苯膦酸C6H5HPO(OH)的第一性原理核磁共振计算：归属、通过局部场实验确定张量取向以及分子运动的影响

First principles NMR calculations of phenylphosphinic acid C6H5HPO(OH): assignments, orientation of tensors by local field experiments and effect of molecular motion.

作者信息

Gervais C, Coelho C, Azaïs T, Maquet J, Laurent G, Pourpoint F, Bonhomme C, Florian P, Alonso B, Guerrero G, Mutin P H, Mauri F

机构信息

Université Pierre et Marie Curie-Paris 6, UMR 7574 Laboratoire de Chimie de la Matière Condensée de Paris, Paris F-75005, France.

出版信息

J Magn Reson. 2007 Jul;187(1):131-40. doi: 10.1016/j.jmr.2007.03.018. Epub 2007 Apr 7.

DOI:10.1016/j.jmr.2007.03.018

PMID:17481933

Abstract

The complete set of NMR parameters for (17)O enriched phenylphosphinic acid C(6)H(5)HP( *)O(*OH) is calculated from first principles by using the Gauge Including Projected Augmented Wave (GIPAW) approach [C.J. Pickard, F. Mauri, All-electron magnetic response with pseudopotentials: NMR chemical shifts, Phys. Rev. B 63 (2001) 245101/1-245101/13]. The analysis goes beyond the successful assignment of the spectra for all nuclei ((1)H, (13)C, (17)O, (31)P), as: (i) the (1)H CSA (chemical shift anisotropy) tensors (magnitude and orientation) have been interpreted in terms of H bonding and internuclear distances. (ii) CSA/dipolar local field correlation experiments have allowed the orientation of the direct P-H bond direction in the (31)P CSA tensor to be determined. Experimental and calculated data were compared. (iii) The overestimation of the calculated (31)P CSA has been explained by local molecular reorientation and confirmed by low temperature static (1)H-->(31)P CP experiments.

摘要

采用含规范投影增强波（GIPAW）方法[C.J.皮卡德、F.毛里，《赝势全电子磁响应：核磁共振化学位移》，《物理评论B》63（2001年）245101/1 - 245101/13]从第一性原理计算了富含¹⁷O的苯次膦酸C₆H₅HP（*）O（*OH）的完整核磁共振参数集。分析超越了对所有原子核（¹H、¹³C、¹⁷O、³¹P）光谱的成功归属，具体如下：（i）¹H化学位移各向异性（CSA）张量（大小和方向）已根据氢键和核间距离进行了解释。（ii）CSA/偶极局部场相关实验已确定³¹P CSA张量中直接P - H键方向的取向。对实验数据和计算数据进行了比较。（iii）计算得到的³¹P CSA的高估已通过局部分子重排得到解释，并通过低温静态¹H→³¹P交叉极化实验得到证实。