Cluster Model Studies of Condensed Phase Phenomena
EMSL Project ID
25395
Abstract
This proposal is a continuation of research under EMSL User Proposal #8592. This program is aimed at obtaining a microscopic understanding of solution chemistry and solvation of negatively charged ions using cluster models in the gas phase. Our primary experimental technique is photoelectron spectroscopy coupled with electrospray ionization.1,2 Experimental and ab initio calculations are combined to 1) obtain a molecular-level understanding of the solvation and stabilization of singly and multiply charged anions important in the condensed phase; 2) understand the molecular processes and initial steps of dissolution of salt molecules in polar solvents; 3) probe the structure and dynamics of solution and air/solution interface. A central theme of this research program lies at obtaining a molecular-level understanding of environmental materials and solution chemistry, which is important to address issues related to waste storage, subsurface and atmospheric contaminant transport, and other primary DOE missions. Steady progress has been made to achieve the goals described above, and a selected set of publications are listed below.1-11Temperature is a known critical issue in gas phase spectroscopy and ion chemistry. Recently we have developed a second generation electrospray photoelectron spectroscopy apparatus, which is able to selectively trap ions under low temperature conditions.12,13 A low temperature trap is valuable to suppress thermal broadening in the photoelectron spectra and help stabilize weakly bound clusters. In addition, temperature dependent studies are possible, which can be used to investigate entropic effects on ion confirmations and isomer populations. We anticipate that the second generation electrospray photoelectron spectroscopy apparatus will significantly expand our capability and flexibility to study solution phase species in the gas phase, and propose specific tasks 1-4 in the following to address many novel and outstanding issues related to condensed phase phenomena.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2007-06-01
End Date
2010-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Wang XB, and LS Wang. 2008. "Development of a Low-Temperature Photoelectron Spectroscopy Instrument Using an Electrospray Ion Source and a Cryogenically Controlled Ion Trap." Review of Scientific Instruments 79(7):Art. No. 073108. doi:10.1063/1.2957610
Wang XB, AP Sergeeva, J Yang, X Xing, AI Boldyrev, and LS Wang. 2009. "Photoelectron Spectroscopy of Cold Hydrated Sulfate Clusters, SO42?(H2O)N ((N = 4?7): Temperature-Dependent Isomer Populations." Journal of Physical Chemistry A 113(19):5567-5576.
Wang XB, AP Sergeeva, X Xing, M massaouti, karpuschkin, O Hampe, AI Boldyrev, MM Kappes, and LS Wang. 2009. "Probing the electronic stability of multiply charged anions:sulfonated pyrene tri- and tetraanions." Journal of the American Chemical Society 131(28):9836-9842.
Wang XB, B Jagoda-Cwiklik, C Chi, X Xing, M Zhou, P Jungwirth, and LS Wang. 2009. "Microsolvation of the acetate anion [CH3CO-2(H2O)n,n=1-3]: A photoelectron spectroscopy and ab initio computational study." Chemical Physics Letters 477(1-3):41-44.
Wang XB, C Chi, M Zhou, IV Kuvychko, K Seppelt, AA Popov, SH Strauss, OV boltalina, and LS Wang. 2010. "Photoelectron Spectroscopy of C60Fn- and C60Fm2- (n=17,33,35,43,45,47;m=34,46) in the Gas Phase and the Generation and Characterization of C1-C60F47- and D2-C60F44 in Solution." Journal of Physical Chemistry A 114(4):1756-1765.
Wang XB, J Yang, and LS Wang. 2008. "Observation of Entropic Effect on Conformation Changes of Complex Systems Under Well-Controlled Temperature Condition." Journal of Physical Chemistry A 112(2):172-175. doi:10.1021/jp711205z
Wang XB, K Kowalski, LS Wang, and SS Xantheas. 2010. "Stepwise hydration of the cyanide anion: A temperature-controlled photoelectron spectroscopy and ab initio computational study of CN-(H2O)n(n=2-5)." Journal of Chemical Physics 132(12):124306/1-10. doi:10.1063/1.3360306
Wang XB, K Matheis, IN Ioffe, AA Goryunkov, J Yang, MM Kappes, and LS Wang. 2008. "High Resolution and Low-Temperature Photoelectron Spectroscopy of an Oxygen-Linked Fullerene Dimer Dianion: C120O2-." Journal of Chemical Physics 128(11):Art. No. 114307.
Wang XB, Q Fu, and J Yang. 2010. "Electron Affinities and Electronic Structures of o-, m-, and p- Hydroxyphenoxyl Radicals: A Combined Low-Temperature Photoelectron Spectroscopic and Ab initio Calculation Study." Journal of Physical Chemistry A 114(34):9083-9089.
Wang XB, X Xing, and LS Wang. 2008. "Observation of H-2 Aggregation onto a Doubly Charged Anion in a Temperature-Controlled Ion Trap." Journal of Physical Chemistry A 112(51):13271-13274.
Xing X, XB Wang, and LS Wang. 2008. "Imaging Intramolecular Coulomb Repulsions in Multiply Charged Anions." Physical Review Letters 101(8):Art. no. 083003. doi:10.1103/PhysRevLett.101.083003
Xing X, XB Wang, and LS Wang. 2009. "Photoelectron Angular Distribution and Molecular Structure in Multiply Charged Anions." Journal of Physical Chemistry A 113(6):945-948.
Xing, X., XB Wang, and LS Wang. 2009. "Photoelectron Imaging of Multiply Charged Anions: Effects of Intramolecular Coulomb Repulsion and Photoelectron Kinetic Energies on Photoelectron Angular Distributions." Journal of Chemical Physics 130: Art. No. 074301
Yang J, XB Wang, X Xing, and LS Wang. 2008. "Photoelectron Spectroscopy of Anions at 118.2 nm: Observation of High Electron Binding Energies in Superhalogens MCI4- (M=Sc, Y, La)." Journal of Chemical Physics 128(20):Art. No. 201102. doi:10.1063/1.2938390
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