DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Bond-bending isomerism of Au2I3-: Competition between covalent bonding and aurophilicity

Abstract

We report a joint photoelectron spectroscopy and theoretical investigation of the gaseous Au2I3 cluster, which is found to exhibit two types of isomers due to competition between Au–I covalent bonding and Au–Au aurophilic interactions. The covalent bonding favors a bent IAuIAuI structure with an obtuse Au–I–Au angle (100.7°), while aurophilic interactions pull the two Au atoms much closer, leading to an acutely bent structure (72.0°) with an Au–Au distance of 3.08 Å. The two isomers are separated by a small barrier and are nearly degenerate with the obtuse isomer being slightly more stable. At low temperature, only the obtuse isomer is observed; distinct experimental evidence is observed for the co-existence of a combination of isomers with both acute and obtuse bending angles at room temperature. As a result, the two bond-bending isomers of Au2I3 reveal a unique example of one molecule being able to oscillate between different structures as a result of two competing chemical forces.

Authors:
 [1];  [2];  [3];  [3];  [3];  [3];  [3];  [4];  [5];  [1];  [3];  [1]
  1. Tsinghua Univ., Beijing (China)
  2. Chinese Academy of Sciences (CAS), Shanghai (China)
  3. Brown Univ., Providence, RI (United States)
  4. Tsinghua Univ., Beijing (China); Chinese Academy of Sciences (CAS), Shanghai (China)
  5. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1239322
Report Number(s):
LA-UR-15-21694
Journal ID: ISSN 2041-6520; CSHCBM
Grant/Contract Number:  
1263745; 21433005, 21201106, and 21221062; AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ab initio calculation; bond-bending isomer; aurophilicity; photoelectron spectroscopy; chemical bonding

Citation Formats

Li, Wan -Lu, Liu, Hong -Tao, Jian, Tian, Lopez, Gary V., Piazza, Zachary A., Huang, Dao -Ling, Chen, Teng -Teng, Su, Jing, Yang, Ping, Chen, Xin, Wang, Lai -Sheng, and Li, Jun. Bond-bending isomerism of Au2I3-: Competition between covalent bonding and aurophilicity. United States: N. p., 2015. Web. doi:10.1039/C5SC03568F.
Li, Wan -Lu, Liu, Hong -Tao, Jian, Tian, Lopez, Gary V., Piazza, Zachary A., Huang, Dao -Ling, Chen, Teng -Teng, Su, Jing, Yang, Ping, Chen, Xin, Wang, Lai -Sheng, & Li, Jun. Bond-bending isomerism of Au2I3-: Competition between covalent bonding and aurophilicity. United States. https://doi.org/10.1039/C5SC03568F
Li, Wan -Lu, Liu, Hong -Tao, Jian, Tian, Lopez, Gary V., Piazza, Zachary A., Huang, Dao -Ling, Chen, Teng -Teng, Su, Jing, Yang, Ping, Chen, Xin, Wang, Lai -Sheng, and Li, Jun. Tue . "Bond-bending isomerism of Au2I3-: Competition between covalent bonding and aurophilicity". United States. https://doi.org/10.1039/C5SC03568F. https://www.osti.gov/servlets/purl/1239322.
@article{osti_1239322,
title = {Bond-bending isomerism of Au2I3-: Competition between covalent bonding and aurophilicity},
author = {Li, Wan -Lu and Liu, Hong -Tao and Jian, Tian and Lopez, Gary V. and Piazza, Zachary A. and Huang, Dao -Ling and Chen, Teng -Teng and Su, Jing and Yang, Ping and Chen, Xin and Wang, Lai -Sheng and Li, Jun},
abstractNote = {We report a joint photoelectron spectroscopy and theoretical investigation of the gaseous Au2I3– cluster, which is found to exhibit two types of isomers due to competition between Au–I covalent bonding and Au–Au aurophilic interactions. The covalent bonding favors a bent IAuIAuI– structure with an obtuse Au–I–Au angle (100.7°), while aurophilic interactions pull the two Au atoms much closer, leading to an acutely bent structure (72.0°) with an Au–Au distance of 3.08 Å. The two isomers are separated by a small barrier and are nearly degenerate with the obtuse isomer being slightly more stable. At low temperature, only the obtuse isomer is observed; distinct experimental evidence is observed for the co-existence of a combination of isomers with both acute and obtuse bending angles at room temperature. As a result, the two bond-bending isomers of Au2I3– reveal a unique example of one molecule being able to oscillate between different structures as a result of two competing chemical forces.},
doi = {10.1039/C5SC03568F},
journal = {Chemical Science},
number = 1,
volume = 7,
place = {United States},
year = {Tue Oct 13 00:00:00 EDT 2015},
month = {Tue Oct 13 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Bond-stretch isomerism in transition metal complexes: a reevaluation of crystallographic data
journal, May 1993


