这里会显示出您选择的修订版和当前版本之间的差别。
两侧同时换到之前的修订记录前一修订版后一修订版 | 前一修订版 | ||
adf:nmr-openshell [2016/08/31 17:48] – [如何计算开壳层体系的NMR化学位移] liu.jun | adf:nmr-openshell [2020/11/20 10:30] (当前版本) – 移除 liu.jun | ||
---|---|---|---|
行 1: | 行 1: | ||
- | ======如何计算开壳层体系的NMR化学位移(待完善)====== | ||
- | |||
- | 对开壳层体系的NMR化学位移计算,有两种可选的方式: | ||
- | - 使用Spin-Orbit方法 | ||
- | * 优点:简单方便,因为考虑Spin-Orbit的话,开壳层和闭壳层的概念就消失了,统一的方式进行处理 | ||
- | * 缺点:ADF2013及其之前的版本,得到的结果对度规不变性,略有损害(非常微小) | ||
- | - 使用Scalar方法 | ||
- | * 优点:严格的度规不变性 | ||
- | * 缺点:需要加一个关键词 | ||
- | |||
- | 以下使用ADF2016进行演示: | ||
- | |||
- | =====Spin-Orbit计算NMR化学位移(适用于ADF2014及其以上版本)===== | ||
- | |||
- | ====参数设置==== | ||
- | 略过结构优化的过程。以参数设置如下: | ||
- | |||
- | {{ : | ||
- | |||
- | 注意,因为使用了Spin-Orbit,所以Spin polarization和Unrestricted都不需要设置了,设置了也不会读取,因为这两个概念在考虑Spin-Orbit coupling之后,就不成立了。 | ||
- | |||
- | {{ : | ||
- | |||
- | 上图中,可以按元素选择(可以选择H atoms表示计算所有的H原子的NMR化学位移,C、P类似),也可以在左边窗口按住shift键,分别选中自己关心的原子,然后点击NMR shielding for atoms后面的➕,来设定自己希望计算的原子。 | ||
- | |||
- | 计算结果是否显示各向同性屏蔽常数、是否显示所有的(含顺磁和逆磁)屏蔽张量,如果要显示,就打勾。 | ||
- | |||
- | 使用Spin-Orbit需要设置symmetry为Nosym: | ||
- | |||
- | {{ : | ||
- | |||
- | 保存任务并运行,提交任务的方式,参考:[[adf: | ||
- | |||
- | ==== 结果查看==== | ||
- | |||
- | 点击SCM LOGO > Logfile,弹出logfile窗口,得到所选择的5和H原子的化学位移: | ||
- | |||
- | <code bash> | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | < | ||
- | </ | ||
- | |||
- | |||
- | |||
- | 点击SCM LOGO > Output,弹出out窗口之后,选择Other properties > NMR Shielding (NMR program),可以看到详细的数据(包括顺磁、逆磁、自旋轨道耦合三者对屏蔽张量、各向同性化学位移对贡献): | ||
- | |||
- | <code bash> | ||
- | **** N U C L E U S : H(8) | ||
- | |||
- | | ||
- | | ||
- | |||
- | |||
- | ================================================================================ | ||
- | |||
- | |||
- | === UNSCALED: PARAMAGNETIC NMR SHIELDING TENSORS (ppm) | ||
- | |||
- | === | ||
- | ----------------------------------- | ||
- | | ||
- | | ||
- | | ||
- | ----------------------------------- | ||
- | isotropic = 0.000 isotropic = 265.196 | ||
- | |||
- | === | ||
- | ----------------------------------- | ||
- | | ||
- | | ||
- | -7.868 | ||
- | ----------------------------------- | ||
- | isotropic = 0.879 isotropic = 3.287 | ||
- | |||
- | *********************************** | ||
- | CARTESIAN AXIS REPRESENTATION | ||
- | |||
- | ==== total paramagnetic tensor | ||
- | ----------------------------------- | ||
- | | ||
- | -153.781 | ||
- | | ||
- | ----------------------------------- | ||
- | isotropic = 269.362 | ||
- | |||
- | *********************************** | ||
- | ----------------------------------- | ||
- | PRINCIPAL AXIS REPRESENTATION | ||
- | |||
- | ==== Principal components: | ||
- | |||
- | -166.916 | ||
- | |||
- | ==== Principal Axis System: | ||
- | |||
- | -0.842 | ||
- | -0.505 | ||
- | | ||
- | ----------------------------------- | ||
- | |||
- | ================================================================================ | ||
- | |||
- | |||
- | === UNSCALED: DIAMAGNETIC NMR SHIELDING TENSORS (ppm) | ||
- | |||
- | === | ||
- | ----------------------------------- | ||
- | | ||
- | | ||
- | | ||
- | ----------------------------------- | ||
- | isotropic = 0.000 isotropic = | ||
- | |||
