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Periodic density functional theory study of the high‐pressure behavior of crystalline 7,2′‐anhydro‐ β ‐ d ‐arabinosylorotidine
Author(s) -
Guo Ying,
Liu Qingqing,
Zhao Xingqiang
Publication year - 2017
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3590
Subject(s) - chemistry , density functional theory , crystallography , ring (chemistry) , atom (system on chip) , covalent bond , crystal structure , band gap , anisotropy , molecule , absorption spectroscopy , electronic structure , computational chemistry , condensed matter physics , optics , organic chemistry , physics , computer science , embedded system
In this work, a detailed study of the structural, electronic, and absorption properties of crystalline 7,2′‐anhydro‐ β ‐ d ‐arabinosylorotidine (Cyclo ara‐O) in the pressure range of 0–350 GPa is performed by density functional theory calculations. The detail analysis of the crystal with increasing pressure shows that complex transformations occur in Cyclo ara‐O under compression. In addition, the b ‐direction is much stiffer than the a ‐ and c ‐axis at 0–330 GPa, suggesting that the Cyclo ara‐O crystal is anisotropic in the certain pressure region. In the pressure range of 110–290 GPa, repeated formations and disconnections of covalent bonds in O7–O6* and C3–C6* occur several times, resulting in a new six‐atom ring that forms at 220, 270, and 290 GPa, while a five‐atom ring and seven‐atom ring form between two adjacent molecules at 300 and 340 GPa, respectively. Then, the analysis of the band gap and DOS (PDOS) of Cyclo ara‐O indicates that its electronic character has changed at 300 GPa into an excellent insulator, but the electron transition is much easier at 350 GPa. Moreover, the relatively high optical activity with the pressure increases of Cyclo ara‐O is seen from the absorption spectra, and two obvious structural transformations are also observed at 180 and 230 GPa, respectively. Copyright © 2016 John Wiley & Sons, Ltd.