Optimization and Validation of Efficient Models for Predicting Polythiophene Self-Assembly

Overview

Journal Polymers (Basel)

Publisher MDPI

Date 2019 Apr 10

PMID 30961230

Citations 4

Authors

Evan D Miller

Matthew L Jones

Michael M Henry

Paul Chery

Kyle Miller

Eric Jankowski

Affiliations

Soon will be listed here.

Abstract

We develop an optimized force-field for poly(3-hexylthiophene) (P3HT) and demonstrate its utility for predicting thermodynamic self-assembly. In particular, we consider short oligomer chains, model electrostatics and solvent implicitly, and coarsely model solvent evaporation. We quantify the performance of our model to determine what the optimal system sizes are for exploring self-assembly at combinations of state variables. We perform molecular dynamics simulations to predict the self-assembly of P3HT at ∼350 combinations of temperature and solvent quality. Our structural calculations predict that the highest degrees of order are obtained with good solvents just below the melting temperature. We find our model produces the most accurate structural predictions to date, as measured by agreement with grazing incident X-ray scattering experiments.

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References

Jackson N, Kohlstedt K, Savoie B, Olvera de la Cruz M, Schatz G, Chen L . Conformational order in aggregates of conjugated polymers. J Am Chem Soc. 2015; 137(19):6254-62. DOI: 10.1021/jacs.5b00493. View

Feig M, Brooks 3rd C . Recent advances in the development and application of implicit solvent models in biomolecule simulations. Curr Opin Struct Biol. 2004; 14(2):217-24. DOI: 10.1016/j.sbi.2004.03.009. View

Wu G, Robertson D, Brooks 3rd C, Vieth M . Detailed analysis of grid-based molecular docking: A case study of CDOCKER-A CHARMm-based MD docking algorithm. J Comput Chem. 2003; 24(13):1549-62. DOI: 10.1002/jcc.10306. View

Mazzio K, Luscombe C . The future of organic photovoltaics. Chem Soc Rev. 2014; 44(1):78-90. DOI: 10.1039/c4cs00227j. View

Groves C, Kimber R, Walker A . Simulation of loss mechanisms in organic solar cells: A description of the mesoscopic Monte Carlo technique and an evaluation of the first reaction method. J Chem Phys. 2010; 133(14):144110. DOI: 10.1063/1.3483603. View

Van Lehn R, Atukorale P, Carney R, Yang Y, Stellacci F, Irvine D . Effect of particle diameter and surface composition on the spontaneous fusion of monolayer-protected gold nanoparticles with lipid bilayers. Nano Lett. 2013; 13(9):4060-7. PMC: 4177149. DOI: 10.1021/nl401365n. View

Kim H, Bedrov D, Smith G . Molecular Dynamics Simulation Study of the Influence of Cluster Geometry on Formation of C60 Fullerene Clusters in Aqueous Solution. J Chem Theory Comput. 2015; 4(2):335-40. DOI: 10.1021/ct700211y. View

Chen C, Depa P, Garcia Sakai V, Maranas J, Lynn J, Peral I . A comparison of united atom, explicit atom, and coarse-grained simulation models for poly(ethylene oxide). J Chem Phys. 2006; 124(23):234901. DOI: 10.1063/1.2204035. View

Coffey D, Reid O, Rodovsky D, Bartholomew G, Ginger D . Mapping local photocurrents in polymer/fullerene solar cells with photoconductive atomic force microscopy. Nano Lett. 2007; 7(3):738-44. DOI: 10.1021/nl062989e. View

10.

Obata S, Shimoi Y . Control of molecular orientations of poly(3-hexylthiophene) on self-assembled monolayers: molecular dynamics simulations. Phys Chem Chem Phys. 2013; 15(23):9265-70. DOI: 10.1039/c3cp44150d. View

11.

Huang D, Faller R, Do K, Moule A . Coarse-Grained Computer Simulations of Polymer/Fullerene Bulk Heterojunctions for Organic Photovoltaic Applications. J Chem Theory Comput. 2015; 6(2):526-37. DOI: 10.1021/ct900496t. View

12.

Damasceno P, Engel M, Glotzer S . Predictive self-assembly of polyhedra into complex structures. Science. 2012; 337(6093):453-7. DOI: 10.1126/science.1220869. View

13.

Lane T, Shukla D, Beauchamp K, Pande V . To milliseconds and beyond: challenges in the simulation of protein folding. Curr Opin Struct Biol. 2012; 23(1):58-65. PMC: 3673555. DOI: 10.1016/j.sbi.2012.11.002. View

14.

Peumans P, Uchida S, Forrest S . Efficient bulk heterojunction photovoltaic cells using small-molecular-weight organic thin films. Nature. 2003; 425(6954):158-62. DOI: 10.1038/nature01949. View

15.

Sidky H, Colon Y, Helfferich J, Sikora B, Bezik C, Chu W . SSAGES: Software Suite for Advanced General Ensemble Simulations. J Chem Phys. 2018; 148(4):044104. DOI: 10.1063/1.5008853. View

16.

Bhatta R, Yimer Y, Perry D, Tsige M . Improved force field for molecular modeling of poly(3-hexylthiophene). J Phys Chem B. 2013; 117(34):10035-45. DOI: 10.1021/jp404629a. View

17.

Clarke T, Durrant J . Charge photogeneration in organic solar cells. Chem Rev. 2010; 110(11):6736-67. DOI: 10.1021/cr900271s. View

18.

Hoover . Canonical dynamics: Equilibrium phase-space distributions. Phys Rev A Gen Phys. 1985; 31(3):1695-1697. DOI: 10.1103/physreva.31.1695. View

19.

Izvekov S, Parrinello M, Burnham C, Voth G . Effective force fields for condensed phase systems from ab initio molecular dynamics simulation: a new method for force-matching. J Chem Phys. 2004; 120(23):10896-913. DOI: 10.1063/1.1739396. View

20.

Dang M, Hirsch L, Wantz G . P3HT:PCBM, best seller in polymer photovoltaic research. Adv Mater. 2011; 23(31):3597-3602. DOI: 10.1002/adma.201100792. View