Bond-stretch isomerism in transition-metal complexes
journal, July 1988

  • Jean, Yves.; Lledos, Agusti.; Burdett, Jeremy K.
  • Journal of the American Chemical Society, Vol. 110, Issue 14
  • DOI: 10.1021/ja00222a004

Electronic mechanisms associated with bond-stretch isomerism in transition metal complexes
journal, January 1988

  • Jean, Yves; Lledos, Agusti; Burdett, Jeremy K.
  • Journal of the Chemical Society, Chemical Communications, Issue 2
  • DOI: 10.1039/c39880000140

Do bond-stretch isomers really exist?
journal, October 1992


Bond-Stretch Isomers: Fact or Artifact?
journal, March 1992

  • Mayer, James M.
  • Angewandte Chemie International Edition in English, Vol. 31, Issue 3
  • DOI: 10.1002/anie.199202861

Bond-stretch isomerism: a case study of a quiet controversy
journal, April 2002


Bond stretch isomerism in rhombic silicon carbide (C2Si2)
journal, October 1989

  • Sudhakar, Pamidighantam V.; Guner, Osman F.; Lammertsma, Koop
  • The Journal of Physical Chemistry, Vol. 93, Issue 21
  • DOI: 10.1021/j100358a004

Bond-stretch isomerism and polytopal rearrangements in (CH)5+, (CH)5-, and (CH)4CO
journal, March 1972

  • Stohrer, Wolf D.; Hoffmann, Roald
  • Journal of the American Chemical Society, Vol. 94, Issue 5
  • DOI: 10.1021/ja00760a039

Oligomerization of Digoldacetylide Complexes through Angular Head-to-Tail Aurophilic Bonding
journal, August 2003

  • Liau, Ruei-Yang; Schier, Annette; Schmidbaur, Hubert
  • Organometallics, Vol. 22, Issue 16
  • DOI: 10.1021/om030164z

Ba3Ge4: Polymerization of Zintl Anions in the Solid and Bond Stretching Isomerism
journal, December 1998


Hybridization vs. Bond Stretching Isomerism in Ru(II) Cyclometalated Complexes of 2-Phenylpyridine
journal, December 2011


[(Cp*RuCl)2(μ-Cl)2]: Bond-Stretch or Spin-State Isomerism?
journal, September 2000


Theoretical studies of bond stretch isomerism in silabicyclobutanes
journal, April 1989

  • Boatz, Jerry A.; Gordon, Mark S.
  • The Journal of Physical Chemistry, Vol. 93, Issue 8
  • DOI: 10.1021/j100345a009

Bond-Stretch Isomers and Spin-State Isomers: A Comment on the Article “Bond-Stretch Isomers: Fact not Fiction”[1]
journal, July 1994


Bond-Stretch Isomers: Fact not Fiction
journal, March 1994

  • Gütlich, Philipp; Goodwin, Harold A.; Hendrickson, David N.
  • Angewandte Chemie International Edition in English, Vol. 33, Issue 4
  • DOI: 10.1002/anie.199404251

