请教ORCA下稀土有机配合物第一激发态S1的确定

bomsaude · 发表于 Post on 2014-12-10 23:28:19

本帖最后由 bomsaude 于 2014-12-11 01:47 编辑

对于如何从ORCA激发态计算结果认定如下图中的S1，S2等，概念不是很清楚。

Jablonski 图

采用ZINDO/S方法，计算激发单重态和三重态
部分输出结果如下：
-----------------------------
CIS-EXCITED STATES (SINGLETS)
-----------------------------
the weight of the individual excitations are printed if larger than 0.01
STATE 1: E= 0.137489 au 3.741 eV 30175.3 cm**-1
114a -> 141a : 0.035487 (c= 0.18838008)
117a -> 129a : 0.850349 (c= -0.92214378)
117a -> 134a : 0.050635 (c= -0.22502313)
117a -> 141a : 0.012054 (c= 0.10979105)
123a -> 129a : 0.017717 (c= -0.13310372)
STATE 2: E= 0.137603 au 3.744 eV 30200.3 cm**-1
115a -> 142a : 0.034893 (c= 0.18679791)
118a -> 130a : 0.853358 (c= 0.92377387)
118a -> 136a : 0.047871 (c= 0.21879363)
118a -> 142a : 0.012915 (c= 0.11364303)
124a -> 130a : 0.017141 (c= 0.13092420)
STATE 3: E= 0.139450 au 3.795 eV 30605.7 cm**-1
113a -> 140a : 0.037234 (c= -0.19296218)
116a -> 128a : 0.848805 (c= 0.92130640)
116a -> 133a : 0.054491 (c= 0.23343215)
116a -> 140a : 0.011363 (c= 0.10659555)
122a -> 128a : 0.017420 (c= -0.13198674)
STATE 4: E= 0.153628 au 4.180 eV 33717.4 cm**-1
120a -> 129a : 0.033877 (c= -0.18405750)
121a -> 130a : 0.030135 (c= -0.17359370)
125a -> 128a : 0.079585 (c= 0.28210779)
126a -> 129a : 0.431686 (c= -0.65702835)
127a -> 130a : 0.379315 (c= 0.61588588)
STATE 5: E= 0.155648 au 4.235 eV 34160.9 cm**-1
119a -> 128a : 0.048892 (c= 0.22111534)
119a -> 133a : 0.015714 (c= 0.12535552)
125a -> 128a : 0.819393 (c= -0.90520349)
126a -> 129a : 0.024124 (c= -0.15531784)
127a -> 130a : 0.053597 (c= 0.23151127)
STATE 6: E= 0.158463 au 4.312 eV 34778.6 cm**-1
120a -> 129a : 0.019230 (c= -0.13867048)
121a -> 130a : 0.021959 (c= 0.14818627)
126a -> 129a : 0.445288 (c= -0.66729897)
127a -> 130a : 0.463390 (c= -0.68072737)
STATE 7: E= 0.167102 au 4.547 eV 36674.7 cm**-1
121a -> 135a : 0.142165 (c= 0.37704801)
122a -> 128a : 0.015229 (c= 0.12340567)
124a -> 130a : 0.386201 (c= -0.62145047)
124a -> 135a : 0.011504 (c= -0.10725873)
124a -> 136a : 0.185572 (c= 0.43078088)
127a -> 135a : 0.199740 (c= 0.44692299)
STATE 8: E= 0.167141 au 4.548 eV 36683.2 cm**-1
119a -> 131a : 0.144838 (c= 0.38057562)
122a -> 128a : 0.371350 (c= 0.60938490)
122a -> 133a : 0.182631 (c= -0.42735330)
123a -> 129a : 0.013875 (c= -0.11779095)
124a -> 130a : 0.014028 (c= 0.11843945)
125a -> 131a : 0.193348 (c= 0.43971361)
。。。。。。

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现在想问的是
1 这里的STATE X 和S1，S2什么关系？
2 怎么计算这里的轨道跃迁贡献比？

