Buckling, Fluctuations and Collapse in Semiflexible Polyelectrolytes

We present a systematic statistical mechanical analysis of the conformational properties of a stiff polyelectrolyte chain with intrachain attractions that are due to counterion correlations. We show that the mean-field solution corresponds to an Euler-like buckling instability. The effect of the conformational fluctuations on the buckling instability is investigated, first, qualitatively, within the harmonic (semiclassical'') theory, then, systematically, within a 1/d-expansion, where d denotes the dimension of embedding space. Within the semiclassical’’ approximation, we predict that the effect of fluctuations is to renormalize the effective persistence length to smaller values, but not to change the nature of the mean-field (i.e., buckling) behavior. Based on the 1/d-expansion we are, however, led to conclude that thermal fluctuations are responsible for a change of the buckling behavior which is turned into a polymer collapse. A phase diagram is constructed in which a sequence of collapse transitions terminates at a buckling instability that occurs at a place that varies with the magnitude of the bare persistence length of the polymer chain, as well as with the strength and range of the attractive potential.