Are Crystal Polymorphs Predictable? The Case of Sexithiophene
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- 作者：Raffaele Guido Della Valle ; Elisabetta Venuti ; Aldo Brillante Alberto Girlando
- 刊名：Journal of Physical Chemistry A
- 出版年：2008
- 出版时间：July 24, 2008
- 年：2008
- 卷：112
- 期：29
- 页码：6715-6722
- 全文大小：204K
- 年卷期：v.112,no.29(July 24, 2008)
- ISSN：1520-5215
文摘
Using sexithiophene as a benchmark compound, we present a very effective strategy for searching the potential energy minima of a crystalline material, described in terms of rigid molecules with Coulombic and atom−atom interactions. The strategy involves uniform sampling of the many-body energy hypersurface, mechanical identification of all constraints deriving from the crystallographic symmetry, and a “sight−resight” method, originally introduced in wildlife ecology, for assessing the completeness of the search. Thousands of distinct potential energy minima, with a surprising variety of structural arrangements, are identified for sexithiophene. Despite the large number of competing minima, the system presents a small number of deep minima, with very different structures and not particularly congested in energy or density. The two deepest minima correspond to the structures of the two known experimental polymorphs, which are satisfactorily described.