文献给出的S1数据是

STATE 6: E= 0.158463 au 4.312 eV 34778.6 cm**-1，选择振子强度最强的，下面有数值。

其模拟的吸收光谱图如下：

文献选择T1是

STATE 1: E= 0.092070 au 2.505 eV 20207.0 cm**-1

这里T1为什么选择了State 1？

CIS EXCITED STATES (TRIPLETS)
-----------------------------
the weight of the individual excitations are printed if larger than 0.01
STATE 1: E= 0.092070 au 2.505 eV 20207.0 cm**-1
121a -> 130a : 0.176536 (c= -0.42016136)
121a -> 136a : 0.087092 (c= -0.29511292)
124a -> 135a : 0.011170 (c= 0.10568614)
127a -> 130a : 0.624059 (c= 0.78997432)
127a -> 136a : 0.061427 (c= 0.24784459)
127a -> 142a : 0.031255 (c= -0.17679119)
STATE 2: E= 0.092187 au 2.509 eV 20232.7 cm**-1
120a -> 129a : 0.164088 (c= -0.40507754)
120a -> 134a : 0.085917 (c= -0.29311528)
123a -> 132a : 0.011720 (c= 0.10825979)
126a -> 129a : 0.635538 (c= -0.79720667)
126a -> 134a : 0.063984 (c= -0.25295140)
126a -> 141a : 0.030682 (c= -0.17516309)
STATE 3: E= 0.092234 au 2.510 eV 20243.0 cm**-1
119a -> 128a : 0.153578 (c= -0.39189023)
119a -> 133a : 0.085880 (c= -0.29305282)
122a -> 131a : 0.014464 (c= -0.12026440)
125a -> 128a : 0.656988 (c= 0.81054812)
125a -> 133a : 0.055049 (c= 0.23462593)
125a -> 140a : 0.026947 (c= -0.16415478)
STATE 4: E= 0.105037 au 2.858 eV 23053.0 cm**-1
119a -> 128a : 0.212747 (c= 0.46124537)
119a -> 133a : 0.094815 (c= -0.30792084)
119a -> 140a : 0.017654 (c= -0.13286933)
122a -> 131a : 0.380767 (c= -0.61706315)
125a -> 128a : 0.026135 (c= 0.16166398)
125a -> 133a : 0.239046 (c= -0.48892329)
STATE 5: E= 0.105109 au 2.860 eV 23068.8 cm**-1
121a -> 130a : 0.198177 (c= -0.44517045)
121a -> 136a : 0.091941 (c= 0.30321828)
121a -> 142a : 0.019089 (c= 0.13816266)
124a -> 135a : 0.378723 (c= -0.61540473)
124a -> 136a : 0.012107 (c= -0.11003267)
127a -> 130a : 0.037930 (c= -0.19475745)
127a -> 136a : 0.234920 (c= 0.48468534)
STATE 6: E= 0.105138 au 2.861 eV 23075.2 cm**-1
120a -> 129a : 0.202887 (c= -0.45042950)
120a -> 134a : 0.094732 (c= 0.30778631)
120a -> 141a : 0.019135 (c= -0.13833106)
123a -> 132a : 0.381651 (c= -0.61777913)
126a -> 129a : 0.034953 (c= 0.18695741)
126a -> 134a : 0.232093 (c= -0.48175992)
STATE 7: E= 0.129836 au 3.533 eV 28495.7 cm**-1
114a -> 141a : 0.037223 (c= -0.19293360)
117a -> 129a : 0.762828 (c= 0.87340050)
117a -> 134a : 0.052041 (c= 0.22812499)
117a -> 141a : 0.013294 (c= -0.11529837)
120a -> 129a : 0.012050 (c= -0.10977282)
123a -> 129a : 0.068344 (c= 0.26142687)
123a -> 134a : 0.011990 (c= -0.10949845)
STATE 8: E= 0.129965 au 3.537 eV 28524.1 cm**-1
115a -> 142a : 0.036292 (c= -0.19050444)
118a -> 130a : 0.758836 (c= -0.87111203)
118a -> 136a : 0.048952 (c= -0.22125116)
118a -> 142a : 0.014214 (c= -0.11922413)
121a -> 130a : 0.012128 (c= -0.11012838)
124a -> 130a : 0.071317 (c= -0.26705199)
124a -> 136a : 0.014570 (c= 0.12070657)
。。。。。。

