Relationship between the energyV0of the quasi-free-electron and its mobility in fluid argon, krypton, and xenon

Atomic and Molecular Low-n Rydberg States in Near Critical Point Fluids

“…(1) is the sum of several individual Hamiltonians, namely the Hamiltonian for the free dopant, the Hamiltonian for the free perturber, and the Hamiltonian for the dopant/perturber intermolecular correlation. The Hamiltonian H FD for the free dopant is [48] ( 2 ) where α = e, g with e and g representing the excited state and ground state of the free dopant. The Hamiltonian H FP for the free non-interacting perturber is given by [48] …”

“…However, high-n Rydberg states are usually too sensitive to perturber density fluctuations, which makes these individual dopant states impossible to investigate. (Nevertheless, under the assumption that high-n Rydberg state energies behave similarly to the ionization threshold of the dopant, dopant high-n Rydberg state behavior in supercritical fluids can be probed indirectly by studying the energy of the quasi-free electron, through photoinjection [2][3][4][5][6][7][8][9][10][11] and field ionization [12][13][14][15][16][17][18][19].) Low-n Rydberg states, on the other hand, are excellent spectroscopic probes to investigate excited state/fluid interactions.…”

Electrons in Nonpolar Liquids

“…Whereas previous studies found a minimum in Vi at a density of 12 x 1021 ~m -~, [66] the new study indicates the minimum is at 14.4 x 1021 cm-3 (see Fig 8.3). This is very close to the density of 14.1 x 1021 cm-3 at which the electron mobility reaches a maximum in krypton, [67] are given in Early pulse radiolysis studies of alkanes at room temperature showed that the solvated electron absorption begins around 1 pm and increases with increasing wavelength to 1.6 pm for n-hexane, cyclohexane and 2-methylbutane.…”

Adiabatic dynamics of an excess electron in argon

“…To find the cause of this anomalous behavior, we have studied the relatively simple electron-argon system. The local maximum near the critical density in the low-field drift mobility p~( p ) of the electron in argon at p = 1.2 X ~m -~ (ref 2) has been attributed, as in other liquids, to the minimum at p = 1.103 X 1022 cm-3 (ref 3) in the bottom of the conduction band energy Vo(p), as was first conjectured by Holroyd and C i~l l i n i .~ It is argued that when V,(p) is low enough, trapping of the electron becomes energetically less favorable and the electron will remain longer in the conduction band. An alternative explanation of the maximum in p&) originates from Lekner,s who proposed that the effective scattering length could become zero near the critical density.…”