Accidental Degeneracy in Crystalline Aspirin: New Insights from High-Level ab Initio Calculations

被引：57

作者：

Wen, Shuhao ^{[1
]}

Beran, Gregory J. O. ^{[1
]}

机构：

[1] Univ Calif Riverside, Dept Chem, Riverside, CA 92521 USA

来源：

CRYSTAL GROWTH & DESIGN | 2012年 / 12卷 / 05期

基金：

美国国家科学基金会;

关键词：

DENSITY-FUNCTIONAL THEORY; LATTICE ENERGIES; POLYMORPHISM; FREQUENCIES; PREDICTION; MOLECULES;

D O I：

10.1021/cg300358n

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We perform the first high-level ab initio calculations (MP2) on crystalline aspirin using a newly developed fragment-based QM/MM method. Contrary to earlier density functional theory predictions, the two polymorphs are virtually degenerate, which is consistent with experimentally observed intergrowth structures. This near-degeneracy arises "accidentally" from a competition between intramolecular relaxation (form I) and intermolecular hydrogen bonding (form II).

引用

页码：2169 / 2172

页数：4

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