Probing the Electronic Structures of Atomic Clusters and Solution Phase Species in the Gas Phase
EMSL Project ID
25392
Abstract
This proposal is a continuation of research under EMSL User Proposal #1391a. Clusters provide intermediate molecular systems bridging the gap between atoms and condensed matter. Their finite and controlled size in principle makes easier for a detailed molecular-level understanding and provides ideal models to address questions in catalysis and solid materials.1 The electronic structure of metal clusters and its evolution with size are important questions in cluster science. A powerful technique to elucidate the electronic structure of metal clusters is photoelectron spectroscopy (PES), in which electron binding energies of a cluster are measured, giving directly the electronic energy levels. The electronic structure, along with the geometrical structures, plays a key role in determining the chemical and physical properties of a cluster. Multiply charged anions (MCAs) are ubiquitous in the condensed phase and constitute an important class of complex anions in the solution phase. Free MCAs have been difficult to study and very few of them are known in the gas phase previously. We have developed an experimental technique combining electrospray ionization (ESI) with PES, which allows us not only to probe free MCAs, but also to access a wide variety of solution phase anions in the gas phase.2,3 Gas-phase solvated clusters have been used as models to obtain insight into the solution phase. The combination of ESI and PES also provides a general and sensitive tool to probe solution phase species and solvated clusters of both simple and complex anions in the gas phase.
We plan to exploit the development made during the past period, including the theoretical collaborations, and propose researches in the following six general areas. 1. Au clusters and other 4d and 5d transition metal clusters. 2. CO- and O2-adsorbed Au clusters: toward a molecular understanding of the CO oxidation by Au nanoparticles. 3. One-dimensional clusters: (MCN)n- (M = Cu, Ag, Au). 4. Singly and multiply charged transition metal cyanide complexes M(CN)xn-, and linear coinage metal cyanide complex clusters (MCN)nCN-. 5. Polynuclear ligated metal clusters, such as Pd6Ru6(CO)242-, Ru11H(CO)273-, Os20(CO)402-, etc. 6. Amino acid-halide anion complexes: searching for gaseous zwitterions.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2007-05-31
End Date
2010-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Vibrationally Resolved Photoelectron Spectroscopy of Di-Gold Carbonyl Clusters Au2(CO)n− (n = 1−3): Experiment and Theory
Wang YL, HJ Zhai, L Xu, J Li, and LS Wang. 2010. "Vibrationally Resolved Photoelectron Spectroscopy of Di-Gold Carbonyl Clusters Au2(CO)n-(n=1-3): Experiment and Theory." Journal of Physical Chemistry A 114(3):1247-1254. doi:10.1021/jp903558v
Structural Transitions from Pyramidal to Fused Planar to Tubular to Core/Shell Compact in Gold Clusters: Aun- (n = 21−25)
Bulusu S, X Li, LS Wang, and XC Zeng. 2007. "Structural Transitions from Pyramidal to Fused Planar to Tubular to Core/Shell Compact in Gold Clusters: Au-n (n=21-25)." Journal of Physical Chemistry C 111(11):4190-4198. doi:10.1021/jp068897v
Cleavage of [4Fe—4S]-Type Clusters: Breaking the Symmetry
Niu S, and T Ichiye. 2009. "Cleavage of [4Fes4S]-Type Clusters: Breaking the Symmetry." Journal of Physical Chemistry A 113(19):5710-5717. doi:10.1021/jp900402y
Detecting Weak Interactions between Au− and Gas Molecules: A Photoelectron Spectroscopic and Ab Initio Study
Gao Y, W Huang, J Woodford, LS Wang, and XC Zeng. 2009. "Detecting Weak Interactions between Au- and Gas Molecules: A Photoelectron Spectroscopic and Ab Initio Study." Journal of the American Chemical Society 131(27):9484-9485. doi:10.1021/ja903043d.
Au10−: isomerism and structure-dependent O2 reactivity
Huang W, and LS Wang. 2009. "Au10-: isomerism and structure-dependent O2 reactivity." Physical Chemistry Chemical Physics. PCCP 11(15):2663-2667. doi:10.1039/b823159a.
