Neutral vanadium sulfide clusters are generated by the reaction of seeded hydrogen sulfide in a helium carrier gas with laser ablated vanadium metal within a supersonic nozzle.The exiting clusters are expanded into a vacuum in a molecular beam and are ionized by both ultraviolet (UV) and vacuum UV (VUV) laser radiation.The generated ions are detected by a time of flight mass spectrometer.With single photon ionization (SPI) employing VUV (118 nm) radiation,sulfur rich clusters (VmS_n,n>m+1) and hydrogen containing clusters (V_mS_nH_x,x>0)are observed.With multiphoton ionization (MPI) through nanosecond UV (193 nm) radiation,these sulfur rich and hydrogen containing clusters cannot be observed,indicating severe fragmentation generated by MPI and the importance of SPI in determining the neutral vanadium sulfide cluster distribution.With MPI through femtosecond UV (226 nm) radiation,a few sulfur rich and hydrogen containing clusters are detected,but most clusters observed by SPI are still undetected even by femtosecond MPI.Density functional theory calculations are applied to optimize energies and structures of the clusters with m=1-3 and n=0-7.The experimental results are well interpreted based on the calculations.The calculated and experimental results for vanadium sulfides are compared with those of vanadium oxides in literature.
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