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adf:nmr-openshell [2016/08/31 17:22] – [结果查看] liu.jun | adf:nmr-openshell [2018/04/08 21:11] – [如何使用相对论方法计算开壳层体系NMR化学位移(顺磁、逆磁)] liu.jun | ||
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- | ======如何计算开壳层体系的NMR化学位移====== | + | ======如何使用相对论方法计算开壳层体系NMR化学位移(顺磁、逆磁)====== |
+ | =====必读===== | ||
+ | 推荐参数,参考[[adf: | ||
- | 对开壳层体系的NMR化学位移计算,有两种可选的方式: | + | 对开壳层体系的NMR化学位移计算,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),ADF新版本修正了度规不变性。 |
- | - 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 | + | 注意:ADF计算得到的数据,需要先用计算得到的氢谱或碳谱位移与实验对照,得到平移量,用该平移量来校正所有其他元素、原子的化学位移数据。 |
- | * 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: | 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===== |
- | + | ||
- | ====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。 | + | 上图中,Shieding for all如果勾选的话,比如勾选H atoms的话,所有H原子的NMR |
- | 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。 | + | 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: |
- | 使用Spin-Orbit需要设置symmetry为Nosym: | + | {{ : |
- | {{ : | + | ADFjobs窗口选中任务,之后点击Job > |
- | 保存任务并运行,提交任务的方式,参考:[[adf:parallel]]。 | + | ===== 结果查看===== |
+ | 在logfile中列出了每个原子总的化学位移: | ||
+ | {{ :adf:nmr-openshell01.png? | ||
- | ==== 结果查看==== | + | 点击SCM LOGO > Spectra,显示NMR的强度: |
- | 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 |
- | < | + | |
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- | </ | + | |
- | + | ||
- | + | ||
- | + | ||
- | 点击SCM LOGO > Output,弹出out窗口之后,选择Other properties | + | |
<code bash> | <code bash> | ||
+ | ################################################################################ | ||
+ | ******************************************************************************** | ||
**** N U C L E U S : H(8) | **** N U C L E U S : H(8) | ||
行 75: | 行 41: | ||
| | ||
+ | NBO: we are working with a Cartesian (6d/10f) basis | ||
================================================================================ | ================================================================================ | ||
- | === UNSCALED: | + | === PARAMAGNETIC NMR SHIELDING TENSORS (ppm) |
=== | === | ||
----------------------------------- | ----------------------------------- | ||
- | | + | |
- | | + | |
- | | + | |
----------------------------------- | ----------------------------------- | ||
- | isotropic = 0.000 isotropic = 265.196 | + | isotropic = 0.000 isotropic = 6.073 |
=== | === | ||
----------------------------------- | ----------------------------------- | ||
- | 0.486 | + | -23.435 |
- | 1.820 -0.612 -4.628 0.011 0.008 -4.314 | + | 0.000 0.397 -1.827 0.000 0.000 0.000 |
- | -7.868 -4.628 2.764 -7.607 -4.314 | + | -0.000 -1.827 -0.540 -0.000 0.000 |
----------------------------------- | ----------------------------------- | ||
- | isotropic = 0.879 | + | isotropic = -7.859 |
*********************************** | *********************************** | ||
行 102: | 行 69: | ||
==== total paramagnetic tensor | ==== total paramagnetic tensor | ||
----------------------------------- | ----------------------------------- | ||
- | -47.954 | + | |
- | -153.781 | + | -0.000 |
- | 119.347 131.501 717.337 | + | -0.000 10.817 -4.718 |
----------------------------------- | ----------------------------------- | ||
- | isotropic = 269.362 | + | isotropic = -6.956 |
*********************************** | *********************************** | ||
行 114: | 行 81: | ||
==== Principal components: | ==== Principal components: | ||
- | | + | -23.042 0.506 1.668 |
==== Principal Axis System: | ==== Principal Axis System: | ||
- | -0.842 | + | -0.000 |
- | -0.505 -0.844 0.181 | + | -0.861 0.000 0.508 |
- | 0.189 0.096 0.977 | + | 0.508 0.000 0.861 |
----------------------------------- | ----------------------------------- | ||
行 126: | 行 93: | ||
- | === UNSCALED: | + | === DIAMAGNETIC NMR SHIELDING TENSORS (ppm) |
=== | === | ||
----------------------------------- | ----------------------------------- | ||
- | | + | |
- | | + | |
- | | + | |
----------------------------------- | ----------------------------------- | ||
- | isotropic = 0.000 isotropic = 30.687 | + | isotropic = 0.000 isotropic = 30.708 |
*********************************** | *********************************** | ||
行 141: | 行 108: | ||
==== total diamagnetic tensor | ==== total diamagnetic tensor | ||
----------------------------------- | ----------------------------------- | ||
- | | + | |
- | 8.895 30.030 0.016 | + | 0.000 41.131 -9.103 |
- | | + | -0.000 -9.103 30.421 |
----------------------------------- | ----------------------------------- | ||
- | isotropic = 30.687 | + | isotropic = 30.708 |
*********************************** | *********************************** | ||
行 153: | 行 120: | ||
==== Principal components: | ==== Principal components: | ||
- | 20.540 25.180 46.342 | + | 20.573 25.214 46.337 |
==== Principal Axis System: | ==== Principal Axis System: | ||
- | -0.001 0.479 -0.878 | + | 1.000 0.000 -0.000 |
- | -0.001 -0.878 -0.479 | + | -0.000 0.496 -0.868 |
- | 1.000 -0.000 -0.001 | + | 0.000 |
----------------------------------- | ----------------------------------- | ||
行 165: | 行 132: | ||
- | === UNSCALED: SPIN-ORBIT | + | === |
- | === | ||
- | ----------------------------------- | ||
- | | ||
- | | ||
- | | ||
- | ----------------------------------- | ||
- | isotropic = 0.000 isotropic = | ||
- | |||
- | === | ||
- | ----------------------------------- | ||
- | | ||
- | | ||
- | -0.002 | ||
- | ----------------------------------- | ||
- | isotropic = 0.000 isotropic = | ||
- | |||
*********************************** | *********************************** | ||
CARTESIAN AXIS REPRESENTATION | CARTESIAN AXIS REPRESENTATION | ||
- | ==== total spin-orbit | + | ==== total shielding |
----------------------------------- | ----------------------------------- | ||
- | -12.791 -1.759 -0.003 | + | 21.079 -0.000 -0.000 |
- | -1.759 -11.795 | + | -0.000 24.475 |
- | -0.003 | + | -0.000 |
----------------------------------- | ----------------------------------- | ||
- | isotropic = -8.114 | + | isotropic = 23.752 |
*********************************** | *********************************** | ||
行 200: | 行 151: | ||
==== Principal components: | ==== Principal components: | ||
- | -14.122 -10.465 0.244 | + | 21.079 23.268 26.909 |
==== Principal Axis System: | ==== Principal Axis System: | ||
- | 0.798 0.603 -0.001 | + | 1.000 0.000 -0.000 |
- | 0.603 -0.798 0.002 | + | 0.000 -0.818 0.576 |
- | -0.001 0.002 | + | |
----------------------------------- | ----------------------------------- | ||
- | |||
- | ================================================================================ | ||
- | |||
- | |||
- | === 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===== |