Simulation of dilute solutions of linear and star-branched polymers by dissipative particle dynamics

M. M. Nardai, G. Zifferer
2009 Journal of Chemical Physics  
A most promising off-lattice technique in order to simulate not only static but in addition dynamic behavior of linear and star-branched chains is the dissipative particle dynamics ͑DPD͒ method. In this model the atomistic representation of polymer molecules is replaced by a ͑coarse-grained͒ equivalent chain consisting of beads which are repulsive for each other in order to mimic the excluded volume effect ͑successive beads in addition are linked by springs͒. Likewise solvent molecules are
more » ... molecules are combined to beads which in turn are repulsive for each other as well as for the polymer segments. The system is relaxed by molecular dynamics solving Newton's laws under the influence of short ranged conservative forces ͑i.e., repulsion between nonbonded beads and a proper balance of repulsion and attraction between bonded segments͒ and dissipative forces due to friction between particles, the latter representing the thermostat in conjunction with proper random forces. A variation of the strength of the repulsion between different types of beads allows the simulation of any desired thermodynamic situation. Static and dynamic properties of isolated linear and star-branched chains embedded in athermal, exothermal, and endothermal solvent are presented and theta conditions are examined. The generally accepted scaling concept for athermal systems is fairly well reproduced by linear and star-branched DPD chains and theta conditions appear for a unique parameter independent of functionality as in the case of Monte Carlo simulations. Furthermore, the correspondence between DPD and Monte Carlo data referring to the shape of chains and stars is fairly well, too. For dilute solutions the Zimm behavior is expected for dynamic properties which is indeed realized in DPD systems.
doi:10.1063/1.3231854 pmid:19791917 fatcat:oq5zbjyrcngndevcuvxzqwmmqi