Structural Transition of Gold Nanoclusters: From the Golden Cage to the Golden Pyramid
Huang W, S Bulusu, R Pal, XC Zeng, and LS Wang. 2009. "Structural Transition of Gold Nanoclusters: From the Golden Cage to the Golden Pyramid ." ACS Nano 3(5):1225-1230. doi:10.1021/nn900232d.
Chemisorption-induced Structural Changes and Transition from Chemisorption to Physisorption in Au6(CO)n− (n = 4−9)
Zhai HJ, LL Pan, B Dai, B Kiran, J Li, and LS Wang. 2008. "Chemisorption-Induced Structural Changes and Transition from Chemisorption to Physisorption in Au6(CO)n-(n=4-9)." Journal of Physical Chemistry C 112(31):11920-11928. doi:10.1021/jp803161b.
Experimental and theoretical investigation of three-dimensional nitrogen-doped aluminum clusters Al8N− and Al8N
Wang L, W Huang, LS Wang, BB Averkiev, and AI Boldyrev. 2009. "Experimental and theoretical investigation of three-dimensional nitrogen-doped aluminum clusters AI8N- and AI8N." Journal of Chemical Physics 130(13):134303-1 to 134303-7. doi:10.1063/1.3097761.
Probing the Intrinsic Electronic Structure of the Bis(dithiolene) Anions [M(mnt)2]2- and [M(mnt)2]1- (M = Ni, Pd, Pt; mnt = 1,2-S2C2(CN)2) in the Gas Phase by Photoelectron Spectroscopy
Waters T, H Woo, XB Wang, and LS Wang. 2006. "Probing the Intrinsic Electronic Structure of the Bis(dithiolene) Anions [M(mnt)2]2- and [M(mnt)2]1- (M=Ni, Pd, Pt; mnt=1,2-S2C2(CN)2) in the Gas Phase By Photoelectron Spectroscopy." Journal of the American Chemical Society 128(13):4282-4291. doi:10.1021/ja056342s.
Photoelectron Spectroscopy of the Bis(dithiolene) Anions [M(mnt)2]n- (M = Fe − Zn; n = 1, 2): Changes in Electronic Structure with Variation of Metal Center and with Oxidation
Waters T, XB Wang, H Woo, and LS Wang. 2006. "Photoelectron Spectroscopy of the Bis(dithiolene) Anions [M(mnt)2]n-(M ) Fe - Zn; n ) 1, 2): Changes in Electronic Structure with Variation of Metal Center and with Oxidation." Inorganic Chemistry 45(15):5841-5851. doi:10.1021/ic060255z
Photoelectron Spectroscopy of Free Multiply Charged Keggin Anions α-[PM12O40]3- (M = Mo, W) in the Gas Phase
Waters T, X Huang, XB Wang, H Woo, RA O'Hair, AG Wedd, and LS Wang. 2006. "Photoelectron Spectroscopy of Free Multiply Charged Keggin Anions r-[PM12O40]3- (M ) Mo, W) in the Gas Phase." Journal of Physical Chemistry A 110(37):10737-10741. doi:10.1021/jp063594m.
Negative electron binding energies observed in a triply charged anion: Photoelectron spectroscopy of 1-hydroxy-3,6,8-pyrene-trisulfonate
Yang J, X Xing, XB Wang, LS Wang, AP Sergeeva, and AI Boldyrev. 2008. "Negative Electron Binding Energies Observed in a Triply Charged Anion: Photoelectron Spectroscopy of 1-Hydroxy-3, 6, 8-Pyrene-Trisulfonate ." Journal of Chemical Physics 128(9):Art. No. 091102. doi:10.1063/1.2889001
Are Carboxyl Groups the Most Acidic Sites in Amino Acids? Gas-Phase Acidities, Photoelectron Spectra, and Computations on Tyrosine, p-Hydroxybenzoic Acid, and Their Conjugate Bases
Z Tian, X-B Wang, L-S Wang, and SR Kass. 2009. Are Carboxyl Groups the Most Acidic Sites in Amino Acids? Gas-Phase Acidities, Photoelectron Spectra, and Computations on Tyrosine, p-Hydroxybenzoic Acid, and Their Conjugate Bases. JACS 131(3), 1174-1181. DOI 10.1021/ja807982k.