We consider self-avoiding walks terminally attached to a surface at which they can adsorb. A force is applied, normal to the surface, to desorb the walk and we investigate how the behaviour depends on the vertex of the walk at which the force is applied. We use rigorous arguments to map out some features of the phase diagram, including bounds on the locations of some phase boundaries, and we use Monte Carlo methods to make quantitative predictions about the locations of these boundaries and the nature of the various phase transitions.
We consider a self-avoiding walk on the $d$-dimensional hypercubic lattice, terminally attached to an impenetrable hyperplane at which it can adsorb. When a force is applied the walk can be pulled off the surface and we consider the situation where the force is applied at the middle vertex of the walk. We show that the temperature dependence of the critical force required for desorption differs from the corresponding value when the force is applied at the end-point of the walk. This is of interest in single molecule pulling experiments since it shows that the required force can depend on where…
We study uniform 3-star polymers with one branch tethered to an attractive surface and another branch pulled by a force away from the surface. Each branch of the 3-star lattice is modelled as a self-avoiding walk on the simple cubic lattice with one endpoint of each branch joined at a common node. Recent theoretical work (Ref.~1) found four phases for this system: free, fully adsorbed, ballistic and mixed. The mixed phase occurs between the ballistic and fully adsorbed phase. We investigate this system by using the flatPERM Monte Carlo algorithm with special restrictions on the endpoint moves …
We consider a simple cubic lattice self-avoiding walk model of 3-star polymers adsorbed at a surface and then desorbed by pulling with an externally applied force. We determine rigorously the free energy of the model in terms of properties of a self-avoiding walk, and show that the phase diagram includes 4 phases, namely a ballistic phase where the extension normal to the surface is linear in the length, an adsorbed phase and a mixed phase, in addition to the free phase where the model is neither adsorbed nor ballistic. In the adsorbed phase all three branches or arms of the star are adsorbed …
We analyze the phase diagrams of self-avoiding walk models of uniform branched polymers adsorbed at a surface and subject to an externally applied vertical pulling force which, at critical values, desorbs the polymer. In particular, models of adsorbed branched polymers with homeomorphism types stars, tadpoles, dumbbells and combs are examined. These models generalize earlier results on linear, ring and $3$-star polymers. In the case of star polymers we confirm a phase diagram with four phases (a free, an adsorbed, a ballistic, and a mixed phase) first seen in the paper by Janse van Rensburg EJ…
We consider a model of star copolymers, based on self-avoiding walks, where the arms of the star can be chemically distinct. The copolymeric star is attached to an impenetrable surface at a vertex of unit degree and the different monomers constituting the star have different interaction strengths with the surface. When the star is adsorbed at the surface it can be desorbed by applying a force, either at a vertex of degree 1 or at the central vertex of the star. We give some rigorous results about the free energy of the system and use these to establish the general form of the phase diagrams, a…
We consider self-avoiding walks terminally attached to an impenetrable surface at which they can adsorb. We call the vertices farthest away from this plane the top vertices and we consider applying a force at the plane containing the top vertices. This force can be directed away from the adsorbing surface or towards it. In both cases we prove that the free energy (in the thermodynamic limit) is identical to the free energy when the force is applied at the last vertex. This means that the criterion determining the critical force - temperature curve is identical for the two ways in which the for…
We consider self-avoiding lattice polygons, in the hypercubic lattice, as a model of a ring polymer adsorbed at a surface and either being desorbed by the action of a force, or pushed towards the surface. We show that, when there is no interaction with the surface, then the response of the polygon to the applied force is identical (in the thermodynamic limit) for two ways in which we apply the force. When the polygon is attracted to the surface then, when the dimension is at least 3, we have a complete characterization of the critical force--temperature curve in terms of the behaviour, (a) whe…
