Electronic Structure and Anion Photoelectron Spectroscopy of Uranium–Gold Clusters UAun–, n = 3–7

Harris, Rachel M.; Zhu, Zhaoguo; Tufekci, Burak A.; Deepika, None; Jena, Purusottam; Peterson, Kirk A.; Bowen, Kit H.

doi:10.1021/acs.jpca.3c03452

Electronic Structure and Anion Photoelectron Spectroscopy of Uranium–Gold Clusters UAu_n^–, n = 3–7

Journal Article · Thu Aug 17 04:00:00 EDT 2023 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.3c03452· OSTI ID:1995534

^[1]; ^[2]; Tufekci, Burak A. ^[2]; Deepika ^[3]; ^[3]; ^[4]; ^[2]

Johns Hopkins University, Baltimore, MD (United States); The Johns Hopkins Universty
Johns Hopkins University, Baltimore, MD (United States)
Virginia Commonwealth University, Richmond, VA (United States)
Washington State University, Pullman, WA (United States)

A collaborative effort between experiment and theory towards elucidating the electronic and molecular structures of uranium-gold clusters is presented. Anion photoelectron spectra of UAu_n^–(n=3-7) were taken at third (355 nm) and fourth (266 nm) harmonics of a Nd:YAG laser, as well as excimer (ArF 193nm) photon energies, where the experimental adiabatic electron affinities (AEA) and vertical detachment energies (VDE) values were measured. Complementary first principles calculations were subsequently carried out to corroborate experimentally determined electron detachment energies and to determine the geometry and electronic structure for each cluster. Except for the ring-like neutral isomer of UAu₆ where one unpaired electron is spread over the Au atoms, all other neutral and anionic UAu_n clusters (n = 3 - 7) were calculated to possess open-shell electrons with the unpaired electrons localized on the central U atom. The smaller clusters closely resemble the analogous UF_n species, but significant deviations are seen starting with UAu₅ where a competition between U-Au and Au-Au bonding begins to become apparent. The UAu₆ system appears to mark a transition where Au-Au interactions begin to dominate, where both a ring-like and two heavily distorted octahedral structures around the central U atom are to be nearly isoenergetic. With UAu₇, only ring-like structures are calculated. Altogether, the calculated electron detachment energies are in good agreement with the experimental values

View Accepted Manuscript (DOE)

Research Organization:: Johns Hopkins University, Baltimore, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: SC0022977; FG02-96ER45579; AC02-05CH11231

OSTI ID:: 1995534

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 34 Vol. 127; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (64)

