We
present the results from an extensive atomistic molecular dynamics
simulation study of poly(ethylene oxide) (PEO) doped with various
amounts of lithium-bis(trifluoromethane)sulfonimide (LiTFSI) salt
under the influence of external electric field strengths up to 1 V/nm.
The motivation stems from recent experimental reports on the nonlinear
response of mobilities to the application of an electric field in
such electrolyte systems and arising speculations on field-induced
alignment of the polymer chains, creating channel-like structures
that facilitate ion passage. Hence, we systematically examine the
impact of electric field on the lithium coordination environment,
polymer structure, as well as ionic transport properties and further
present a procedure to quantify the susceptibility of both structural
and dynamical observables to the external field. Our investigation
reveals indeed a coiled-to-stretched transformation of the PEO strands
along with a concurrent nonlinear behavior of the dynamic properties.
However, from studying the temporal response of the unperturbed electrolyte
system to field application, we are able to exclude a structurally
conditioned enhancement of ion transport and surprisingly observe
a slowing down. A microscopic understanding is achieved.