title: Effect of through-space electron transfer on infrared spectrum of amorphous selenium.
abstract: In this paper we present theoretical analyses on an infrared (IR) spectrum of amorphous selenium. The system is described by a 216-atom-chain model, and a set of molecular-dynamics simulations is performed to generate vitreous structures and vibrational modes. To describe an electronic structure of the system we employ a complete neglect of differential overlap model parametrized by ab initio cluster calculations. An IR intensity is evaluated with the Berry-phase formula for an electronic polarization. The effect of the through-space electron transfer on the IR spectrum is studied by artificially changing the magnitude of matrix elements associated with the electron transfer between nonbonded atoms in the chain. We find that the through-space electron transfer leads to (i) the enhancement of the bending IR peak at 135 cm(-1) and (ii) the appearance of a new low-frequency peak around 50 cm(-1), thus resulting in a good agreement with the experiment. The mechanism is discussed by a simple dipole model.
authors.affiliation: Department of Physics, Graduate School of Science, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 133-0033, Japan. kazuma@cms.phys.s.u-tokyo.ac.jp
authors.forename: Kazuma
authors.initials: K
authors.lastname: Nakamura
authors.forename: Shinji
authors.initials: S
authors.lastname: Tsuneyuki