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Factors Affecting Dissolution: Polymorphism, Amorphism and Pseudopolymorphism01:21

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Polymorphism refers to the existence of a drug substance in multiple crystalline forms, known as polymorphs. Recently, this term has been expanded to include solvates (forms containing a solvent), amorphous forms (non-crystalline forms), and desolvated solvates (forms from which the solvent has been removed).
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The various IMFs between identical molecules of a substance are examples of cohesive forces. The molecules within a liquid are surrounded by other molecules and are attracted equally in all directions by the cohesive forces within the liquid. However, the molecules on the surface of a liquid are attracted only by about one-half as many molecules. Because of the unbalanced molecular attractions on the surface molecules, liquids contract to form a shape that minimizes the number...
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Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
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Surface tension is a fundamental property of fluids, occurring at the boundary between a liquid and a gas or between two immiscible liquids. This phenomenon arises from the cohesive forces between molecules at the fluid's surface, creating an effect similar to a stretched elastic membrane. Inside each fluid, molecules are equally attracted in all directions by neighboring molecules, but surface molecules experience a net inward force, resulting in surface tension.
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Crystal Polymorphism Induced by Surface Tension.

Cédric Schoonen1, James F Lutsko1

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|December 23, 2022
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Summary
This summary is machine-generated.

Classical density functional theory (cDFT) accurately predicts surface tensions for hard spheres and Lennard-Jones (LJ) crystals. cDFT reveals a size-dependent stability crossover from bcc to fcc LJ clusters, clarifying theoretical and simulation discrepancies.

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Area of Science:

  • Condensed Matter Physics
  • Statistical Mechanics
  • Computational Chemistry

Background:

  • Understanding fluid-solid interfaces and crystal polymorphism is crucial in materials science.
  • Classical Density Functional Theory (cDFT) offers a theoretical framework for studying phase transitions.
  • Discrepancies exist between theoretical predictions and simulation results for crystal stability.

Purpose of the Study:

  • To calculate fluid-solid surface tensions for face-centered cubic (fcc) and body-centered cubic (bcc) crystals using cDFT.
  • To investigate the relative stability of bcc and fcc Lennard-Jones (LJ) clusters.
  • To extend previous findings on the stability of the bcc phase in contact with a vapor.

Main Methods:

  • Utilized classical density functional theory (cDFT) to compute surface tensions.
  • Employed hard sphere and Lennard-Jones (LJ) particle models.
  • Parametrized a capillary model using bulk and interfacial energies from LJ calculations.

Main Results:

  • cDFT "explicitly stable" functionals perform comparably to state-of-the-art methods for hard spheres.
  • Calculated surface tensions align well with simulation results for both hard spheres and LJ particles.
  • Observed a crossover in stability from bcc to fcc phases as LJ cluster size increases.
  • Confirmed the instability of the bcc phase when in contact with a vapor.

Conclusions:

  • cDFT is a valuable tool for understanding crystallization processes and polymorphism.
  • The study resolves long-standing tensions between theoretical expectations and simulation data regarding LJ cluster stability.
  • Findings provide insights into the phase behavior of simple model systems.