Theoretical chemistry of gold. III
journal, January 2008

  • Pyykkö, Pekka
  • Chemical Society Reviews, Vol. 37, Issue 9
  • DOI: 10.1039/b708613j

Theoretical chemistry of gold. II
journal, November 2005


Strong Closed-Shell Interactions in Inorganic Chemistry
journal, May 1997


Theoretical Chemistry of Gold
journal, August 2004


Aurophilic interactions as a subject of current research: an up-date
journal, January 2012

  • Schmidbaur, Hubert; Schier, Annette
  • Chem. Soc. Rev., Vol. 41, Issue 1
  • DOI: 10.1039/C1CS15182G

A briefing on aurophilicity
journal, January 2008

  • Schmidbaur, Hubert; Schier, Annette
  • Chemical Society Reviews, Vol. 37, Issue 9
  • DOI: 10.1039/b708845k

“Aurophilicity” as a Consequence of Relativistic Effects: The Hexakis(triphenylphosphaneaurio)methane Dication[(Ph3PAu)6C]2⊕
journal, November 1988

  • Scherbaum, Franz; Grohmann, Andreas; Huber, Brigitte
  • Angewandte Chemie International Edition in English, Vol. 27, Issue 11
  • DOI: 10.1002/anie.198815441

Aurophilicity as Concerted Effect: Relativistic MO Calculations on Carbon-Centered Gold Clusters
journal, October 1989

  • Rösch, Notker; Görling, Andreas; Ellis, Donald E.
  • Angewandte Chemie International Edition in English, Vol. 28, Issue 10
  • DOI: 10.1002/anie.198913571

Ab initio Calculations on the(ClAuPH3)2 Dimer with Relativistic Pseudopotential: Is the“Aurophilic Attraction” a Correlation Effect?
journal, May 1991

  • Pyykkö, Pekka; Zhao, Yongfang
  • Angewandte Chemie International Edition in English, Vol. 30, Issue 5
  • DOI: 10.1002/anie.199106041

Aurophilic attractions between a closed-shell molecule and a gold cluster
journal, January 2011

  • Pyykkö, Pekka; Xiong, Xiao-Gen; Li, Jun
  • Faraday Discussions, Vol. 152
  • DOI: 10.1039/c1fd00018g

Aurophilicity: The Effect of the Neutral Ligand L on [{ClAuL}2] Systems
journal, January 2011

  • Muñiz, Jesús; Wang, Cong; Pyykkö, Pekka
  • Chemistry - A European Journal, Vol. 17, Issue 1
  • DOI: 10.1002/chem.201001765

Oligomerization of Au(CN) 2 - and Ag(CN) 2 - Ions in Solution via Ground-State Aurophilic and Argentophilic Bonding
journal, October 2000

  • Rawashdeh-Omary, Manal A.; Omary, Mohammad A.; Patterson, Howard H.
  • Journal of the American Chemical Society, Vol. 122, Issue 42
  • DOI: 10.1021/ja001545w

Study of ligand effects in aurophilic interactions using local correlation methods
journal, January 2013

  • Andrejić, Milica; Mata, Ricardo A.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 41
  • DOI: 10.1039/c3cp52931b

Nearly Degenerate Isomers of C(BH) 2 : Cumulene, Carbene, or Carbone?
journal, October 2013

  • Barua, Shiblee R.; Allen, Wesley D.; Kraka, Elfi
  • Chemistry - A European Journal, Vol. 19, Issue 47
  • DOI: 10.1002/chem.201302181

Li 5 as a pseudorotating planar cluster
journal, May 1994


Structure of the NaxClx+1− (x=1–4) clusters via ab initio genetic algorithm and photoelectron spectroscopy
journal, September 2004