Theoretical Chemistry of Gold Pyykkö, Pekka Angewandte Chemie International Edition, Vol. 43, Issue 34 https://doi.org/10.1002/anie.200300624	journal	August 2004
[SiAu4]: Aurosilane Kiran, Boggavarapu; Li, Xi; Zhai, Hua-Jin Angewandte Chemie International Edition, Vol. 43, Issue 16 https://doi.org/10.1002/anie.200353602	journal	April 2004
Preparation and Characterization of Uranium-Iron Triple-Bonded UFe(CO) ₃ ⁻ and OUFe(CO) ₃ ⁻ Complexes Chi, Chaoxian; Wang, Jia-Qi; Qu, Hui Angewandte Chemie International Edition, Vol. 56, Issue 24 https://doi.org/10.1002/anie.201703525	journal	May 2017
Gold Behaves as Hydrogen in the Intermolecular Self-Interaction of Metal Aurides MAu4 (M=Ti, Zr, and Hf) Jung, Jaehoon; Kim, Hyemi; Kim, Jong Chan Chemistry - An Asian Journal, Vol. 6, Issue 3 https://doi.org/10.1002/asia.201000742	journal	January 2011
A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl ₅ ⁻ and UCl ₅ Su, Jing; Dau, Phuong Diem; Xu, Chao-Fei Chemistry - An Asian Journal, Vol. 8, Issue 10 https://doi.org/10.1002/asia.201300627	journal	July 2013
Fluxionality and σ-Aromaticity in Small Yttrium-Doped Gold Clusters Lin, Ling; Höltzl, Tibor; Gruene, Philipp ChemPhysChem, Vol. 9, Issue 17 https://doi.org/10.1002/cphc.200800580	journal	December 2008
ThH ₅ : An Actinide‐Containing Superhalogen Molecule Marshall, Mary; Zhu, Zhaoguo; Harris, Rachel ChemPhysChem, Vol. 22, Issue 1 https://doi.org/10.1002/cphc.202000918	journal	December 2020
Saturnenes Like Th@Au ₆ D _6h : Ring‐Current Evidence for Au−Au Bonding Along the Gold Ring Pyykkö, Pekka; Taubert, Stefan Israel Journal of Chemistry, Vol. 62, Issue 1-2 https://doi.org/10.1002/ijch.202100139	journal	February 2022
Multiwfn: A multifunctional wavefunction analyzer Lu, Tian; Chen, Feiwu Journal of Computational Chemistry, Vol. 33, Issue 5 https://doi.org/10.1002/jcc.22885	journal	December 2011
NBO 7.0 : New vistas in localized and delocalized chemical bonding theory Glendening, Eric D.; Landis, Clark R.; Weinhold, Frank Journal of Computational Chemistry https://doi.org/10.1002/jcc.25873	journal	June 2019
Molpro: a general-purpose quantum chemistry program package: Molpro Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82	journal	July 2011
Systematically convergent basis sets for transition metals. II. Pseudopotential-based correlation consistent basis sets for the group 11 (Cu, Ag, Au) and 12 (Zn, Cd, Hg) elements Peterson, Kirk A.; Puzzarini, Cristina Theoretical Chemistry Accounts, Vol. 114, Issue 4-5 https://doi.org/10.1007/s00214-005-0681-9	journal	August 2005
Covalency in f-element complexes Neidig, Michael L.; Clark, David L.; Martin, Richard L. Coordination Chemistry Reviews, Vol. 257, Issue 2 https://doi.org/10.1016/j.ccr.2012.04.029	journal	January 2013
Energy-consistent pseudopotentials for group 11 and 12 atoms: adjustment to multi-configuration Dirac–Hartree–Fock data Figgen, Detlev; Rauhut, Guntram; Dolg, Michael Chemical Physics, Vol. 311, Issue 1-2 https://doi.org/10.1016/j.chemphys.2004.10.005	journal	April 2005
On the electronic structure and chemical bonding of titanium tetraauride: TiAu 4 and TiAu 4 − Erdogdu, Yusuf; Jian, Tian; Lopez, Gary V. Chemical Physics Letters, Vol. 610-611 https://doi.org/10.1016/j.cplett.2014.07.018	journal	August 2014
Intramolecular bonding properties in actinide embedded nearly planar superatoms Cheng, Aihua; Wang, Jianpeng; Zhang, Qingyue Chemical Physics Letters, Vol. 752 https://doi.org/10.1016/j.cplett.2020.137574	journal	August 2020
Theoretical chemistry of gold. II Pyykkö, Pekka Inorganica Chimica Acta, Vol. 358, Issue 14 https://doi.org/10.1016/j.ica.2005.06.028	journal	November 2005
Anion photoelectron spectroscopic and relativistic coupled-cluster studies of uranyl dichloride anion, UO2Cl2− Marshall, Mary; Zhu, Zhaoguo; Liu, Junzi Journal of Molecular Spectroscopy, Vol. 379 https://doi.org/10.1016/j.jms.2021.111496	journal	May 2021
