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[交流] 【求助】大家帮忙看一下我做的激发态已有5人参与

各位帮忙看一下我做的激发态，

输入如下：
#p LC-WPBE/6-31g(d) td=(nstates=20,direct,singlet) scrf=(pcm,solvent=t
oluene) pop=full

结果为：
Excited State 1:    Singlet-EU    2.1766 eV  569.61 nm  f=0.0148  =0.000
   94 -> 96       0.46537
   95 -> 97       0.53687
   94 <- 96       0.11978
   95 <- 97       0.11527
感觉应该不会出现94 <- 96 和 95 <- 97呀，各位帮忙分析一下原因吧！！！

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1楼2010-07-13 08:58:12

已阅回复此楼关注TA 给TA发消息送TA红花 TA的回帖

c111999

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引用回帖:

Originally posted by yongleli at 2010-07-21 17:06:33:

请给个文献？

我记得
K. Burke, J. Werschnik, and E. K. U. Gross, J. Chem.
Phys. 123: 062206(2005)
说过，Casida推导过，TD-DFT计算方程最后能化简
为一个非Hermite矩阵的本征值问题：

(A B)(x ...

谢谢指正 -1

TDDFT/TDHF相当于CISD，更准确地说是CCSD
J. Chem. Phys., Vol. 109, No. 19, 15 November 1998

“the TDDFT results rival the very accurate
equation of motion coupled cluster singles and doubles
（EOM-CCSD） calculations”

关于为何TDDFT比CIS好的原因
“Mathematically, this is also identical to computing matrix ele-
ments between doubly excited states and the ground state.
Thus we see that RPA includes higher order correlation ef-
fects through double excitations that are not being accounted
for in the conﬁguration interaction singles method.”

关于去激发态无物理意义
Chem. Rev. 2005, 105, 4009−4037

This statement ought to reflect the attempt to give a math-
ematical procedure a physical meaning, but of course,
the “de-excitations” are nonphysical since one cannot
de-excite the Hartree Fock ground state. Historically
one can justify this statement, since TDHF (RPA) has
been constructed to include correlation effects in the
ground state by virtue of some classes of “doubly
excited“ Slater determinants, and in this context, one
can indeed speak about “de-excited” states.
……
This again is indicated by the magni-
tude of the Y amplitudes, which are a measure of the
ground-state correlation and which, as a consequence,
should be small compared to the X amplitudes.

[ Last edited by c111999 on 2010-7-21 at 21:46 ]