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We study the behavior of single linear polyelectrolytes condensed bytrivalent salt under the action of electric fields through computersimulations. The chain is unfolded when the strength of the electric field isstronger than a critical value. This critical electric field follows a scalinglaw against chain length and the exponent of the scaling law is $-0.77(1)$,smaller than the theoretical prediction, $-3\nu/2$ [Netz, Phys. Rev. Lett. 90(2003) 128104], and the one obtained by simulations in tetravalent saltsolutions, $-0.453(3)$ [Hsiao and Wu, J. Phys. Chem. B 112 (2008) 13179]. Itdemonstrates that the scaling exponent depends sensitively on the salt valence.Hence, it is easier to unfold chains condensed by multivalent salt of smallervalence. Moreover, the absolute value of chain electrophoretic mobilityincreases drastically when the chain is unfolded in an electric field. Thedependence of the mobility on electric field and chain length provides aplausible way to impart chain-length dependence in free-solutionelectrophoresis via chain unfolding transition induced by electric fields.Finally, we show that, in addition to an elongated structure, a condensed chaincan be unfolded into an U-shaped structure. The formation of this structure inour study is purely a result of the electric polarization, but not of theelasto-hydrodynamics dominated in sedimentation of polymers.

Unfolding Polyelectrolytes in Trivalent Salt Solutions Using DC Electric Fields: A Study by Langevin Dynamics Simulations