Translational Entropy Research Articles

Interface-packing analysis of F1-ATPase using integral equation theory and manifold learning

It has been shown that the translational entropy of water plays a key role in biological processes such as protein folding and ligand binding. Under the physiological condition, tightly packed protein conformations like native structures are achieved so that the translational entropy of water is maximized. In this study, we investigate the rotation mechanism of a rotary protein motor, F1-ATPase, by analyzing the packing at the interfaces between the subunits. The packing at the interface between a subunit pair is analyzed using the change in the solvent entropy upon forming subunit pair, ∆S. It is found that as the γ subunit rotates, the ∆S value of a α-β subunit pair decrease because the interface packing becomes loose. However, because the interface packing of another α-β subunit pair becomes tighter upon the rotation, ∆S of this α-β subunit pair increases, leading to a compensation of the decrease in ∆S. Such compensation would be necessary to maximize the solvent entropy of F1-ATPase. In this study, packing at the interfaces between the subunits is also analyzed using a manifold-learning technique, and it is suggested a possibility that a qualitative estimation of the ∆S values of some α-β subunit pairs can be predicted using a manifold-learning technique.

Upside-Down Adsorption: The Counterintuitive Influences of Surface Entropy and Surface Hydroxyl Density on Hydrogen Spillover.

Although hydrogen spillover is often invoked to explain anomalies in catalysis, spillover remains a poorly understood phenomenon. Hydrogen spillover (H*) is best described as highly mobile H atom equivalents that arise when H2 migrates from a metal nanoparticle to an oxide or carbon support. In the 60 years since its discovery, few methods have become available to quantify or characterize H*-support interactions. We recently showed in situ infrared spectroscopy and volumetric chemisorption can quantify reversible H2 adsorption on Au/TiO2 catalysts, where adsorbed hydrogen exists as H* and interacts with titania surface hydroxyl (TiOH) groups. Here, we report parallel thermogravimetric analysis and Fourier transform infrared spectroscopy methods for systematically manipulating the surface TiOH density. We examine the role of surface hydroxylation on spillover thermodynamics using van't Hoff studies to determine apparent adsorption enthalpies and entropies at constant H* coverage, which is necessary to maintain constant H* translational entropy. Although surface TiOH groups are the likely adsorption sites, the data show removing hydroxyl groups increases spillover. This surprising finding─that adsorption increases as the adsorption site density decreases─is associated with improved thermodynamics on dehydroxylated surfaces. A strong adsorption enthalpy-entropy correlation implicates the changing surface entropy of the titania support itself (i.e., an initial state effect) is deeply intertwined with the H* configurational entropy. These effects are surprising and should apply to all low-coverage adsorbates where entropy terms dominate more traditional enthalpic considerations. Moreover, this study points toward a kinetic test for invoking spillover in a reaction mechanism: namely, in situ dehydroxylation should enhance spillover processes.

Non-covalent interactions and charge transfer in the CO activation by low-valent group 14 complexes.

The CO activation by low-valent group 14 catalysts encompasses the rupture of varied covalent bonds in a single transition state through a concerted pathway. The bond between the central main group atom and the hydride in the complex is elongated to trigger the formation of the C-H bond with CO accompanied by the concomitant formation of the E-O bond between the complex and CO to lead the corresponding formate product. Prior studies have established that besides the apolar nature of CO , its initial interaction with the complex is primarily governed by electrostatic interactions. Notably, other stabilizing interactions and the transfer of charge between catalysts and CO during the initial phases of the reaction have been ignored. In this study, we have quantified the non-covalent interactions and charge transfer that facilitate the activation of CO by group 14 main group complex. Our findings indicate that electrostatic interactions predominantly stabilize the complex and CO in the reactant region. However, induction energy becomes the main stabilizing force as the reaction progresses towards the transition state, surpassing electrostatics. Induction contributes about 50% to the stabilization at the transition state, followed by electrostatics (40%) and dispersion interactions (10%). Atomic charges calculated with the minimal basis iterative stockholder (MBIS) method reveal larger charge transfer for the back-side reaction path in which CO approaches the catalysts in contrast to the front-side approach. Notably, it was discovered that a minor initial bending of CO to approximately initiates the charge transfer process for all systems. Furthermore, our investigation of group 14 elements demonstrates a systematic reduction in both activation energies and charge transfer to CO while descending in group 14. All studied reactions were characterized along the reaction coordinate obtained with the intrinsic reaction coordinate (IRC) methodology at the M06-2X/6-31g(d,p) level of theory. Gibbs free energy in toluene was computed using electronic energies at the DLPNO-CCSD(T)/cc-pVTZ-SSD(E) level of theory. Vibrational and translational entropy corrections were applied to provide a more accurate description of the obtained Gibbs free energies. To better characterize the changes in the reaction coordinate for all reactions, the reaction force analysis (RFA) has been employed. It enables the partition of the reaction coordinate into the reactant, transition state, and product regions where different stages of the mechanism occur. A detailed characterization of the main non-covalent driving forces in the initial stages of the activation of CO by low-valent group 14 complexes was performed using symmetry-adapted perturbation theory (SAPT). The SAPT0-CT/def2-SVP method was employed for these computations. Charge transfer descriptors based on atomic population using the MBIS scheme were also obtained to complement the SAPT analyses.