Relativistic Effects Stabilize the Planar Wheel-like Structure of Actinide-Doped Gold Clusters: An@Au ₇ (An = Th to Cm) Zhang, Peng; Liu, Haitao; Zou, Wenli The Journal of Physical Chemistry A, Vol. 124, Issue 40 https://doi.org/10.1021/acs.jpca.0c02148	journal	August 2020
Mapping the Electronic Structure of the Uranium(VI) Dinitride Molecule, UN ₂ Liu, Gaoxiang; Zhang, Chaoqun; Ciborowski, Sandra M. The Journal of Physical Chemistry A, Vol. 124, Issue 32 https://doi.org/10.1021/acs.jpca.0c03735	journal	July 2020
Th ₂ O ^– , Th ₂ Au ^– , and Th ₂ AuO _1,2 ^– Anions: Photoelectron Spectroscopic and Computational Characterization of Energetics and Bonding Zhu, Zhaoguo; Marshall, Mary; Harris, Rachel M. The Journal of Physical Chemistry A, Vol. 125, Issue 1 https://doi.org/10.1021/acs.jpca.0c09766	journal	December 2020
Photoelectron Spectroscopic and ab Initio Computational Studies of the Anion, HThO^– Marshall, Mary; Zhu, Zhaoguo; Liu, Junzi The Journal of Physical Chemistry A, Vol. 125, Issue 9 https://doi.org/10.1021/acs.jpca.0c11539	journal	March 2021
Double σ-Aromaticity in a Planar Zinc-Doped Gold Cluster: Au₉Zn^– Kulichenko, Maksim; Chen, Wei-Jia; Zhang, Yang-Yang The Journal of Physical Chemistry A, Vol. 125, Issue 21 https://doi.org/10.1021/acs.jpca.1c02954	journal	May 2021
Coupled Cluster Studies of Platinum–Actinide Interactions. Thermochemistry of PtAnO ^{n +} ( n = 0–2 and An = U, Np, Pu) Feng, Rulin; Glendening, Eric D.; Peterson, Kirk A. The Journal of Physical Chemistry A, Vol. 125, Issue 24 https://doi.org/10.1021/acs.jpca.1c03675	journal	June 2021
Interaction of Th with H^0/–/+: Combined Experimental and Theoretical Thermodynamic Properties Vasiliu, Monica; Peterson, Kirk A.; Marshall, Mary The Journal of Physical Chemistry A, Vol. 126, Issue 2 https://doi.org/10.1021/acs.jpca.1c07598	journal	January 2022
Probing the Electronic Structure and Chemical Bonding of Mono-Uranium Oxides with Different Oxidation States: UO _x ^– and UO _x ( x = 3–5) Su, Jing; Li, Wei-Li; Lopez, Gary V. The Journal of Physical Chemistry A, Vol. 120, Issue 7 https://doi.org/10.1021/acs.jpca.5b11354	journal	February 2016
Prediction of Structures and Atomization Energies of Coinage Metals, (M)_n, n < 20: Extrapolation of Normalized Clustering Energies to Predict the Cohesive Energy Persaud, Rudradatt Randy; Chen, Mingyang; Dixon, David A. The Journal of Physical Chemistry A, Vol. 124, Issue 9 https://doi.org/10.1021/acs.jpca.9b11801	journal	February 2020
Signature of Au as a Halogen Shah, Aaron; Banjade, Huta; Long, Zhen-Chao The Journal of Physical Chemistry Letters, Vol. 13, Issue 21 https://doi.org/10.1021/acs.jpclett.2c00910	journal	May 2022
Relativistic effects in structural chemistry Pyykko, Pekka Chemical Reviews, Vol. 88, Issue 3 https://doi.org/10.1021/cr00085a006	journal	May 1988
Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning Kaltsoyannis, Nikolas Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic3006025	journal	June 2012
Metal-metal bonds involving actinides. Functionalization of activated carbon-hydrogen bonds and unusual oligomerization chemistry mediated by a thorium-ruthenium complex Sternal, Richard S.; Sabat, Michal; Marks, Tobin J. Journal of the American Chemical Society, Vol. 109, Issue 25 https://doi.org/10.1021/ja00259a072	journal	December 1987
Synthesis and x-ray structure of (C5Me5)2Th(.mu.-PPh2)2Pt(PMe3): a complex with a thorium-platinum bond Hay, P. J.; Ryan, R. R.; Salazar, K. V. Journal of the American Chemical Society, Vol. 108, Issue 2 https://doi.org/10.1021/ja00262a031	journal	January 1986
An organothorium-nickel phosphido complex with a short thorium-nickel distance. The structure of Th(.eta.5-C5Me5)2(.mu.-PPh2)2Ni(CO)2 Ritchey, J. M.; Zozulin, A. J.; Wrobleski, D. A. Journal of the American Chemical Society, Vol. 107, Issue 2 https://doi.org/10.1021/ja00288a039	journal	January 1985
