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:uv_rel [2017/10/26 20:41] – [参数设置] liu.jun | adf:uv_rel [2020/11/12 15:10] (当前版本) – 移除 liu.jun |
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======考虑相对论效应的紫外可见吸收谱的计算(标量相对论:Scalar)====== | |
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我们以简单的水分子来进行说明。[[https://www.jianguoyun.com/p/DXrp8tsQmZ2ZBhjQqC0|计算文件下载(点击)]] | |
=====参数设置===== | |
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{{ :adf:scalaruv01.png?600 }} | |
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{{ :adf:scalaruv02.png?600 }} | |
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=====结果查看===== | |
====没有考虑旋归耦合的结果==== | |
ADF LOGO > Output > Response properties > All Singlet-Singlet Excitation Energies:列出的是,考虑相对论对动能修正的S0→Sn激发能。 | |
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ADF LOGO > Output > Response properties > All Singlet-Triplet Excitation Energies:列出的是,考虑相对论对动能修正的S0→Tn激发能。 | |
====考虑旋归耦合的结果==== | |
ADF LOGO > Output > Response properties > All Spin-Orbital Coupling Excitation Energies:列出的是,将自旋轨道耦合作为微扰,对上面两项进行修正之后的激发能: | |
<code bash> | |
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All Spin-Orbital Coupling Excitation Energies | |
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no. E/a.u. E/eV f tau/s Symmetry | |
------------------------------------------------------------------ | |
1: 0.24253 6.59960 0.1347E-05 0.3927E-03 A1 | |
2: 0.24253 6.59959 0.000 A2 | |
3: 0.24253 6.59959 0.2343E-06 0.2258E-02 B2 | |
4: 0.25952 7.06182 0.6207E-01 0.7446E-08 B1 | |
5: 0.31182 8.48517 0.000 A2 | |
6: 0.31182 8.48518 0.2602E-05 0.1230E-03 B1 | |
7: 0.31182 8.48517 0.3603E-06 0.8884E-03 B2 | |
8: 0.31607 8.60065 0.5494E-07 0.5671E-02 A1 | |
9: 0.31607 8.60065 0.5869E-07 0.5308E-02 B1 | |
10: 0.31607 8.60066 0.3430E-06 0.9083E-03 B2 | |
11: 0.32408 8.81871 0.000 A2 | |
12: 0.33193 9.03239 0.9239E-01 0.3057E-08 A1 | |
13: 0.38272 10.41441 0.3310E-06 0.6419E-03 A1 | |
14: 0.38272 10.41441 0.000 A2 | |
15: 0.38272 10.41440 0.4175E-08 0.5090E-01 B1 | |
16: 0.39748 10.81609 0.1995E-01 0.9873E-08 B2 | |
17: 0.46570 12.67233 0.4076E-06 0.3520E-03 A1 | |
18: 0.46570 12.67233 0.000 A2 | |
19: 0.46570 12.67233 0.1571E-06 0.9133E-03 B1 | |
20: 0.48806 13.28083 0.9515E-07 0.1373E-02 A1 | |
21: 0.48806 13.28080 0.000 A2 | |
22: 0.48806 13.28079 0.1860E-04 0.7024E-05 B2 | |
23: 0.49096 13.35983 0.1505 0.8582E-09 B2 | |
24: 0.51258 13.94798 0.3061E-01 0.3869E-08 B1 | |
25: 0.51457 14.00212 0.2328E-09 0.5049 A1 | |
26: 0.51457 14.00214 0.1320E-05 0.8905E-04 B2 | |
27: 0.51457 14.00217 0.4126E-04 0.2849E-05 B1 | |
28: 0.52248 14.21750 0.000 A2 | |
29: 0.52248 14.21753 0.2941E-05 0.3877E-04 B1 | |
30: 0.52248 14.21752 0.8118E-06 0.1404E-03 B2 | |
31: 0.52688 14.33701 0.000 A2 | |
32: 0.55682 15.15176 0.000 A2 | |
33: 0.55682 15.15178 0.1462E-05 0.6865E-04 B1 | |
34: 0.55682 15.15178 0.2860E-07 0.3510E-02 B2 | |
35: 0.56209 15.29535 0.2285E-01 0.4312E-08 A1 | |
36: 0.57018 15.51550 0.3776E-06 0.2535E-03 A1 | |
37: 0.57019 15.51555 0.000 A2 | |
38: 0.57019 15.51553 0.1316E-07 0.7275E-02 B1 | |
39: 0.58458 15.90720 0.4851E-02 0.1877E-07 A1 | |
40: 0.62298 16.95204 0.1281 0.6260E-09 B2 | |
</code> | |
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但修正之后,由于自旋不再守恒,因此不能再严格区分单重态还是三重态,而是上面所有激发态在一起列出。具体谁对应着原先的单重态、三重态?往上滚动鼠标,就可以看到这些态是来自微扰前的什么态。例如: | |
<code bash> | |
1: 0.24253 6.59960 0.1347E-05 0.3927E-03 A1 | |
</code> | |
它来自A1不可约表示,并且是第一个来自A1的激发态。那么我们往前一点翻阅到A1不可约表示: | |
<code bash> | |
Symmetry A1 | |
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Excit. no.: 10 Matrix dim.: 10 Total dim.: 10 | |
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Excitation energies E under spin-orbital coupling in a.u. and eV | |
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no. E/a.u. E/eV f Err/a.u. Ecorr/eV | |
---------------------------------------------------------------- | |
1 0.2425 6.5996 0.1347E-05 0.4936E-03 0.00000 | |
2 0.3161 8.6007 0.5494E-07 0.7835E-03 0.00000 | |
3 0.3319 9.0324 0.9239E-01 0.3694E-03 0.00000 | |
4 0.3827 10.4144 0.3310E-06 0.8174E-03 0.00000 | |
5 0.4657 12.6723 0.4076E-06 0.5252E-03 0.00000 | |
6 0.4881 13.2808 0.9515E-07 0.7380E-03 0.00000 | |
7 0.5146 14.0021 0.2328E-09 0.8170E-03 0.00000 | |
8 0.5621 15.2954 0.2285E-01 0.6914E-03 0.00000 | |
9 0.5702 15.5155 0.3776E-06 0.7900E-03 0.00000 | |
10 0.5846 15.9072 0.4851E-02 0.5948E-03 0.00000 | |
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Major singlet group excitation contributions for the above excitations | |
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Excitation Singlet group Excitation weight Contribution | |
Nr. excited states energy /eV (sum=1) to f | |
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1: Triplet 1B1 6.5996 1.0000 | |
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2: Triplet 1A2 8.6007 1.0000 | |
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3: Singlet 1A1 9.0324 1.0000 0.9239E-01 | |
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4: Triplet 1B2 10.4144 1.0000 | |
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5: Triplet 2B2 12.6723 1.0000 | |
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6: Triplet 2B1 13.2809 1.0000 | |
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7: Triplet 2A2 14.0022 1.0000 | |
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8: Singlet 2A1 15.2953 1.0000 0.2285E-01 | |
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9: Triplet 3B2 15.5155 0.9999 | |
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10: Singlet 3A1 15.9071 0.9999 0.4851E-02 | |
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</code> | |
可以看到A1不可约表示的第一个激发态: | |
<code bash> | |
1: Triplet 1B1 6.5996 1.0000 | |
</code> | |
它是Triplet,权重为1。表示它是100%的三重态。我们看第九个态: | |
<code bash> | |
9: Triplet 3B2 15.5155 0.9999 | |
</code> | |
表示这个激发态经过旋归耦合微扰以后,三重态只占99.99%了,已经不是严格意义的三重态。 | |