Simulation of polymeric mixed ionic and electronic conductors with a combined classical and quantum mechanical model

TY - JOUR

T1 - Simulation of polymeric mixed ionic and electronic conductors with a combined classical and quantum mechanical model

AU - Landi, Alessandro

AU - Reisjalali, Maryam

AU - Lliott, Joshua D.

AU - Matta, Micaela

AU - Carbone, Paola

AU - Troisi, Alessandro

N1 - Publisher Copyright: © 2023 The Royal Society of Chemistry.

PY - 2023/1/31

Y1 - 2023/1/31

N2 - In organic polymeric materials with mixed ionic and electronic conduction (OMIEC), the excess charge in doped polymers is very mobile and the dynamics of the polymer chain cannot be accurately described with a model including only fixed point charges. Ions and polymer are comparatively slower and a methodology to capture the correlated motions of excess charge and ions is currently unavailable. Considering a prototypical interface encountered in this type of materials, we constructed a scheme based on the combination of MD and QM/MM to evaluate the classical dynamics of polymer, water and ions, while allowing the excess charge of the polymer chains to rearrange following the external electrostatic potential. We find that the location of the excess charge varies substantially between chains. The excess charge changes across multiple timescales as a result of fast structural fluctuations and slow rearrangement of the polymeric chains. Our results indicate that such effects are likely important to describe the phenomenology of OMIEC, but additional features should be added to the model to enable the study of processes such as electrochemical doping.

AB - In organic polymeric materials with mixed ionic and electronic conduction (OMIEC), the excess charge in doped polymers is very mobile and the dynamics of the polymer chain cannot be accurately described with a model including only fixed point charges. Ions and polymer are comparatively slower and a methodology to capture the correlated motions of excess charge and ions is currently unavailable. Considering a prototypical interface encountered in this type of materials, we constructed a scheme based on the combination of MD and QM/MM to evaluate the classical dynamics of polymer, water and ions, while allowing the excess charge of the polymer chains to rearrange following the external electrostatic potential. We find that the location of the excess charge varies substantially between chains. The excess charge changes across multiple timescales as a result of fast structural fluctuations and slow rearrangement of the polymeric chains. Our results indicate that such effects are likely important to describe the phenomenology of OMIEC, but additional features should be added to the model to enable the study of processes such as electrochemical doping.

UR - http://www.scopus.com/inward/record.url?scp=85148609075&partnerID=8YFLogxK

U2 - 10.1039/d2tc05103f

DO - 10.1039/d2tc05103f

M3 - Article

AN - SCOPUS:85148609075

SN - 2050-7526

VL - 11

SP - 8062

EP - 8073

JO - Journal of Materials Chemistry C

JF - Journal of Materials Chemistry C

IS - 24

ER -