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Experimental chemical physics of droplets and clusters

Citation

Lobo, Julio Danin (2001) Experimental chemical physics of droplets and clusters. Dissertation (Ph.D.), California Institute of Technology. https://resolver.caltech.edu/CaltechTHESIS:03172014-143110747

Abstract

Time-of-flight measurements of energetic He atoms, field ionization of cryogenic liquid helium clusters, and time-of-flight and REMPI spectroscopy of radical salt clusters were investigated experimentally. The excited He atoms were generated in a corona discharge. Two strong neutral peaks were observed, accompanied by a prompt photon peak and a charged peak. All peaks were correlated with the pulsing of the discharge. The neutral hyperthermal and metastable atoms were formed by different mechanisms at different stages of the corona discharge. Positively charged helium droplets were produced by ionization of liquid helium in an electrostatic spraying experiment. The fluid emerging from a thin glass capillary was ionized by a high voltage applied to a needle inside the capillary. Fine droplets (less than 10 µm in diameter) were produced in showers with currents as high as 0.4 µA at 2-4 kV. The high currents resulting from field ionization in helium and the low surface tension of He I, led to charge densities that greatly exceeded the Rayleigh limit, thus resulting in coulombic explosion of the liquid. In contrast, liquid nitrogen formed a well-defined Taylor cone with droplets having diameters comparable to the jet (≈100 µm) at lower currents (10 nA) and higher voltages (8 kV). The metal-halide clusters of calcium and chlorine were generated by laser ablation of calcium metal in a Ar/CCl4 expansion. A visible spectrum of the Ca2Cl3 cluster was observed from 651 to 630 nm by 1 +1' REMPI. The spectra were composed of a strong origin band at 15 350.8 cm-1 and several weak vibronic bands. Density functional calculations predicted three minimum energy isomers. The spectrum was assigned to the 2B2 ← X 2A1 transition of a planar C2V structure having a ring of two Cl and two Ca atoms and a terminal Cl atom. The ring isomer of Ca2Cl3 has the unpaired electron localized on one Ca2+ ion to form a Ca+ chromophore. A second electronic band of Ca2Cl3 was observed at 720 nm. The band is sharply different from the 650 nm band and likely due to a different isomer.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Okumura, Mitchio
Thesis Committee:
  • Kuppermann, Aron
  • Beauchamp, Jack L.
  • Lewis, Nathan Saul
Defense Date:17 May 2001
Record Number:CaltechTHESIS:03172014-143110747
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:03172014-143110747
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8140
Collection:CaltechTHESIS
Deposited By: Benjamin Perez
Deposited On:17 Mar 2014 22:11
Last Modified:02 Dec 2020 02:49

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