Photoelectron Emission Spectroscopy of Solutions: An Interpretation

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Abstract
The process of photoelectron emission (PEE) by solutions is decomposed into two steps: generation of electrons in unbound states in solution by irradiation; escape of unbound electrons into the gas above the solution. The transition rate for the first step is expressed in terms of the photon energy and the energy for transition to the continuum. The complete absorption band for bound-unbound transitions in solution is calculated. Experimental PEE currents for different emitters (solvated electrons in liquid ammonia or hexamethyl phosphoric triamide, ferrocyanide in water) vary linearly with photon energy after normalization to a constant transition rate. This result is interpreted by assuming that unbound electrons undergo a random walk in solution and lose their kinetic energy at a rate inversely proportional to their speed. The Schottky effect on PEE is also interpreted.