In this paper we present simulations of a surface-adsorbed polymer subject to an elongation force. The polymer is modelled by a self-avoiding walk on a regular lattice. It is confined to a half-space by an adsorbing surface with attractions for every vertex of the walk visiting the surface, and the last vertex is pulled perpendicular to the surface by a force. Using the recently proposed flatPERM algorithm, we calculate the phase diagram for a vast range of temperatures and forces. The strength of this algorithm is that it computes the complete density of states from one single simulation. We …
We consider a self-avoiding walk model of polymer adsorption where the adsorbed polymer can be desorbed by the application of a force, concentrating on the case of the square lattice. Using series analysis methods we investigate the behaviour of the free energy of the system when there is an attractive potential $ε$ with the surface and a force $f$ applied at the last vertex, normal to the surface, and extract the phase boundary between the ballistic and adsorbed phases. We believe this to be exact to graphical accuracy. We give precise estimates of the location of the transition from the free…
A phase diagram for a surface-interacting long flexible polymer chain in a two-dimensional poor solvent where the possibility of collapse exists is determined using exact enumeration method. A model of a self-attracting self avoiding walk (SASAW) on a square lattice was considered and up to 28 steps in series were evaluated. A new adsorbed state having the conformation of a surface attached globule is found. Four phases (i) desorbed expanded, (ii) desorbed collapsed, (iii) adsorbed expanded and (iv) surface attached globule are found to meet at a point on the adsorption line.
A phase diagram for a surface interacting long flexible partially directed polymer chain in a two-dimensional poor solvent where the possibility of collapse in the bulk exists is determined using exact enumeration method. We used a model of self attracting self-avoiding walk and evaluated 30 steps in series. An intermediate phase in between the desorbed collapsed and adsorbed expanded phases having the conformation of a surface attached globule is found. The four phases, viz. (i) desorbed expanded, (ii) desorbed collapsed, (iii) adsorbed expanded, (iv) surface attached globule are found to mee…
We study the interaction problem of a linear polymer chain, floating in fractal containers that belong to the three-dimensional Sierpinski gasket (3D SG) family of fractals, with a surface-adsorbed linear polymer chain. Each member of the 3D SG fractal family has a fractal impenetrable 2D adsorbing surface, which appears to be 2D SG fractal. The two-polymer system is modelled by two mutually crossing self-avoiding walks. By applying the Monte Carlo Renormalization Group (MCRG) method, we calculate the critical exponents $ϕ$, associated with the number of contacts of the 3D SG floating polymer …
We investigate the phase diagram of a self-avoiding walk model of a 3-star polymer in two dimensions, adsorbing at a surface and being desorbed by the action of a force. We show rigorously that there are four phases: a free phase, a ballistic phase, an adsorbed phase and a mixed phase where part of the 3-star is adsorbed and part is ballistic. We use both rigorous arguments and Monte Carlo methods to map out the phase diagram, and investigate the location and nature of the phase transition boundaries. In two dimensions, only two of the arms can be fully adsorbed in the surface and this alters …
Fekete's lemma shows the existence of limits in subadditive sequences. This lemma, and generalisations of it, also have been used to prove the existence of thermodynamic limits in statistical mechanics. In this paper it is shown that the two variable supermultiplicative relation $$ p_{n_1}(m_1)\,p_{n_2}(m_2) \leq p_{n_1+n_2}(m_1 + m_2) $$ together with mild assumptions, imply the existence of the limit $$ \log \mathcal{P}_\#(ε) = \lim_{n\to\infty} \frac{1}{n} \log p_n(\lfloor εn \rfloor).$$ This is a generalisation of Fekete's lemma. The existence of $\mathcal{P}_\#(ε)$ are proven for models o…
Self-avoiding walks are a simple and well-known model of long, flexible polymers in a good solvent. Polymers being pulled away from a surface by an external agent can be modelled with self-avoiding walks in a half-space, with a Boltzmann weight $y = e^f$ associated with the pulling force. This model is known to have a critical point at a certain value $y_c$ of this Boltzmann weight, which is the location of a transition between the so-called free and ballistic phases. The value $y_c=1$ has been conjectured by several authors using numerical estimates. We provide a relatively simple proof of th…