On the Stabilizing Effect of Aspartate and Glutamate and Its Counteraction by Common Denaturants.

By performing differential scanning calorimetry(DSC) measurements on RNase A, we studied the stabilization provided by the addition of potassium aspartate(KAsp) or potassium glutamate (KGlu) and found that it leads to a significant increase in the denaturation temperature of the protein. The stabilization proves to be mainly entropic in origin. A counteraction of the stabilization provided by KAsp or KGlu is obtained by adding common denaturants such as urea, guanidinium chloride, or guanidinium thiocyanate. A rationalization of the experimental data is devised on the basis of a theoretical approach developed by one of the authors. The main contribution to the conformational stability of globular proteins comes from the gain in translational entropy of water and co-solute ions and/or molecules for the decrease in solvent-excluded volume associated with polypeptide folding (i.e., there is a large decrease in solvent-accessible surface area). The magnitude of this entropic contribution increases with the number density and volume packing density of the solution. The two destabilizing contributions come from the conformational entropy of the chain, which should not depend significantly on the presence of co-solutes, and from the direct energetic interactions between co-solutes and the protein surface in both the native and denatured states. It is the magnitude of the latter that discriminates between stabilizing and destabilizing agents.

Electrified Nano-Gaps Under AC Field: A Molecular Dynamics Study

Solid-Liquid Interfaces (SLIs) hold immense significance in various areas such as materials science, chemistry, physics, biology and medicine [1]. Many studies aim to decipher the molecular details of SLIs through analytical, computational or experimental methods [2]-[3], each optimized for different aspects of SLIs. Analytical methods are mainly based on the mean field approximation and work best for dilute solutions. Computational methods are bound by their maximum accessible time and length scales, while the limitation of experimental approach tend to lie in minimum values accessible of these scales. The concomitant deployment of both the approaches is a powerful tool in studying SLIs.In the current study both the computational and experimental tools are employed to study the interface of silica with aqueous saline solutions under electric fields. Molecular Dynamics (MD) simulation are utilized to investigate the relative response of the ions and waters exposed to an external AC field in a nanoscale silica-elecrolyte-gold system. Complementary experimental measurements are conducted with atomic force microscopy (AFM) which measures the dielectric force exerted on the nanoscale AFM probe. The impact of external factors such as salt concentration, AC voltage frequency and the system size is systematically investigated.Simulations reveal both the transient and stable response of water and ions as the main component of the system to the AC field. In the transient response, the water electric dipole increases monotonically with the voltage at the first cycle while it takes longer for ions to react to the field, limited by their diffusion time. When the ionic response becomes large enough to screen the field, the dipole moment of water molecules decreases and lead the phase of the applied field. The lag in the ionic response is owing to the time required for the ionic diffusion, while the lead in the water response is due to ionic lag.To obtain the stable response through MD simulation, Fourier transform was deployed with the results showing that electric dipole of ions and water have a periodic behavior with a frequency similar to the AC field and waters in lead and ions in lag. The dipole-voltage plots for ions and waters depicted an energy transfer between water and ions in each cycle. Decreasing the frequency to 10MHz, no energy exchange was observed concomitant to the removal of water lead. Besides, in the frequency range of 100MHz-200MHz in which the water phase lead reaches its maximum value, there is also a maximum in the energy exchange. Thus, there is a direct relation between the water-ion energy exchange and lead in the water response.The stable response is affected by various factors including the separation distance between the surfaces, the ionic concentration and the AC frequency. The MD observations of a decrease in the water lead and ionic lag with reducing the electrolyte gap could explain AFM measurements where the dielectric force appears to decrease for small gaps, a counter-intuitive result if bulk electrolyte properties are assumed. The simulation results also show that the sum of the electric dipole of water and ions is always in phase with the applied voltage implying that the field is totally screened by the combination of both of them. To provide the same amount of screening in larger separation distance the electric dipole of ions has to increase to counteract its larger lag which is observed in the ionic dipole values. As the ionic dipole despite water molecules are caused by translational entropy, larger ionic dipole translates to larger forces which is observed in the AFM experiments.[1] Taketoshi et al. Japanese Journal of Applied Physics (2021).[2] T. Fukuma and R. Garcia, ACS nano (2018).[3] J.M. Andanson and A. Baiker, Chemical Society Reviews (2010).

