On the Mechanism Broadening of Optical Spectrum of a Solvated Electron in Ammonia

The solvated electron is self-trapped (polaron) owing to strong interaction with the quantum polarization field. If the electron and quantum field are strongly coupled then the collective localized state of the field and quasi-particle is formed. In such a formation the electron motion is rather intricate. On the one hand the electron oscillated within a rather deep polarization potential well and undergoes the optical transitions, and on the other, it moves together with the center of inertia of the system and participates in the thermal random walk. The problem is to separate these motions correctly, rigorously taking into account the conservation laws. This can be conveniently done using Bogolyubov-Tyablikov method of canonical transformation to the collective coordinates. This transformation removes the translational degeneracy and allows one to develop the successive approximation algorithm for the energy and wave function while simultaneously fulfilling the law of conservation of total momentum of the system. The resulting equations determine the electron transitions and depend explicitly on the translational velocity of the quasi-particle as whole. The frequency of optical transition is calculated for the solvated electron in ammonia, and an estimate is made for the thermal-induced spectral bandwidth.

Authors:

• V.K. Mukhomorov

Keywords:

• Canonical transformations
• solvated electron
• width of the optical spectrum.

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