Double-exponential decay of orientational correlations in semiflexible polyelectrolytes

In this paper we revisited the problem of persistence length of polyelectrolytes. We performed a series of Molecular Dynamics simulations using the Debye-Ḧuckel approximation for electrostatics to test several equations which go beyond the classical description of Odijk, Skolnick and Fixman (OSF). The data confirm earlier observations that in the limit of large contour separations the decay of orientational correlations can be described by a single-exponential function and the decay length can be described by the OSF relation. However, at short countour separations the behaviour is more complex. Recent equations which introduce more complicated expressions and an additional length scale could describe the results very well on both the short and the long length scale. The equation of Manghi and Netz when used without adjustable parameters could capture the qualitative trend but deviated in a quantitative comparison. Better quantitative agreement within the estimated error could be obtained using three equations with one adjustable parameter: 1) the equation of Manghi and Netz; 2) the equation proposed by us in this paper; 3) the equation proposed by Cannavacciuolo and Pedersen. Two characteristic length scales can be identified in the data: the intrinsic or bare persistence length and the electrostatic persistence length. All three equations use a single parameter to describe a smooth crossover from the short-range behaviour dominated by the intrinsic stiffness of the chain to the long-range OSF-like behaviour.© Springer-Verlag 2012.Initial part of this work was done within the project funded by the Grant Agency of the Charles University in Prague, project number 43-257269. Further support came from the MSMT of the Czech Republic, Research plan MSM0021620857 and from the Grant Agency of the Czech Republic, grants P205/11/J043 and P106/12/0143.Peer Reviewe

Double-exponential decay of orientational correlations in semiflexible polyelectrolytes

In this paper we revisited the problem of persistence length of polyelectrolytes. We performed a series of Molecular Dynamics simulations using the Debye-Hückel approximation for electrostatics to test several equations which go beyond the classical description of Odijk, Skolnick and Fixman (OSF). The data confirm earlier observations that in the limit of large contour separations the decay of orientational correlations can be described by a single-exponential function and the decay length can be described by the OSF relation. However, at short countour separations the behaviour is more complex. Recent equations which introduce more complicated expressions and an additional length scale could describe the results very well on both the short and the long length scale. The equation of Manghi and Netz when used without adjustable parameters could capture the qualitative trend but deviated in a quantitative comparison. Better quantitative agreement within the estimated error could be obtained using three equations with one adjustable parameter: 1) the equation of Manghi and Netz; 2) the equation proposed by us in this paper; 3) the equation proposed by Cannavacciuolo and Pedersen. Two characteristic length scales can be identified in the data: the intrinsic or bare persistence length and the electrostatic persistence length. All three equations use a single parameter to describe a smooth crossover from the short-range behaviour dominated by the intrinsic stiffness of the chain to the long-range OSF-like behaviour

Double-exponential decay of orientational correlations in semiflexible polyelectrolytes

In this paper we revisited the problem of persistence length of polyelectrolytes. We performed a series of Molecular Dynamics simulations using the Debye-Hückel approximation for electrostatics to test several equations which go beyond the classical description of Odijk, Skolnick and Fixman (OSF). The data confirm earlier observations that in the limit of large contour separations the decay of orientational correlations can be described by a single-exponential function and the decay length can be described by the OSF relation. However, at short countour separations the behaviour is more complex. Recent equations which introduce more complicated expressions and an additional length scale could describe the results very well on both the short and the long length scale. The equation of Manghi and Netz when used without adjustable parameters could capture the qualitative trend but deviated in a quantitative comparison. Better quantitative agreement within the estimated error could be obtained using three equations with one adjustable parameter: 1) the equation of Manghi and Netz; 2) the equation proposed by us in this paper; 3) the equation proposed by Cannavacciuolo and Pedersen. Two characteristic length scales can be identified in the data: the intrinsic or bare persistence length and the electrostatic persistence length. All three equations use a single parameter to describe a smooth crossover from the short-range behaviour dominated by the intrinsic stiffness of the chain to the long-range OSF-like behaviour