Counterion Release from Macroion Assemblies of Planar Geometry.

Macroions such as nanoparticles, polyelectrolytes, ionic gels, and amphiphiles can form condensed, often self-assembled, phases that are embedded in a solvent region. The condensed phase contains not only the partially or fully immobile charges of their macroions but also corresponding counterions that are mobile and thus free to migrate out of their confinement into the solvent region where they benefit from high translational entropy. Based on the nonlinear Poisson-Boltzmann model for monovalent ions, we quantify the corresponding fraction of released counterions for a planar slab geometry of the macroion phase. Slab thickness, extension of the solvent phase, fixed background charge density provided by the macroions, and dielectric constants inside slab and solvent combine into three dimensionless parameters that the fraction of released counterions depends on. We calculate that fraction and analyze the limits of a thin macroion phase, a large solvent phase, and linearized theory, where simple analytic results become available. Of particular interest is the presence of a single-planar interface that separates a bulk macroion phase from an extended solvent region. We calculate the apparent surface charge density that emerges due to the released counterions. Our model yields a comprehensive description of counterion partitioning between a planar macroion phase and a solvent region on the level of mean-field electrostatics in the absence of added salt ions.

Ion Coupling, Bonding, and Transfer in Narrow Carbon Nanotubes.

Narrow carbon nanotubes (nCNT) are unique mimics of biological channels with water-ion selectivity attractive for applications such as water purification and osmotic energy harvesting, yet their understanding is still incomplete. Here, an ab initio computation is employed to develop the full picture of ion transfer in nCNT including specificity and coupling between ions. The thermodynamic costs of ion transfer are computed for single ions and ion pairs and used to evaluate different local coupling scenarios including strong (pairing) and weak (free-ion) coupling as well as "electroneutrality breakdown" (EB), possible for cations only due to their chemisorption-like interaction with nCNT. The results also indicate that nCNT behaves as a highly polarizable metal-like shell, which eliminates the dielectric energy when CNT accommodates coupled cation and anion. This allows facile computation and comparison of the full transfer costs, including translation entropy, for different ions in different coupling modes to identify the dominant regime. EB transfer appears most favorable for K+, while anions strongly favor transfer as pairs, except for chloride which favors weak coupling and, at neutral pH, transfers as a trace ion coupled to both cation and OH-. The results demonstrate that, in general, observed ion permeation and conduction in nCNT, especially for anions, reflect a complex ion-specific and composition-dependent interplay between different ions.

The impact of text type on Chinese-English translation effort: an investigation with reference to translation entropy

Various factors affect translation effort. This research aims to explore the impact of source text type on Chinese-English translation effort with reference to translation entropy. An eye-tracking and key-logging experiment was conducted. Thirty-one student translators translated four text types, namely legal, advertising, news, and poetic texts. Data analyses show that there is a significant difference in participants’ effort of translating the four texts, which can be seen in such indicators as subjective ratings, fixation, pause, translation time, and edits. We further studied participants’ translations and calculated the translation entropy for each text type, which is a measure of uncertainty in translation. Analysis shows that there is a significant difference in translation entropy among the four text types, which provides evidence that source text features affect translation uncertainty and, hence, translation effort to search for appropriate options. The discussions are intended to provide further insight into the impact of text type on the translation process, and the result confirms the reliability of translation entropy as a predictor of translation effort.

