Monosaccharide-Water Complexes: Vibrational Spectroscopy and Anharmonic Potentials
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- 作者：Lin Jin ; John P. Simons ; R. Benny Gerber
- 刊名：The Journal of Physical Chemistry A
- 出版年：2012
- 出版时间：November 26, 2012
- 年：2012
- 卷：116
- 期：46
- 页码：11088-11094
- 全文大小：419K
- 年卷期：v.116,no.46(November 26, 2012)
- ISSN：1520-5215
文摘
Ab initio vibrational self-consistent field (VSCF) calculations are used to predict the vibrational spectra of an extended series of monosaccharide路D2O complexes, including glucose, galactose, mannose, xylose, and fucose in their 伪 and 尾 anomeric forms, and compared with recently published experimental data for their (phenyl-tagged) complexes. Anharmonic VSCF-PT2 frequencies are calculated directly, using ab initio hybrid HF/MP2 potentials, to assess their accuracy in reproducing the vibrational anharmonicities and provide a more rigorous basis for vibrational and structural assignments. The average discrepancies between the calculated and experimental frequencies are 1.0鈥?.5%, and the first-principles spectroscopic calculations, free of any empirical scaling, yield results of high accuracy. They encourage confidence in their future application to the assignment of other carbohydrate systems, both free and complexed, and an improved understanding of their intra- and intermolecular carbohydrate interactions.