- | *********************************** | ||
- | CARTESIAN AXIS REPRESENTATION | ||
- | |||
- | ==== total diamagnetic tensor | ||
- | ----------------------------------- | ||
- | 41.492 | ||
- | | ||
- | | ||
- | ----------------------------------- | ||
- | isotropic = | ||
- | |||
- | *********************************** | ||
- | ----------------------------------- | ||
- | PRINCIPAL AXIS REPRESENTATION | ||
- | |||
- | ==== Principal components: | ||
- | |||
- | 20.540 | ||
- | |||
- | ==== Principal Axis System: | ||
- | |||
- | -0.001 | ||
- | -0.001 | ||
- | | ||
- | ----------------------------------- | ||
- | |||
- | ================================================================================ | ||
- | |||
- | |||
- | === UNSCALED: SPIN-ORBIT NMR SHIELDING TENSORS (ppm) | ||
- | |||
- | === | ||
- | ----------------------------------- | ||
- | | ||
- | | ||
- | | ||
- | ----------------------------------- | ||
- | isotropic = 0.000 isotropic = | ||
- | |||
- | === | ||
- | ----------------------------------- | ||
- | | ||
- | | ||
- | -0.002 | ||
- | ----------------------------------- | ||
- | isotropic = 0.000 isotropic = | ||
- | |||
- | *********************************** | ||
- | CARTESIAN AXIS REPRESENTATION | ||
- | |||
- | ==== total spin-orbit tensor | ||
- | ----------------------------------- | ||
- | | ||
- | -1.759 | ||
- | -0.003 | ||
- | ----------------------------------- | ||
- | isotropic = | ||
- | |||
- | *********************************** | ||
- | ----------------------------------- | ||
- | PRINCIPAL AXIS REPRESENTATION | ||
- | |||
- | ==== Principal components: | ||
- | |||
- | | ||
- | |||
- | ==== Principal Axis System: | ||
- | |||
- | | ||
- | | ||
- | -0.001 | ||
- | ----------------------------------- | ||
- | |||
- | ================================================================================ | ||
- | |||
- | |||
- | === UNSCALED: TOTAL NMR SHIELDING TENSOR (ppm) | ||
- | |||
- | *********************************** | ||
- | CARTESIAN AXIS REPRESENTATION | ||
- | |||
- | ==== total shielding tensor | ||
- | ----------------------------------- | ||
- | | ||
- | -146.646 | ||
- | | ||
- | ----------------------------------- | ||
- | isotropic = 291.935 | ||
- | |||
- | *********************************** | ||
- | ----------------------------------- | ||
- | PRINCIPAL AXIS REPRESENTATION | ||
- | |||
- | ==== Principal components: | ||
- | |||
- | -135.121 | ||
- | |||
- | ==== Principal Axis System: | ||
- | |||
- | -0.840 | ||
- | -0.508 | ||
- | | ||
- | ----------------------------------- | ||
- | </ | ||
- | |||
- | 其中TOTAL NMR SHIELDING TENSOR等于PARAMAGNETIC NMR SHIELDING TENSORS、DIAMAGNETIC NMR SHIELDING TENSORS、SPIN-ORBIT NMR SHIELDING TENSORS之和;isotropic也类似,isotropic = 291.935实际上就是顺磁、逆磁、旋轨耦合三者对isotropic加和。 | ||
- | |||
- | =====Scalar方法计算开壳层NMR化学位移===== | ||
- | |||
- | ====参数设置==== | ||
- | 与Spin-Orbit非常类似,差别:Spin Polarization、Unrestricted需要正确设置,Relativity设置为Scalar,Symmetry使用默认Auto即可: | ||
- | |||
- | {{ : | ||
- | |||
- | 保存任务,之后,修改*.run文件。即,增加一行ALLINONE,在nmr输入文件中,如下图所示: | ||
- | |||
- | {{ : | ||
- | |||
- | ADFjobs窗口选中任务,之后点击Job > | ||
- | |||
- | ==== 结果查看==== | ||
- | |||