Entropy-driven polymer collapse on increasing the temperature: The case of poly(N-vinylcaprolactam)

Poly(N-vinylcaprolactam), PNVCL, chains undergo a temperature-induced, reversible and endothermic collapse in water at around 32 °C. The entropy gain driving PNVCL collapse has to come from water molecules, but it cannot be associated with their passage from the polymer hydration shell to the bulk because there is no difference in their tetrahedral structural order. I have shown that the water entropy gain comes from the decrease in solvent-excluded volume effect associated with chain collapse: there is a marked increase in the spatial configurations accessible to water molecules, leading to a large gain in their translational entropy. This mechanism, even though generic, proves to be effective solely in water and aqueous solutions because the magnitude of the solvent-excluded volume effect is amplified by the large number density of water, stemming from the strength of H-bonds and the small size of water molecules.

A Unified Description of Salt Effects on the Liquid-Liquid Phase Separation of Proteins.

Protein aggregation via liquid-liquid phase separation (LLPS) is ubiquitous in nature and is intimately connected to many human diseases. Although it is widely known that the addition of salt has crucial impacts on the LLPS of proteins, full understanding of the salt effects remains an outstanding challenge. Here, we develop a molecular theory that systematically incorporates the self-consistent field theory for charged macromolecules into the solution thermodynamics. The electrostatic interaction, hydrophobicity, ion solvation, and translational entropy are included in a unified framework. Our theory fully captures the long-standing puzzles of the nonmonotonic salt concentration dependence and the specific ion effect. We find that proteins show salting-out at low salt concentrations due to ionic screening. The solubility follows the inverse Hofmeister series. In the high salt concentration regime, protein continues salting-out for small ions but turns to salting-in for larger ions, accompanied by the reversal of the Hofmeister series. We reveal that the solubility at high salt concentrations is determined by the competition between the solvation energy and translational entropy of the ion. Furthermore, we derive an analytical criterion for determining the boundary between the salting-in and salting-out regimes, which is in good agreement with experimental results for various proteins and salt ions.

Non‐monotonic salt concentration dependence of inverted electrokinetic flow

AbstractModeling of electrokinetic flows is crucial to understand numerous phenomena associated with electrochemistry, biophysics, and colloidal science. Here, we incorporate the modified Gaussian renormalized fluctuation theory into transport equations for electrolyte solutions to study the ion‐correlation‐induced inversion of electrokinetic flows, also known as charge inversion. We are able to capture the non‐monotonic dependence of inverted streaming current and reversed electrophoretic mobility on salt concentration. By analyzing the double‐layer structure, we elucidate that this non‐monotonicity is a consequence of the competition between spatially varying ion correlations and the translational entropy of the ions. We find that for practical values of surface charge densities, the excluded volume effect does not play any significant role. In a significant improvement over existing theories, our theoretical predictions are in quantitative agreement with experimental measurements for charge inversion in trivalent salts.

Water-Structure-Specific Entropic Dominance in the Filling of Boron Nitride Nanotubes

The filling of nanometer and sub-nanometer channels/tubes with water governs applications ranging from desalination and filtration to nanoscale energy conversion. Here, we report the most nonintuitive entropy-dominated filling of mildly hydrophilic boron nitride nanotubes (BNNTs) with diameters ranging from 0.85 to 1.69 nm. For all the BNNT sizes, water inside the BNNT is more stable than water in the bulk. The factor dictating the favorable nature of the entropy depends on the specific-BNNT-diameter-dictated structure of the water molecules. For example, for the 0.85 nm BNNT, the rotational entropic component dominates due to the presence of a significant fraction of the dangling water OH bonds that do not participate in hydrogen bonding. The fraction of such dangling OH bonds (the average HBs per molecule) decreases (increases) with an increase in the BNNT diameter, leading to a progressively reduced contribution of the rotational entropy. For the 1 nm BNNT, the translational entropic component dominates due to the enhanced in-plane motion of the water molecules caused by the single-file nature of water molecules spanning a significant radial expanse inside the BNNT. For larger BNNTs, translational entropy decreases with an increase in the BNNT diameter, although it remains the dominant factor governing the entropy-driven filling of BNNTs. This favorable translational entropy for larger BNNTs can be associated with (1) the presence of chain-like regions formed by water in 1.13 nm BNNT and (2) the presence of a high specific water volume and reduced number of HBs per molecule (as compared with bulk water) in 1.27, 1.41, 1.55, and 1.69 nm BNNTs.