  • Alexandrova, Anastassia N.; Boldyrev, Alexander I.; Fu, You-Jun
  • The Journal of Chemical Physics, Vol. 121, Issue 12
  • DOI: 10.1063/1.1783276

Covalent gold
journal, January 2010

  • Wang, Lai-Sheng
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 31
  • DOI: 10.1039/c003886e

Photoelectron Imaging and Spectroscopy of MI 2 (M = Cs, Cu, Au): Evolution from Ionic to Covalent Bonding
journal, October 2010

  • Wang, Yi-Lei; Wang, Xue-Bin; Xing, Xiao-Peng
  • The Journal of Physical Chemistry A, Vol. 114, Issue 42
  • DOI: 10.1021/jp103173d

Photodetachment photoelectron spectroscopy of multiply charged anions using electrospray ionization
journal, April 1999

  • Wang, Lai-Sheng; Ding, Chuan-Fan; Wang, Xue-Bin
  • Review of Scientific Instruments, Vol. 70, Issue 4
  • DOI: 10.1063/1.1149694

Probing the 2D to 3D Structural Transition in Gold Cluster Anions Using Argon Tagging
journal, April 2009


Photoelectron spectroscopy of size‐selected transition metal clusters: Fe n , n =3–24
journal, June 1995

  • Wang, Lai‐Sheng; Cheng, Han‐Song; Fan, Jiawen
  • The Journal of Chemical Physics, Vol. 102, Issue 24
  • DOI: 10.1063/1.468817

Photoelectron spectra of aluminum cluster anions: Temperature effects and ab initio simulations
journal, October 1999


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992


Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes
journal, December 2003

  • Staroverov, Viktor N.; Scuseria, Gustavo E.; Tao, Jianmin
  • The Journal of Chemical Physics, Vol. 119, Issue 23
  • DOI: 10.1063/1.1626543

Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids
journal, September 2003


A long-range correction scheme for generalized-gradient-approximation exchange functionals
journal, August 2001

  • Iikura, Hisayoshi; Tsuneda, Takao; Yanai, Takeshi
  • The Journal of Chemical Physics, Vol. 115, Issue 8
  • DOI: 10.1063/1.1383587

A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004

  • Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
  • Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
  • DOI: 10.1016/j.cplett.2004.06.011

A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples
journal, February 1982

  • Purvis, George D.; Bartlett, Rodney J.
  • The Journal of Chemical Physics, Vol. 76, Issue 4
  • DOI: 10.1063/1.443164

An efficient reformulation of the closed‐shell coupled cluster single and double excitation (CCSD) equations
journal, December 1988

  • Scuseria, Gustavo E.; Janssen, Curtis L.; Schaefer, Henry F.
  • The Journal of Chemical Physics, Vol. 89, Issue 12
  • DOI: 10.1063/1.455269

The Construction and Interpretation of Mcscf Wavefunctions
journal, October 1998


Energy-consistent pseudopotentials for group 11 and 12 atoms: adjustment to multi-configuration Dirac–Hartree–Fock data
journal, April 2005


On the Spectroscopic and Thermochemical Properties of ClO, BrO, IO, and Their Anions
journal, December 2006

  • Peterson, Kirk A.; Shepler, Benjamin C.; Figgen, Detlev
  • The Journal of Physical Chemistry A, Vol. 110, Issue 51
  • DOI: 10.1021/jp065887l

Molecular Orbital Studies of Hydrogen Bonds. III. C=O···H–O Hydrogen Bond in H 2 CO···H 2 O and H 2 CO···2H 2 O
journal, August 1971

  • Morokuma, Keiji
  • The Journal of Chemical Physics, Vol. 55, Issue 3
  • DOI: 10.1063/1.1676210

A simple measure of electron localization in atomic and molecular systems
journal, May 1990

  • Becke, A. D.; Edgecombe, K. E.
  • The Journal of Chemical Physics, Vol. 92, Issue 9
  • DOI: 10.1063/1.458517

