Studies of polaron motion

The one-dimensional molecular-crystal model of polaron motion, described in the preceding paper, is here analyzed for the case in which the electronic-overlap term of the total Hamiltonian is a small perturbation. In zeroth order —i.e., in the absence of this term—the electron is localized at a given site, p. The vibrational state of the system is specified by a set of quantum-numbers, Nk, giving the degree of excitation of each vibration-mode; the latter differ from the conventional modes in that in each of them, the equilibrium displacement, about which the system oscillates, depends upon the location of the electron. The presence of a nonvanishing electronic-overlap term gives rise to transitions in which the electron jumps to a neighboring site (p → p ± 1), and in which either all of the Nk remain unaltered (“diagonal” transitions) or in which some of them change by ±1 (“nondiagonal” transitions). The two types of transitions play fundamentally different roles. At sufficiently low temperatures, the diagonal transitions are dominant. They give rise to the formation of Bloch-type bands whose widths (see Eq. 37) are each given by the product of the electronic-overlap integral, and a vibrational overlap-integral, the latter being an exponentially falling function of the Nk (and, hence, of temperature). In this low-temperature domain, the role of the nondiagonal transitions is essentially one of scattering. In the absence of other scattering mechanisms, such as impurity scattering, they determine the lifetimes of the polaron-band states and, hence, the mean free path for typical transport quantities, such as electron diffusivity. With rising temperature, the probability of the off-diagonal transitions goes up exponentially. This feature, together with the above-mentioned drop in bandwidth, results, e.g., in an exponentially diminishing diffusivity. Eventually, a temperature, Tt ∼ 12 the Debye θ, is reached at which the energy uncertainty, h̷gt, associated with the finite lifetime of the states, is equal to the bandwidth. At this point, the Bloch states lose their individual characteristics (in particular, those which depend upon electronic wave number); the bands may then be considered as “washed out”. For temperatures >Tt, electron motion is predominantly a diffusion process. The elementary steps of this process consist of the random-jumps between neighboring sites associated with the nondiagonal transitions. In conformance with this picture, the electron diffusivity is, apart from a numerical factor, the product of the square of the lattice distance and the total non-diagonal transition probability, and is therefore an exponentially rising function of temperature. The limit, Jmax, of the magnitude of the electronic overlap term, beyond which the perturbation treatment of the present paper becomes inapplicable, is investigated. For representative values of the parameters entering into the theory, Jmax ∼ 0.12 ev and 0.035 ev for the extreme cases of (a) width of the ground-state polaron-band and (b) high-temperature site-jump probabilities (these numbers correspond to electronic bandwidths of 0.24 ev and 0.07 ev, respectively). For electronic bandwidths in excess of these limits, a treatment based on the adiabatic approach is required; preliminary results of such a treatment are given for the above two cases.