We investigate self-avoiding walk models of linear block copolymers adsorbed at a surface and desorbed by the action of a force. We rigorously establish the dependence of the free energy on the adsorption and force parameters, and the form of the phase diagram for several cases, including $AB$-diblock copolymers and $ABA$-triblock copolymers, pulled from an end vertex and from the central vertex. Our interest in block copolymers is partly motivated by the occurrence of a novel mixed phase in a directed walk model of diblock copolymers \cite{Iliev} and we believe that this paper is the first ri…
We show that when a self-avoiding polymer chain is pulled off a sticky surface by force applied to the end segment, it undergoes a first-order thermodynamic phase transition albeit without phase coexistence. This unusual feature is demonstrated analytically by means of a Grand Canonical Ensemble (GCE) description of adsorbed macromolecules as well as by Monte Carlo simulations of an off-lattice bead-spring model of a polymer chain. Theoretical treatment and computer experiment can be carried out both in the constant-force f statistical ensemble and in the constant-height h ensemble. We find th…
We consider a model of self-avoiding walk on a lattice with on-site repulsion and an attraction for every vertex of the walk visited on the surface to study force-induced desorption of a linear polymer chain adsorbed on an attractive surface and use the exact enumeration technique for analyzing how the critical force for desorption $f_c(T)$ depends on the temperature. The curve $f_c(T)$ gives the boundary separating the adsorbed phase from the desorbed phase. Our results show that in two dimensions where surface is a line the force $f_c(T)$ increases monotonically as temperature is lowered and…
Using extensive Monte Carlo simulations, we investigate the surface adsorption of self-avoiding trails on the triangular lattice with two- and three-body on-site monomer-monomer interactions. In the parameter space of two-body, three-body, and surface interaction strengths, the phase diagram displays four phases: swollen (coil), globule, crystal, and adsorbed. For small values of the surface interaction, we confirm the presence of swollen, globule, and crystal bulk phases. For sufficiently large values of the surface interaction, the system is in an adsorbed state, and the adsorption transitio…
We consider the model of self-avoiding walks on the $d$-dimensional hypercubic lattice interacting with a $d^*$-dimensional defect, where $1\leq d^*<d$. Such an interaction can be attractive or repulsive, and is controlled by a Boltzmann weight $a$ associated with visits to the defect. When $d=3$ and $d^*=1$ or $2$, this can be seen as a model of long linear polymers in a good solvent, interacting with a linear filament or the interface of two liquids of different density. For all combinations of dimensions, there is a critical value $a_{\rm c}$ which separates the desorbed and adsorbed phases…
We investigate the surface adsorption transition of interacting self-avoiding square lattice trails onto a straight boundary line. The character of this adsorption transition depends on the strength of the bulk interaction, which induces a collapse transition of the trails from a swollen to a collapsed phase, separated by a critical state. If the trail is in the critical state, the universality class of the adsorption transition changes; this is known as the special adsorption point. Using flatPERM, a stochastic growth Monte Carlo algorithm, we simulate the adsorption of self-avoiding interact…
Lattice model of directed self avoiding walk is used to investigate adsorption properties of a semiflexible sequential copolymer chain on an impenetrable curved surface on a hexagonal lattice in two dimensions. Walks of the copolymer chains are directed in a direction away from the surface at a suitable value of monomer surface attraction, the copolymer chain gets adsorbed on the surface. To calculate exact value of monomer surface attraction, the directed walk model have been solved analytically using generating function method to discuss results when one type monomer of the copolymer chain h…
Recent theoretical predictions on DNA mechanical separation induced by pulling forces are numerically tested within a model in which self-avoidance for DNA strands is fully taken into account. DNA strands are described by interacting pairs of self avoiding walks (SAW) which are pulled apart by a force applied at the two extremities. The whole phase diagram is spanned by extensive Monte Carlo (MC) simulations and the existence of a low temperature denaturation is confirmed. The basic features of the phase diagram and the re-entrant phase boundary are also obtained with a simple heuristic argume…
