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对质子屏蔽的零点振动效应:从一开始计算的功能组贡献
K Ruud1, P O Astrand, P R Taylor
1San Diego Supercomputer Center and Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive MC0505, La Jolla, California 92093-0505, USA.
零点振动运动显著影响有机分子中的核磁屏蔽常数. 这些振动校正对于精确的化学转移计算至关重要,并且可以转移到原子.
科学领域:
- 计算化学计算化学
- 量子化学 是一个量子化学.
- 分子光谱学 分子光谱学
背景情况:
- 核磁屏蔽常数对于解释NMR光谱至关重要.
- 振动运动可以影响电子属性,包括磁屏蔽.
- 之前的研究经常忽视或近似的振动效应.
研究的目的:
- 研究零点振动运动对有机分子中核磁屏蔽常数的影响.
- 量化振动纠正,包括无和和贡献.
- 评估这些校正在不同分子中的可转移性.
主要方法:
- Ab initio对潜在能量表面和物质表面的计算.
- 包括来自潜在能量表面的无调贡献.
- 包括来自属性表面曲率的波贡献.
- 对大量有机分子进行系统研究.
主要成果:
- 对于屏蔽常数的振动纠正可能是相当大的 (+0.50到-0.70 ppm).
- 忽视这些效应可能会导致超过1ppm的化学转移误差.
- 屏蔽的振动校正表明分子之间具有显著的可转移性.
- 对于碳,或氧屏蔽常数没有观察到类似的可转移性.
结论:
- 零点振动运动效应至关重要,不能忽视准确的NMR化学转移预测.
- 对于屏蔽的可转移振动校正可以进行表格化和利用.
- 需要进一步的研究来了解对其他核的振动效应.
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