Nonlinear Migration Dynamics of Excess Electrons along Linear Oligopeptides Controlled by an Applied Electric Field

Migration of an excess electron along linear oligopeptides governed by the external electric field (E_ex ) which is against the inner dipole electric field is theoretically investigated, including the effects of E_ex on the structural and electronic properties of electron migration. Two structural properties including electron-binding ability and the dipole moment of linear oligopeptides are sensitive to the E_ex values and can be largely modulated by E_ex due to the competition of E_ex and the inner electric field and electron transfer caused by E_ex . In the case of low E_ex values, two structural properties decrease slightly_, while for high E_ex values, the electron-binding ability continually increases strongly, with dipole moments firstly increasing significantly and then increasing more slowly at higher E_ex . Additionally, linear oligopeptides of different chain lengths influence the modulation extent of E_ex and the longer the chain length is, the more sensitive modulation of E_ex is. In addition, electronic properties represented by electron spin densities and singly occupied molecular orbital distributions vary with E_ex intensities, leading to an unusual electron migration behavior. As E_ex increases, an excess electron transfers from the N-terminus to the C-terminus and jumps over a neighboring dipole unit of two termini to other units, respectively, instead of transferring by means of a one-by-one dipole unit hopping mechanism. These findings not only promote a deeper understanding of the connection between E_ex and structural and electronic properties of electron transfer behavior in peptides, but also provide a new insight into the modulation of electron migration along the oligopeptides.