这是本文档旧的修订版!
对开壳层体系的NMR化学位移计算,有两种可选的方式:
以下使用ADF2016进行演示:
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:parallel。
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:
<Aug31-2016> <17:04:27> NMR development version RunTime: Aug31-2016 17:04:27 Nodes: 1 Procs: 2 <Aug31-2016> <17:04:27> >>>> RDEIGZ <Aug31-2016> <17:04:28> >>>> ZSIG <Aug31-2016> <17:04:28> >>>> ZU1 <Aug31-2016> <17:05:27> >>>> ZSIGP <Aug31-2016> <17:05:39> >>>> ZSIGD <Aug31-2016> <17:05:59> >>>> ZSIGS <Aug31-2016> <17:07:25> NMR Shielding ADF-GUI atom H(8): 291.94 ppm <Aug31-2016> <17:07:25> >>>> ZSIGP <Aug31-2016> <17:07:37> >>>> ZSIGD <Aug31-2016> <17:07:56> >>>> ZSIGS <Aug31-2016> <17:09:33> NMR Shielding ADF-GUI atom H(9): 452.54 ppm <Aug31-2016> <17:09:33> >>>> ZSIGP <Aug31-2016> <17:09:46> >>>> ZSIGD <Aug31-2016> <17:10:05> >>>> ZSIGS <Aug31-2016> <17:11:34> NMR Shielding ADF-GUI atom H(10): 556.24 ppm <Aug31-2016> <17:11:34> >>>> ZSIGP <Aug31-2016> <17:11:47> >>>> ZSIGD <Aug31-2016> <17:12:06> >>>> ZSIGS <Aug31-2016> <17:13:38> NMR Shielding ADF-GUI atom H(11): 374.81 ppm <Aug31-2016> <17:13:38> >>>> ZSIGP <Aug31-2016> <17:13:50> >>>> ZSIGD <Aug31-2016> <17:14:11> >>>> ZSIGS <Aug31-2016> <17:15:39> NMR Shielding ADF-GUI atom H(7): 80.25 ppm <Aug31-2016> <17:15:39> NORMAL TERMINATION <Aug31-2016> <17:15:39> END
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):
**** N U C L E U S : H(8) ADF-GUI atom: H(8) Internal NMR numbering of atoms: H(8) ================================================================================ === UNSCALED: PARAMAGNETIC NMR SHIELDING TENSORS (ppm) === paramagnetic b^(1) tensor === paramagnetic u^(1) tensor ----------------------------------- ----------------------------------- 0.000 0.000 0.000 -48.453 -155.612 134.822 0.000 0.000 0.000 -155.612 139.307 140.443 0.000 0.000 0.000 134.822 140.443 704.734 ----------------------------------- ----------------------------------- isotropic = 0.000 isotropic = 265.196 === paramagnetic s^(1) tensor === paramagnetic gauge tensor ----------------------------------- ----------------------------------- 0.486 1.820 -7.868 0.013 0.011 -7.607 1.820 -0.612 -4.628 0.011 0.008 -4.314 -7.868 -4.628 2.764 -7.607 -4.314 9.839 ----------------------------------- ----------------------------------- isotropic = 0.879 isotropic = 3.287 *********************************** CARTESIAN AXIS REPRESENTATION ==== total paramagnetic tensor ----------------------------------- -47.954 -153.781 119.347 -153.781 138.702 131.501 119.347 131.501 717.337 ----------------------------------- isotropic = 269.362 *********************************** ----------------------------------- PRINCIPAL AXIS REPRESENTATION ==== Principal components: -166.916 219.820 755.181 ==== Principal Axis System: -0.842 0.528 0.111 -0.505 -0.844 0.181 0.189 0.096 0.977 ----------------------------------- ================================================================================ === UNSCALED: DIAMAGNETIC NMR SHIELDING TENSORS (ppm) === diamagnetic core tensor === diamagnetic valence tensor ----------------------------------- ----------------------------------- 0.000 0.000 0.000 41.492 8.895 0.026 0.000 0.000 0.000 8.895 30.030 0.016 0.000 0.000 0.000 0.026 0.016 20.540 ----------------------------------- ----------------------------------- isotropic = 0.000 isotropic = 30.687 *********************************** CARTESIAN AXIS REPRESENTATION ==== total diamagnetic tensor ----------------------------------- 41.492 8.895 0.026 8.895 30.030 0.016 0.026 0.016 20.540 ----------------------------------- isotropic = 30.687 *********************************** ----------------------------------- PRINCIPAL AXIS REPRESENTATION ==== Principal components: 20.540 25.180 46.342 ==== Principal Axis System: -0.001 0.479 -0.878 -0.001 -0.878 -0.479 1.000 -0.000 -0.001 ----------------------------------- ================================================================================ === UNSCALED: SPIN-ORBIT NMR SHIELDING TENSORS (ppm) === spin-orbit b^(1) tensor === spin-orbit u^(1) tensor ----------------------------------- ----------------------------------- 0.000 0.000 0.000 -12.782 -1.764 0.000 0.000 0.000 0.000 -1.764 -11.778 0.020 0.000 0.000 0.000 0.000 0.020 0.228 ----------------------------------- ----------------------------------- isotropic = 0.000 isotropic = -8.111 === spin-orbit s^(1) tensor === spin-orbit gauge tensor ----------------------------------- ----------------------------------- 0.010 0.015 -0.002 -0.019 -0.010 -0.002 0.015 -0.012 0.005 -0.010 -0.006 -0.002 -0.002 0.005 0.003 -0.002 -0.002 0.014 ----------------------------------- ----------------------------------- isotropic = 0.000 isotropic = -0.004 *********************************** CARTESIAN AXIS REPRESENTATION ==== total spin-orbit tensor ----------------------------------- -12.791 -1.759 -0.003 -1.759 -11.795 0.022 -0.003 0.022 0.244 ----------------------------------- isotropic = -8.114 *********************************** ----------------------------------- PRINCIPAL AXIS REPRESENTATION ==== Principal components: -14.122 -10.465 0.244 ==== Principal Axis System: 0.798 0.603 -0.001 0.603 -0.798 0.002 -0.001 0.002 1.000 ----------------------------------- ================================================================================ === UNSCALED: TOTAL NMR SHIELDING TENSOR (ppm) *********************************** CARTESIAN AXIS REPRESENTATION ==== total shielding tensor ----------------------------------- -19.253 -146.646 119.370 -146.646 156.938 131.539 119.370 131.539 738.121 ----------------------------------- isotropic = 291.935 *********************************** ----------------------------------- PRINCIPAL AXIS REPRESENTATION ==== Principal components: -135.121 234.638 776.288 ==== Principal Axis System: -0.840 0.531 0.113 -0.508 -0.842 0.181 0.191 0.094 0.977 -----------------------------------
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。