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-----------------------------------------------------------------------------
ABSORPTION SPECTRUM VIA TRANSITION ELECTRIC DIPOLE MOMENTS
-----------------------------------------------------------------------------
State Energy Wavelength fosc T2 TX TY TZ
(cm-1) (nm) (au**2) (au) (au) (au)
-----------------------------------------------------------------------------
1 30175.3 331.4 0.000506940 0.00553 0.05313 0.03649 -0.03710
2 30200.3 331.1 0.000967433 0.01055 -0.07004 -0.06492 -0.03777
3 30605.7 326.7 0.001573307 0.01692 -0.05687 0.10784 -0.04537
4 33717.4 296.6 0.313924309 3.06512 0.15430 -1.57939 -0.73949
5 34160.9 292.7 0.507871261 4.89441 -0.39260 1.68864 -1.37433
6 34778.6 287.5 1.087725687 10.29635 2.40312 1.56649 -1.43786
7 36674.7 272.7 0.010488582 0.09415 0.00522 -0.22890 0.20427
8 36683.2 272.6 0.017251333 0.15482 0.17239 0.35205 0.03410
9 36693.7 272.5 0.010018985 0.08989 -0.06343 0.05108 0.28854
10 38901.5 257.1 0.005686900 0.04813 0.09056 0.06832 0.18777
11 39003.7 256.4 0.004783279 0.04037 -0.03993 0.16170 0.11239
12 39024.9 256.2 0.005129107 0.04327 0.10518 -0.17110 -0.05416
13 42352.3 236.1 0.036533469 0.28398 0.06611 0.19033 -0.49334
14 42439.8 235.6 0.094885245 0.73604 0.02525 -0.75870 -0.39972
15 42659.3 234.4 0.035038435 0.27040 0.07823 -0.46804 0.21265
16 45937.0 217.7 0.048867581 0.35021 0.33438 -0.36750 0.32147
17 46018.1 217.3 0.108264038 0.77452 0.61343 0.08987 0.62462
18 46073.3 217.0 0.090799677 0.64880 0.56730 0.43740 0.36831
19 46168.5 216.6 0.000011166 0.00008 0.00454 -0.00068 0.00765
20 46186.6 216.5 0.012987071 0.09257 0.21096 0.20079 0.08802
21 46212.0 216.4 0.005506377 0.03923 -0.15716 -0.04917 -0.11005
22 46410.1 215.5 0.000607513 0.00431 -0.04386 0.00171 -0.04882
23 47064.9 212.5 0.000003371 0.00002 -0.00234 -0.00362 -0.00223
24 47437.2 210.8 0.000002176 0.00002 -0.00070 -0.00324 0.00203
25 47484.6 210.6 0.000001373 0.00001 -0.00114 0.00109 0.00265
26 20207.0 494.9 spin forbidden (mult=3)
27 20232.7 494.2 spin forbidden (mult=3)
28 20243.0 494.0 spin forbidden (mult=3)
29 23053.0 433.8 spin forbidden (mult=3)
30 23068.8 433.5 spin forbidden (mult=3)
31 23075.2 433.4 spin forbidden (mult=3)
32 28495.7 350.9 spin forbidden (mult=3)
33 28524.1 350.6 spin forbidden (mult=3)
34 28863.0 346.5 spin forbidden (mult=3)
35 29637.1 337.4 spin forbidden (mult=3)
36 29649.3 337.3 spin forbidden (mult=3)
37 29665.3 337.1 spin forbidden (mult=3)
38 30136.9 331.8 spin forbidden (mult=3)
39 30164.5 331.5 spin forbidden (mult=3)
40 30166.2 331.5 spin forbidden (mult=3)
41 32706.8 305.7 spin forbidden (mult=3)
42 33307.1 300.2 spin forbidden (mult=3)
43 33407.4 299.3 spin forbidden (mult=3)
44 36948.7 270.6 spin forbidden (mult=3)
45 37028.8 270.1 spin forbidden (mult=3)
46 37045.3 269.9 spin forbidden (mult=3)
47 37516.3 266.6 spin forbidden (mult=3)
48 37606.3 265.9 spin forbidden (mult=3)
49 37665.2 265.5 spin forbidden (mult=3)
50 42548.9 235.0 spin forbidden (mult=3)
-----------------------------------------------------------------------------
ABSORPTION SPECTRUM VIA TRANSITION VELOCITY DIPOLE MOMENTS
-----------------------------------------------------------------------------
State Energy Wavelength fosc P2 PX PY PZ