Optimized Slater-type basis sets for the elements 1-118
journal, May 2003

  • Van Lenthe, E.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 24, Issue 9
  • DOI: 10.1002/jcc.10255

Relativistic regular two‐component Hamiltonians
journal, September 1993

  • Lenthe, E. van; Baerends, E. J.; Snijders, J. G.
  • The Journal of Chemical Physics, Vol. 99, Issue 6
  • DOI: 10.1063/1.466059

Multiwfn: A multifunctional wavefunction analyzer
journal, December 2011

  • Lu, Tian; Chen, Feiwu
  • Journal of Computational Chemistry, Vol. 33, Issue 5
  • DOI: 10.1002/jcc.22885

”Developing paradigms of chemical bonding: adaptive natural density partitioning
journal, January 2008

  • Zubarev, Dmitry Yu.; Boldyrev, Alexander I.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 34
  • DOI: 10.1039/b804083d

Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint
journal, September 1988

  • Reed, Alan E.; Curtiss, Larry A.; Weinhold, Frank
  • Chemical Reviews, Vol. 88, Issue 6
  • DOI: 10.1021/cr00088a005

On the gold–ligand covalency in linear [AuX 2 ] complexes
journal, January 2015

  • Xiong, Xiao-Gen; Wang, Yi-Lei; Xu, Cong-Qiao
  • Dalton Transactions, Vol. 44, Issue 12
  • DOI: 10.1039/C4DT04031G

Assessment of Theoretical Methods for Complexes of Gold(I) and Gold(III) with Unsaturated Aliphatic Hydrocarbon: Which Density Functional Should We Choose?
journal, October 2011

  • Kang, Runhua; Chen, Hui; Shaik, Sason
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 12
  • DOI: 10.1021/ct200656p

Refinement of the crystal structure of N(CH3)4I5
journal, September 1957


The geometric and electronic structures of I3− and I5− from effective-potential calculations
journal, August 1978


On bonding in transition-metal helide ions
journal, May 1984


The electronic structure and chemical bonding in gold dihydride: AuH2− and AuH2
journal, January 2012

  • Liu, Hong-Tao; Wang, Yi-Lei; Xiong, Xiao-Gen
  • Chemical Science, Vol. 3, Issue 11
  • DOI: 10.1039/c2sc20984e

Evidence of Significant Covalent Bonding in Au(CN) 2
journal, November 2009

  • Wang, Xue-Bin; Wang, Yi-Lei; Yang, Jie
  • Journal of the American Chemical Society, Vol. 131, Issue 45
  • DOI: 10.1021/ja908106e

The mixed cyanide halide Au(i) complexes, [XAuCN]− (X = F, Cl, Br, and I): evolution from ionic to covalent bonding
journal, January 2011

  • Liu, Hong-Tao; Xiong, Xiao-Gen; Dau, Phuong Diem
  • Chemical Science, Vol. 2, Issue 11
  • DOI: 10.1039/c1sc00487e

Theory of d 10 −d 10 Closed-Shell Attraction. III. Rings
journal, June 1998

  • Pyykkö, Pekka; Mendizabal, Fernando
  • Inorganic Chemistry, Vol. 37, Issue 12
  • DOI: 10.1021/ic980121o

Works referencing / citing this record:

Making the unconventional μ 2 -P bridging binding mode more conventional in phosphinine complexes
journal, January 2019

  • Hou, Yuanfeng; Li, Zhongshu; Li, Yaqi
  • Chemical Science, Vol. 10, Issue 11
  • DOI: 10.1039/c8sc05281f

A high-resolution photoelectron imaging and theoretical study of CP and C 2 P
journal, January 2018

  • Czekner, Joseph; Cheung, Ling Fung; Johnson, Eric L.
  • The Journal of Chemical Physics, Vol. 148, Issue 4
  • DOI: 10.1063/1.5008570