title: Experimental and theoretical study of the reactions between neutral vanadium oxide clusters and ethane, ethylene, and acetylene.
abstract: Reactions of neutral vanadium oxide clusters with small hydrocarbons, namely C2H6, C2H4, and C2H2, are investigated by experiment and density functional theory (DFT) calculations. Single photon ionization through extreme ultraviolet (EUV, 46.9 nm, 26.5 eV) and vacuum ultraviolet (VUV, 118 nm, 10.5 eV) lasers is used to detect neutral cluster distributions and reaction products. The most stable vanadium oxide clusters VO2, V2O5, V3O7, V4O10, etc. tend to associate with C2H4 generating products V(m)O(n)C2H4. Oxygen-rich clusters VO3(V2O5)(n=0,1,2...), (e.g., VO3, V3O8, and V5O13) react with C2H4 molecules to cause a cleavage of the C=C bond of C2H4 to produce (V2O5)(n)VO2CH2 clusters. For the reactions of vanadium oxide clusters (V(m)O(n)) with C2H2 molecules, V(m)O(n)C2H2 are assigned as the major products of the association reactions. Additionally, a dehydration reaction for VO3 + C2H2 to produce VO2C2 is also identified. C2H6 molecules are quite stable toward reaction with neutral vanadium oxide clusters. Density functional theory calculations are employed to investigate association reactions for V2O5 + C2H(x). The observed relative reactivity of C2 hydrocarbons toward neutral vanadium oxide clusters is well interpreted by using the DFT calculated binding energies. DFT calculations of the pathways for VO3+C2H4 and VO3+C2H2 reaction systems indicate that the reactions VO3+C2H4 --> VO2CH2 + H2CO and VO3+C2H2 --> VO2C2 + H2O are thermodynamically favorable and overall barrierless at room temperature, in good agreement with the experimental observations.
authors.affiliation: Department of Chemistry, and NSF ERC for Extreme Ultraviolet Science and Technology, Colorado State University, Fort Collins, Colorado 80523, USA.
authors.forename: Feng
authors.initials: F
authors.lastname: Dong
authors.forename: Scott
authors.initials: S
authors.lastname: Heinbuch
authors.forename: Yan
authors.initials: Y
authors.lastname: Xie
authors.forename: Jorge J
authors.initials: JJ
authors.lastname: Rocca
authors.forename: Elliot R
authors.initials: ER
authors.lastname: Bernstein
authors.forename: Zhe-Chen
authors.initials: ZC
authors.lastname: Wang
authors.forename: Ke
authors.initials: K
authors.lastname: Deng
authors.forename: Sheng-Gui
authors.initials: SG
authors.lastname: He
mesh_terms: D000114:Acetylene / Q000737:chemistry*; D003198:Computer Simulation; D004980:Ethane / Q000737:chemistry*; D005030:Ethylenes / Q000737:chemistry*; D005557:Formaldehyde / Q000138:chemical synthesis / Q000737:chemistry; D007834:Lasers; D008956:Models, Chemical; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods; D017968:Vanadium Compounds / Q000737:chemistry*
chemical_list: D005030:Ethylenes; D010087:Oxides; D017968:Vanadium Compounds; D005557:Formaldehyde; C036216:ethylene; D004980:Ethane; D000114:Acetylene