求教对电子跃迁偶极矩的正确理解

youguojian

     我做的是模拟精细光谱（荧光激发光谱或发射光谱），只考虑基态S0到第一激发单重态S1态的跃迁！用模拟出的精细光谱与实验光谱进行对比来探讨FC、HT对光谱的影响！
    在做光谱图的时候采用FCclasses的程序，有一个el文件，里面主要是电子跃迁偶极矩。
el文件中共有3N+2行数据，以吸收为例，
       第一行是td-s0的电子跃迁偶极矩，如下图蓝色部分
      Excited states from <AA,BB:AA,BB> singles matrix:
      ************************************************
      1PDM for each excited state written to RWF  633
      Ground to excited state transition densities written to RWF  633
      Ground to excited state transition electric dipole moments (Au):
       state          X              Y                  Z           Dip. S.      Osc.
         1        -2.4391     -1.9020      0.0000      9.5670      0.9016
         2         0.4099      0.3393      0.0000      0.2832      0.0310
         3         0.0000      0.0000      0.0000      0.0000      0.0000
         4         0.0000      0.0000      0.0000      0.0000      0.0000
         5         0.0000      0.0000      0.1144      0.0131      0.0016

       第二行是td-s1的电子跃迁偶极矩，如下图蓝色部分
     Excited states from <AA,BB:AA,BB> singles matrix:
      *************************************************

     1PDM for each excited state written to RWF  633
      Ground to excited state transition densities written to RWF  633
     Ground to excited state transition electric dipole moments (Au):
       state          X              Y                 Z          Dip. S.        Osc.
         1       -2.5823     -2.1369      0.0000     11.2344      0.9083
         2         0.3638      0.3271      0.0000      0.2394      0.0245
         3         0.0000      0.0000      0.0000      0.0000      0.0000
         4         0.0000      0.0000      0.0000      0.0000      0.0000
         5         0.0000      0.0000      0.1027      0.0105      0.0012
      第三行到3N+2行是从S1态的频率中取出的，如下图蓝色部分
     【s1态频率计算输入为   #p  td(singlets,nstates=5,root=1)   b3lyp/6-311++G**   freq(noraman,hpmode)   scf=(maxcyc=400,conver=8)  iop(2/16=2,2/17=2)】