Electrostatic Interaction on Liquid–Liquid Phase Separation at Low Salt Fraction Revealed by Scattering Techniques

Past studies on salt-doped polymer blends indicate that the electrostatic effect is complicated due to the combined effects of translational entropy of dissociated ions, ion solvation, ion–ion correlation, and ion clustering, especially at high salt concentrations. It still remains a challenge to unveil the electrostatic interaction of dissociated ions on phase separation explicitly in experiments. To address this challenge, the key principle of this study is to have the salt at extremely low concentrations, while its effect on phase separation is significant enough to be detected by scattering techniques. This experimental design enables the solvation of dissociated ions as the dominating factor, carefully avoiding complications from other effects. We characterize concentration fluctuations at full length scales by small-angle laser light scattering, X-ray scattering, and neutron scattering. The measured cloud points, spinodal temperatures, correlation lengths, and effective interaction parameters exhibit significant increase with the salt fraction, indicating that the electrostatic interaction promotes phase separation. We further reveal the electrostatic interaction of cations and anions, respectively. The asymmetric deflection of the phase diagram is quantitatively explained by the composition-dependent solvation of dissociated ions. This fundamental research provides experimental support for the progress of recent theoretical work and is helpful to guide the structural control in polymer electrolytes.

Polymorph Stability and Free Energy of Crystallization of Freely-Jointed Polymers of Hard Spheres.

The free energy of crystallization of monomeric hard spheres as well as their thermodynamically stable polymorph have been known for several decades. In this work, we present semianalytical calculations of the free energy of crystallization of freely-jointed polymers of hard spheres as well as of the free energy difference between the hexagonal closed packed (HCP) and face-centered cubic (FCC) polymorphs. The phase transition (crystallization) is driven by an increase in translational entropy that is larger than the loss of conformational entropy of chains in the crystal with respect to chains in the initial amorphous phase. The conformational entropic advantage of the HCP polymer crystal over the FCC one is found to be ΔschHCP-FCC≈0.331×10-5k per monomer (expressed in terms of Boltzmann's constant k). This slight conformational entropic advantage of the HCP crystal of chains is by far insufficient to compensate for the larger translational entropic advantage of the FCC crystal, which is predicted to be the stable one. The calculated overall thermodynamic advantage of the FCC over the HCP polymorph is supported by a recent Monte Carlo (MC) simulation on a very large system of 54 chains of 1000 hard sphere monomers. Semianalytical calculations using results from this MC simulation yield in addition a value of the total crystallization entropy for linear, fully flexible, athermal polymers of Δs≈0.93k per monomer.

Theoretical and Experimental Assessments of Elementary Steps and Bound Intermediates in Catalytic H2–O2 Reactions on Dispersed Pt Nanoparticles

Kinetic and isotopic data and H2 chemisorption uptakes measured under reaction conditions are combined here with theoretical assessments on model catalytic surfaces at relevant hydrogen (H*) coverages to establish the identity and kinetic relevance of elementary steps and bound species in H2–O2 reactions on Pt surfaces. Turnover rates are proportional to O2 pressure and decrease and then reach constant values as H2 pressures increase, leading to apparent first-order rate parameters (rO2/PO2) that reflect reactive collision probabilities of O2 with surfaces and which depend solely on the H2 pressure at all temperatures (540–680 K). H2–D2 isotopic exchange rates during reactions with O2 are much faster than water formation rates, consistent with quasi-equilibrated H2 dissociation steps and with prevalent H* coverages that can be determined independently from H2 uptakes; such measurements enable the decoupling of non-Langmuirian adsorption parameters from kinetic parameters in rate equations. These data indicate that H2–O2 reactions involve two kinetically-relevant O2 dissociation routes. One channel forms two bound O atoms on bare Pt atom ensembles available within H* adlayers, which react via fast subsequent reactions with H* to form H2O. A parallel O2 dissociation route involves reactions with a H*–H* pair to form weakly bound adsorbed hydrogen peroxide (*HOOH*), a highly reactive species that subsequently cleaves its O–O bond in steps that are not kinetically-relevant. The free-energy barriers are dominated by losses in translational entropy incurred upon the formation of the transition states from their gaseous O2 precursors. Kinetic isotope effects are near unity for both routes because H* is not involved in direct O2 dissociation steps, and the *HOOH* formation transition state occurs very early along the reaction coordinate (with nearly intact O–O and Pt–H bonds from reactant states), as confirmed by DFT-derived energies and isotope effects.

Free and internal energies for the adsorption of short alkanes into the zeolite SSZ-13 from ab initio molecular dynamics simulations.

