and remains the most studied system of all of the monolayer-protected metal clusters. In this Letter, we try to solve a mystery about this cluster: the low-temperature UV-vis absorption spectrum shows double peaks below 2.0 eV while simulation by scalar relativistic time-dependent density functional theory (TDDFT) shows only one peak in this region. Using a recently implemented two-component TDDFT, we show that spin-orbit coupling (SOC) leads to those two peaks by splitting the 1P superatomic HOMO orbitals. This work highlights the importance of SOC in understanding the electronic structure and optical absorption of thiolated gold nanoclusters, which has not been realized previously.

引用

页码：3286 / 3289

页数：4

共 42 条

[1] On the structure of thiolate-protected Au25 [J].

Akola, Jaakko ;

Walter, Michael ;

Whetten, Robert L. ;

Haekkinen, Hannu ;

Groenbeck, Henrik .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (12) :3756-+

[2] Thiolate-Protected Au25 Superatoms as Building Blocks: Dimers and Crystals [J].

Akola, Jaakko ;

Kacprzak, Katarzyna A. ;

Lopez-Acevedo, Olga ;

Walter, Michael ;

Gronbeck, Henrik ;

Hakkinen, Hannu .

JOURNAL OF PHYSICAL CHEMISTRY C, 2010, 114 (38) :15986-15994

[3]

[Anonymous], 2007, TURBOMOLE V6 6 2014

[4]

Atkins P. W., 2011, Molecular Quantum Mechanics

[5] Nonsuperatomic [Au23(SC6H11)16]- Nanocluster Featuring Bipyramidal Au15 Kernel and Trimeric Au3(SR)4 Motif [J].

Das, Anindita ;

Li, Tao ;

Nobusada, Katsuyuki ;

Zeng, Chenjie ;

Rosi, Nathaniel L. ;

Jin, Rongchao .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (49) :18264-18267

[6] Temperature-Dependent Optical Absorption Properties of Monolayer-Protected Au25 and Au38 Clusters [J].

Devadas, Mary Sajini ;

Bairu, Semere ;

Qian, Huifeng ;

Sinn, Ekkehard ;

Jin, Rongchao ;

Ramakrishna, Guda .

JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2011, 2 (21) :2752-2758

[7] Energy-consistent pseudopotentials for group 11 and 12 atoms: adjustment to multi-configuration Dirac-Hartree-Fock data [J].

Figgen, D ;

Rauhut, G ;

Dolg, M ;

Stoll, H .

CHEMICAL PHYSICS, 2005, 311 (1-2) :227-244

[8] Crystal structure of the gold nanoparticle [N(C8H17)4][Au25(SCH2CH2Ph)18] [J].

Heaven, Michael W. ;

Dass, Amala ;

White, Peter S. ;

Holt, Kennedy M. ;

Murray, Royce W. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (12) :3754-+

[9] Structure of a thiol monolayer-protected gold nanoparticle at 1.1 Å resolution [J].

Jadzinsky, Pablo D. ;

Calero, Guillermo ;

Ackerson, Christopher J. ;

Bushnell, David A. ;

Kornberg, Roger D. .

SCIENCE, 2007, 318 (5849) :430-433

[10] The expanding universe of thiolated gold nanoclusters and beyond [J].

Jiang, De-en .

NANOSCALE, 2013, 5 (16) :7149-7160

← 1 2 3 4 5 →