Test job not archived.
1\1\GINC-WORK215\Freq\RB3LYP TD-FC\6-311++G(d,p)\C14H12\DYUL\22-Nov-20
14\0\\#p td(singlets,nstates=5,root=1) b3lyp/6-311++G** freq(noraman,h
pmode) scf=(maxcyc=400,conver=8) iop(2/16=2,2/17=2)\\transstilbene-b3l
yp-s1-freq\\0,1\C,2.459146,3.564997,0.\C,1.285189,2.844564,0.\C,1.2851
89,1.413884,0.\C,2.568238,0.758542,0.\C,3.737419,1.4991,0.\C,3.703384,
2.897989,0.\C,0.062079,0.704662,0.\C,-0.062079,-0.704662,0.\C,-1.28518
9,-1.413884,0.\C,-2.568238,-0.758542,0.\C,-3.737419,-1.4991,0.\C,-3.70
3384,-2.897989,0.\C,-2.459146,-3.564997,0.\C,-1.285189,-2.844564,0.\H,
2.428936,4.648799,0.\H,0.330615,3.361326,0.\H,2.621403,-0.322615,0.\H,
4.694096,0.987592,0.\H,4.6262,3.466498,0.\H,-0.842029,1.303612,0.\H,0.
842029,-1.303612,0.\H,-2.621403,0.322615,0.\H,-4.694096,-0.987592,0.\H
,-4.6262,-3.466498,0.\H,-2.428936,-4.648799,0.\H,-0.330615,-3.361326,0
.\\Version=EM64L-G09RevB.01\State=1-AG\HF=-540.8368829\RMSD=3.696e-09\
RMSF=1.127e-04\ZeroPoint=0.2105286\Thermal=0.2222033\Dipole=0.,0.,0.\D
ipoleDeriv=0.0388706,0.0052033,0.,-0.3761467,-0.0651499,0.,0.,0.,-0.13
78307,0.1182335,0.0019714,0.,0.4246514,0.3624711,0.,0.,0.,-0.1216611,0
.5769346,0.3177105,0.,-0.5229937,-0.4616759,0.,0.,0.,0.0211499,-0.0401
107,0.0657547,0.,0.6281293,0.277755,0.,0.,0.,-0.1569223,0.1538877,0.00
85735,0.,-0.4701318,-0.2413235,0.,0.,0.,-0.1377625,-0.3674837,-0.27713
44,0.,0.2190851,0.0423055,0.,0.,0.,-0.1492209,-0.4511808,-0.2727125,0.
,0.0851218,0.2343145,0.,0.,0.,-0.134085,-0.4511808,-0.2727125,0.,0.085
1218,0.2343145,0.,0.,0.,-0.134085,0.5769346,0.3177105,0.,-0.5229937,-0
.4616759,0.,0.,0.,0.0211499,-0.0401107,0.0657547,0.,0.6281293,0.277755
,0.,0.,0.,-0.1569223,0.1538877,0.0085735,0.,-0.4701318,-0.2413235,0.,0
.,0.,-0.1377625,-0.3674837,-0.2771344,0.,0.2190851,0.0423055,0.,0.,0.,
-0.1492209,0.0388706,0.0052033,0.,-0.3761467,-0.0651499,0.,0.,0.,-0.13
78307,0.1182335,0.0019714,0.,0.4246514,0.3624711,0.,0.,0.,-0.1216611,0
.0920995,0.0243539,0.,-0.0261776,-0.1302514,0.,0.,0.,0.1400157,-0.0033
722,0.1215136,0.,-0.0212932,-0.0063964,0.,0.,0.,0.1209528,0.0467449,-0
.0290494,0.,0.0489353,-0.0480519,0.,0.,0.,0.1452827,-0.1139714,0.02733
07,0.,0.103259,0.052782,0.,0.,0.,0.1313721,-0.0722643,-0.0876494,0.,-0
.072075,0.024176,0.,0.,0.,0.1550237,0.0209709,0.0953811,0.,-0.0202088,
-0.0396816,0.,0.,0.,0.1237607,0.0209709,0.0953811,0.,-0.0202088,-0.039
6816,0.,0.,0.,0.1237607,0.0467449,-0.0290494,0.,0.0489353,-0.0480519,0
.,0.,0.,0.1452827,-0.1139714,0.0273307,0.,0.103259,0.052782,0.,0.,0.,0
.1313721,-0.0722643,-0.0876494,0.,-0.072075,0.024176,0.,0.,0.,0.155023
7,0.0920995,0.0243539,0.,-0.0261776,-0.1302514,0.,0.,0.,0.1400157,-0.0
033722,0.1215136,0.,-0.0212932,-0.0063964,0.,0.,0.,0.1209528\Quadrupol
e=4.4487729,5.0429737,-9.4917467,0.6065116,0.,0.\QuadrupoleDeriv=-0.22
8216,-0.0988853,0.3271012,-0.8645728,0.0000001,0.,-1.9971109,2.9736919
,-0.976581,0.2386771,-0.0000002,0.0000001,0.,0.,0.,0.,-0.6535928,-1.25
81428,-0.4866973,0.2684998,0.2181975,2.1141145,0.,-0.0000001,0.7663764
,-0.7814672,0.0150909,-0.9718895,0.,0.,0.,0.,0.,0.,-0.1566667,-0.88986
15,-0.1434811,0.3556703,-0.2121893,-0.927754,0.,0.,-0.6070708,0.759942
3,-0.1528714,0.0576572,0.,0.,0.,0.,0.,0.,0.3894226,-0.0663626,-0.77977
42,-0.1707761,0.9505503,-0.7456699,0.,-0.0000002,1.482348,-2.1222509,0
.6399028,-0.0600372,0.,-0.0000001,0.,0.,0.,0.,-0.9221898,0.3302635,1.9


   问题： 以上是我做el文件的步骤，我想问的是我在第三步的时候所选择的的蓝色部分是不是电子跃迁偶极矩，与el文件第一行与第二行的跃迁偶极矩是不是一回事！

youguojian

做模拟光谱的朋友和懂电子跃迁偶极矩的朋友帮忙，指导下我！谢谢了

sobereva

完全不是一回事。
第三步是DipoleDeriv，是体系偶极矩对每个原子坐标的导数，和跃迁偶极矩无关。
此文涉及到一些偶极矩对原子坐标导数的讨论，可以看看：《GAPT电荷的原理和性质》
http://sobereva.com/208

youguojian

sobereva 发表于 2015-3-24 00:47
完全不是一回事。
第三步是DipoleDeriv，是体系偶极矩对每个原子坐标的导数，和跃迁偶极矩无关。
此文涉 ...

非常感谢Sob老师，因为怀疑它不是，所以才发问，可我懂的不多，所以需要肯定的否决！

Sob老师，但是在跃迁偶极矩公式（如下图所示）;  等式左边是电子跃迁偶极矩，但是等式右边括号内的分子也应该是电子跃迁偶极矩吧？而不应该是DipoleDeriv（体系偶极矩对每个原子坐标的导数）吧？这样用DipoleDeriv的数值来取代，电子跃迁偶极矩，是不是错误的呢？请老师指教~~

sobereva

你图中的miu到底是跃迁偶极矩还是体系偶极矩？按理说应该是后者。
跃迁偶极矩的公式应当是-<i|r|j>这样才对，r是坐标算符，i和j是前后两个态的电子波函数。