Metal-metal bonds involving actinides. Synthesis and characterization of a complex having an unsupported actinide to transition metal bond Sternal, Richard S.; Brock, Carolyn P.; Marks, Tobin J. Journal of the American Chemical Society, Vol. 107, Issue 26 https://doi.org/10.1021/ja00312a081	journal	December 1985
σ Aromaticity of the Bimetallic Au₅Zn⁺ Cluster Tanaka, Hiromasa; Neukermans, Sven; Janssens, Ewald Journal of the American Chemical Society, Vol. 125, Issue 10 https://doi.org/10.1021/ja029157c	journal	February 2003
When Does Gold Behave as a Halogen? Predicted Uranium Tetraauride and Other MAu ₄ Tetrahedral Species, (M = Ti, Zr, Hf, Th) Gagliardi, Laura Journal of the American Chemical Society, Vol. 125, Issue 25 https://doi.org/10.1021/ja035385a	journal	June 2003
Anomalous Behavior of Atomic Hydrogen Interacting with Gold Clusters Buckart, Stefan; Ganteför, Gerd; Kim, Young Dok Journal of the American Chemical Society, Vol. 125, Issue 46 https://doi.org/10.1021/ja036544t	journal	November 2003
Au as a Surrogate for F: The Case of UAu₆ vs UF₆ Harris, Rachel M.; Zhu, Zhaoguo Journal of the American Chemical Society, Vol. 144, Issue 43 https://doi.org/10.1021/jacs.2c08231	journal	October 2022
Gold as Hydrogen. An Experimental and Theoretical Study of the Structures and Bonding in Disilicon Gold Clusters Si₂Au_n^- and Si₂Au_n (n = 2 and 4) and Comparisons to Si₂H₂ and Si₂H₄ Li, Xi; Kiran, Boggavarapu; Wang, Lai-Sheng The Journal of Physical Chemistry A, Vol. 109, Issue 19 https://doi.org/10.1021/jp0512560	journal	April 2005
Accurate Relativistic Small-Core Pseudopotentials for Actinides. Energy Adjustment for Uranium and First Applications to Uranium Hydride ^† Dolg, Michael; Cao, Xiaoyan The Journal of Physical Chemistry A, Vol. 113, Issue 45 https://doi.org/10.1021/jp9044594	journal	November 2009
Actinide-to-transition metal bonds. Synthesis, characterization, and properties of metal-metal bonded systems having the tris(cyclopentadienyl)actinide fragment Sternal, Richard S.; Marks, Tobin J. Organometallics, Vol. 6, Issue 12 https://doi.org/10.1021/om00155a036	journal	December 1987
Structural and electronic properties of uranium-encapsulated Au14 cage Gao, Yang; Dai, Xing; Kang, Seung-gu Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep05862	journal	July 2014
The Mayer bond order as a tool in inorganic chemistry† Bridgeman, Adam J.; Cavigliasso, Germán; Ireland, Luke R. Journal of the Chemical Society, Dalton Transactions, Issue 14 https://doi.org/10.1039/B102094N	journal	January 2001
Study of the MAu₆(M = Cr, Mo, W) molecular species: A transition from halogenlike to hydrogenlike chemical behavior for gold Gagliardi, Laura; Pyykkö, Pekka Phys. Chem. Chem. Phys., Vol. 6, Issue 11 https://doi.org/10.1039/B404255G	journal	January 2004
Synthesis and structure of [{N(CH2CH2NSiMe3)3}URe(η5-C5H5)2]: a heterobimetallic complex with an unsupported uranium–rhenium bond Gardner, Benedict M.; McMaster, Jonathan; Lewis, William Chemical Communications, Issue 20 https://doi.org/10.1039/B906554G	journal	January 2009
A strong charge-transfer effect in surface-enhanced Raman scattering induced by valence electrons of actinide elements Gao, Yang; Chen, Lei; Dai, Xing RSC Advances, Vol. 5, Issue 41 https://doi.org/10.1039/C5RA03408F	journal	January 2015
Actinide embedded nearly planar gold superatoms: structural properties and applications in surface-enhanced Raman scattering (SERS) Wang, Jianpeng; Xie, Weiyu; Wang, Jia Physical Chemistry Chemical Physics, Vol. 20, Issue 43 https://doi.org/10.1039/C8CP05350B	journal	January 2018
Bonding properties of a superatom system with high-Z elements: insights from energy decomposition analysis Wu, Xiaochen; Gao, Yang; Xie, Weiyu RSC Advances, Vol. 10, Issue 25 https://doi.org/10.1039/D0RA01644F	journal	January 2020
Cobalt–benzene cluster anions: Mass spectrometry and negative ion photoelectron spectroscopy Gerhards, M.; Thomas, O. C.; Nilles, J. M. The Journal of Chemical Physics, Vol. 116, Issue 23 https://doi.org/10.1063/1.1477924	journal	June 2002