(cm-1) (nm) (au**2) (au) (au) (au)
-----------------------------------------------------------------------------
1 30175.3 331.4 0.000204316 0.00004 -0.00236 0.00034 0.00604
2 30200.3 331.1 0.000416936 0.00009 0.00365 0.00852 -0.00041
3 30605.7 326.7 0.000925583 0.00019 0.00195 -0.01353 0.00257
4 33717.4 296.6 0.184509844 0.04252 -0.01978 0.18864 0.08087
5 34160.9 292.7 0.342705282 0.08001 0.05074 -0.20695 0.18604
6 34778.6 287.5 0.687603742 0.16344 -0.31435 -0.18442 0.17496
7 36674.7 272.7 0.004092443 0.00103 0.01357 0.02470 -0.01522
8 36683.2 272.6 0.007789788 0.00195 -0.01326 -0.04144 0.00774
9 36693.7 272.5 0.005893934 0.00148 0.01927 0.00081 -0.03326
10 38901.5 257.1 0.002682988 0.00071 -0.01497 0.00851 -0.02041
11 39003.7 256.4 0.005075882 0.00135 0.02229 -0.02083 -0.02055
12 39024.9 256.2 0.004965836 0.00132 -0.01901 0.02027 0.02350
13 42352.3 236.1 0.016400937 0.00475 0.00499 -0.02463 0.06415
14 42439.8 235.6 0.040357773 0.01171 -0.00571 0.09377 0.05368
15 42659.3 234.4 0.013925679 0.00406 -0.01226 0.05989 -0.01797
16 45937.0 217.7 0.010880840 0.00342 -0.03495 0.03963 -0.02499
17 46018.1 217.3 0.024389057 0.00767 -0.05619 -0.00960 -0.06650
18 46073.3 217.0 0.019163621 0.00603 -0.05889 -0.03479 -0.03683
19 46168.5 216.6 0.000005459 0.00000 -0.00057 0.00005 -0.00118
20 46186.6 216.5 0.004791250 0.00151 -0.02521 -0.02923 -0.00472
21 46212.0 216.4 0.003441056 0.00109 0.02319 0.00908 0.02160
22 46410.1 215.5 0.000949839 0.00030 0.01600 -0.00287 0.00607
23 47064.9 212.5 0.000001062 0.00000 0.00045 0.00032 0.00018
24 47437.2 210.8 0.000001068 0.00000 0.00021 0.00032 -0.00044
25 47484.6 210.6 0.000000502 0.00000 0.00030 -0.00011 -0.00025
26 20207.0 494.9 spin forbidden (mult=3)
27 20232.7 494.2 spin forbidden (mult=3)
28 20243.0 494.0 spin forbidden (mult=3)
29 23053.0 433.8 spin forbidden (mult=3)
30 23068.8 433.5 spin forbidden (mult=3)
31 23075.2 433.4 spin forbidden (mult=3)
32 28495.7 350.9 spin forbidden (mult=3)
33 28524.1 350.6 spin forbidden (mult=3)
34 28863.0 346.5 spin forbidden (mult=3)
35 29637.1 337.4 spin forbidden (mult=3)
36 29649.3 337.3 spin forbidden (mult=3)
37 29665.3 337.1 spin forbidden (mult=3)
38 30136.9 331.8 spin forbidden (mult=3)
39 30164.5 331.5 spin forbidden (mult=3)
40 30166.2 331.5 spin forbidden (mult=3)
41 32706.8 305.7 spin forbidden (mult=3)
42 33307.1 300.2 spin forbidden (mult=3)
43 33407.4 299.3 spin forbidden (mult=3)
44 36948.7 270.6 spin forbidden (mult=3)
45 37028.8 270.1 spin forbidden (mult=3)
46 37045.3 269.9 spin forbidden (mult=3)
47 37516.3 266.6 spin forbidden (mult=3)
48 37606.3 265.9 spin forbidden (mult=3)
49 37665.2 265.5 spin forbidden (mult=3)
50 42548.9 235.0 spin forbidden (mult=3)

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谢谢大家了！

bomsaude · 发表于 Post on 2014-12-11 18:00:46

非常感谢您的指点，现在明白了。

sobereva · 发表于 Post on 2014-12-11 01:15:07

将所有计算出来的激发态按照能量由低到高排序，最低的单重态激发态就是S1，然后S2...一直往上排，也即这里的STATE编号。对于三重态激发态，最低的就是T1。这是理论计算上对S、T编号的排序。但是实验上的序号有时有所差别，把振子强度为0或接近0的态（暗态）给空过去，因此也许比如文献上的S1对应的或许是理论计算的S3。这需要根据激发能来进行对应。

至于贡献，比如117a -> 129a : 0.850349 (c= -0.92214378)，就说明117a -> 129a贡献了85%

PS：如果需要大量贴代码或者输出信息，建议点击<>形状的代码按钮再贴，看着比较简洁工整。

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[ORCA] 请教ORCA下稀土有机配合物第一激发态S1的确定