Electronic structure calculations have become a valuable tool in understanding chemical reactions of hydrocarbons in zeolite pores. However, commonly applied approaches to calculate free energies based on static electronic structure calculations significantly overestimate the entropic penalty for molecular adsorption into zeolite pores. Here, we use ab initio molecular dynamics (AIMD) simulations to model the adsorption of methane, ethane, and propane to purely siliceous and protonated SSZ-13. In our analyses we focus on the internal and Helmholtz free energies of adsorption of each molecule and compare our results to various approaches for the calculation of free energies based on static calculations. We find that only an approach that retains two thirds of the translational entropy of the adsorbate upon adsorption compares favorably with AIMD simulations. However, comparison to experimental measurements of Gibbs free energies of adsorption reported in the literature implies that we might not have captured the full complexity of alkane adsorption in our model. We expect that results in this work will help to develop a better understanding of alkane adsorption in zeolites, and that the provided data will serve as a benchmark for free energy calculations of alkane adsorption in zeolites in the future.

Microbial biofilms are shaped by the constant dialogue between biological and physical forces in the extracellular matrix.

Microbial biofilms are shaped by the constant dialogue between biological and physical forces in the extracellular matrix.

Vapor Swelling of Polymer Brushes Compared to Nongrafted Films.

Polymer brushes, coatings of polymers covalently end-grafted to a surface, have been proposed as a more stable alternative to traditional physisorbed coatings. However, when such coatings are applied in settings such as vapor sensing and gas separation technologies, their responsiveness to solvent vapors becomes an important consideration. It can be anticipated that the end-anchoring in polymer brushes reduces the translational entropy of the polymers and instead introduces an entropic penalty against stretching when vapor is absorbed. Therefore, swelling can be expected to be diminished in brushes compared to nongrafted films. Here, we study the effect of the anchoring-constraint on vapor sorption in polymer coatings using coarse-grained molecular dynamics simulations as well as humidity-controlled ellipsometry on chemically identical polymer brushes and nongrafted films. We find a qualitative agreement between simulations and experiments, with both indicating that brushes certainly swell less than physisorbed films, although this effect is minor for common grafting densities. Our results imply that polymer brushes indeed hold great potential for the intended applications.

Biosorption of Nitrate by Thermodynamic and Kinetics study using Tamarind Fruit Shells

<p>The majority of nitrate (NO3‾) pollutants come from a different type of industries. Even if present in low amounts, these nitrates are harmful to humans and aquatic systems. This research investigated the utilisation of Tamarind Fruit shell (TFS) as biosorbent in the removal of Nitrate from aqueous solution. TFS shell was modified by soaking it with distilled water. Many remediation strategies are available, but they are both costly and ineffectual. However, it has been discovered via significant research that waste materials such as tamarind bark, eggshells, and agricultural wastes are well suited to removing nitrate from waste water using the biosorption process (Panida, et.al., 2010). Biosorption is a nitrate removal process that is both environment friendly and cost-effective. The equilibrium distribution of NO3‾ onto the surface of the TFS can be best explained by Freundlich isotherm. Based upon the reaction of the thermodynamic study the TFS- NO3‾ interaction is an endothermic (Amardeep, et.al., 2013). A substantial chance in the NO3‾ - TFS interaction is expected because of the significant gain in the translational entropy by the displaced synchronised water molecules. Than the Chemiluminescence Analysing techniques Spectroscopic studies shows the biosorption capacity of TFS shows a little variation between 1.25 mg/g for 1 mm size and 2.14 mg/g for 0.13 mm size.</p>

Polymorphism and Perfection in Crystallization of Hard Sphere Polymers

We present results on polymorphism and perfection, as observed in the spontaneous crystallization of freely jointed polymers of hard spheres, obtained in an unprecedentedly long Monte Carlo (MC) simulation on a system of 54 chains of 1000 monomers. Starting from a purely amorphous configuration, after an initial dominance of the hexagonal closed packed (HCP) polymorph and a transitory random hexagonal close packed (rHCP) morphology, the system crystallizes in a final, stable, face centered cubic (FCC) crystal of very high perfection. An analysis of chain conformational characteristics, of the spatial distribution of monomers and of the volume accessible to them shows that the phase transition is caused by an increase in translational entropy that is larger than the loss of conformational entropy of the chains in the crystal, compared to the amorphous state. In spite of the significant local re-arrangements, as reflected in the bending and torsion angle distributions, the average chain size remains unaltered during crystallization. Polymers in the crystal adopt ideal random walk statistics as their great length renders local conformational details, imposed by the geometry of the FCC crystal, irrelevant.