Intrinsic electrophilic properties of nucleosides: Photoelectron spectroscopy of their parent anions Stokes, Sarah T.; Li, Xiang; Grubisic, Andrej The Journal of Chemical Physics, Vol. 127, Issue 8 https://doi.org/10.1063/1.2774985	journal	August 2007
Isomer identification and resolution in small gold clusters Huang, Wei; Pal, Rhitankar; Wang, Lei-Ming The Journal of Chemical Physics, Vol. 132, Issue 5 https://doi.org/10.1063/1.3299292	journal	February 2010
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Photoelectron spectroscopy of metal cluster anions: Cu ⁻ _n , Ag ⁻ _n , and Au ⁻ _n Ho, Joe; Ervin, Kent M.; Lineberger, W. C. The Journal of Chemical Physics, Vol. 93, Issue 10 https://doi.org/10.1063/1.459475	journal	November 1990
Density‐functional thermochemistry. II. The effect of the Perdew–Wang generalized‐gradient correlation correction Becke, Axel D. The Journal of Chemical Physics, Vol. 97, Issue 12 https://doi.org/10.1063/1.463343	journal	December 1992
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Probing the electronic structures of low oxidation-state uranium fluoride molecules UF _x ⁻ ( x = 2−4) Li, Wei-Li; Hu, Han-Shi; Jian, Tian The Journal of Chemical Physics, Vol. 139, Issue 24 https://doi.org/10.1063/1.4851475	journal	December 2013
Strong electron correlation in UO ₂ ⁻ : A photoelectron spectroscopy and relativistic quantum chemistry study Li, Wei-Li; Su, Jing; Jian, Tian The Journal of Chemical Physics, Vol. 140, Issue 9 https://doi.org/10.1063/1.4867278	journal	March 2014
High resolution photoelectron imaging of UO− and UO2− and the low-lying electronic states and vibrational frequencies of UO and UO2 Czekner, Joseph; Lopez, Gary V.; Wang, Lai-Sheng The Journal of Chemical Physics, Vol. 141, Issue 24 https://doi.org/10.1063/1.4904269	journal	December 2014
Correlation consistent basis sets for actinides. I. The Th and U atoms Peterson, Kirk A. The Journal of Chemical Physics, Vol. 142, Issue 7 https://doi.org/10.1063/1.4907596	journal	February 2015
ThAu₂⁻, ThAu₂O⁻, and ThAuOH⁻ anions: Photoelectron spectroscopic and theoretical characterization Zhu, Zhaoguo; Marshall, Mary; Bowen, Kit H. The Journal of Chemical Physics, Vol. 156, Issue 5 https://doi.org/10.1063/5.0079795	journal	February 2022
Effects of 5f-elements on electronic structures and spectroscopic properties of gold superatom model Gao, Yang; Wang, Zhigang Chinese Physics B, Vol. 25, Issue 8 https://doi.org/10.1088/1674-1056/25/8/083102	journal	July 2016
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Probing the 2D to 3D Structural Transition in Gold Cluster Anions Using Argon Tagging Huang, Wei; Wang, Lai-Sheng Physical Review Letters, Vol. 102, Issue 15 https://doi.org/10.1103/PhysRevLett.102.153401	journal	April 2009
Relativistic Effects in Chemistry: More Common Than You Thought Pyykkö, Pekka Annual Review of Physical Chemistry, Vol. 63, Issue 1 https://doi.org/10.1146/annurev-physchem-032511-143755	journal	May 2012

Similar Records

Gold clusters (Au{sub N}, 2{<=}N{<=}10) and their anions

Journal Article · Sat Jul 15 00:00:00 EDT 2000 · Physical Review. B, Condensed Matter and Materials Physics · OSTI ID:20217219

Au as a Surrogate for F: The Case of UAu₆ vs UF₆

Journal Article · Mon Oct 24 00:00:00 EDT 2022 · Journal of the American Chemical Society · OSTI ID:1909835

Photoelectron spectra and structure of the Mn{sub n}{sup −} anions (n = 2–16)

Journal Article · Tue Jul 28 00:00:00 EDT 2015 · Journal of Chemical Physics · OSTI ID:22493458

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Cluster chemistry
Gold
Mathematical methods
Metal clusters
Molecular structure

Electronic Structure and Anion Photoelectron Spectroscopy of Uranium–Gold Clusters UAun–, n = 3–7

Citation Formats

References (64)

Similar Records

Related Subjects

Electronic Structure and Anion Photoelectron Spectroscopy of Uranium–Gold Clusters UAu_n^–, n = 3–7