在有机分子模型中,热力学稳定性是共结晶的不良指标
Yulia Pimonova1, John E Carpenter1, Michael Gruenwald1
1Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, United States.
Journal of the American Chemical Society
|January 19, 2024
概括
固态特性发生改变的共结晶通常是不可预测的. 这项研究表明,即使稳定的共结晶在热力学上是可能的,动力学因素也经常阻止共结晶,这突显了动态过程的重要性.
科学领域:
- 固态化学
- 材料科学
- 计算化学
背景情况:
- 合结晶是调整固态分子特性的关键.
- 大多数分子对无法共结晶,形成单元晶体或无形固体.
- 预测共结晶依赖于计算的晶体结构预测,但动力因素往往被忽视.
研究的目的:
- 调查热力学稳定的共晶能否保证共晶.
- 评估热力学标准在预测共结晶结果中的可靠性.
- 探索动力因素对共结晶成功的影响.
主要方法:
- 在2D中模拟超过2600对不同的奇拉模型分子的结晶.
- 为所有模拟系统计算精确的晶体能量景观.
- 分析了热力学稳定性和观察到的共结晶之间的关系.
主要成果:
- 仅仅热力学稳定性是共同结晶的不可靠预测因素.
- 大多数具有热力学有利的共同晶体的系统并没有共同结晶.
- 当使用形成较少排序的单元晶体的联合形成剂时,合结晶率增加了三倍.
结论:
- 动力因素对共结晶的结果起着决定性的作用.
- 在实践中,热力学稳定的共同晶体的形成并不能确保它们的形成.
- 了解动力障碍对于预测和成功实现共结晶至关重要.
相关概念视频
Stability of Substituted Cyclohexanes
12.6K
This lesson discusses the stability of substituted cyclohexanes with a focus on energies of various conformers and the effect of 1,3-diaxial interactions.
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
12.6K
Entropy and Solvation
7.1K
The process of surrounding a solute with solvent is called solvation. It involves evenly distributing the solute within the solvent. The rule of thumb for determining a solvent for a given compound is that like dissolves like. A good solvent has molecular characteristics similar to those of the compound to be dissolved. For example, polar solutions dissolve polar solutes, and apolar solvents dissolve apolar solutes. A polar solvent is a solvent that has a high dielectric constant (ϵ...
7.1K
Polymer Classification: Crystallinity
2.9K
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.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...
2.9K
Intermolecular Forces and Physical Properties
20.8K
20.8K
Combustion Energy: A Measure of Stability in Alkanes and Cycloalkanes
6.4K
The low reactivity in alkanes can be attributed to the non-polar nature of C–C and C–H σ bonds. Alkanes, therefore, were initially termed as “paraffins,” derived from the Latin words: parum, meaning “too little,” and affinis, meaning “affinity.”
Alkanes undergo combustion in the presence of excess oxygen and high-temperature conditions to give carbon dioxide and water. A combustion reaction is the energy source in natural gas, liquified...
Alkanes undergo combustion in the presence of excess oxygen and high-temperature conditions to give carbon dioxide and water. A combustion reaction is the energy source in natural gas, liquified...
6.4K
Types of Enols and Enolates
2.6K
Aldehydes and ketones form enols, although only about 1% of the enol is present at the equilibrium for simple monocarbonyl compounds. The enol form is undetectable for acetaldehyde, present as only 1.5 × 10−4 % of acetone, and present as only 1.2% of cyclohexanone. Two kinds of regioisomeric enols are possible for unsymmetrical ketones, and their net composition is 1% at equilibrium. This instability is due to the lower bond energy of C=C than the C=O group. The additional...
2.6K


