本帖最后由 是aweia 于 2022-3-29 17:08 编辑
根据ORCA手册，在计算蒽分子的ISC速率时，需要首先计算S1与对应三重态各子态间的旋轨耦合，以下为手册原文
As a simple example, one could compute the excited singlet and ground triplet geometries and Hessians foranthracene using TD-DFT, then compute the SOC matrix elements with a given triplet spin-sublevel by the same method (see the details below), maybe even using CASSCF, MRCI, STEOM-CCSD or some other theory level and finally obtain the ISC rates using an input such as:
!ESD(ISC) NOITER
%ESD ISCISHESSIAN "ANT_S1.hess"
ISCFSHESSIAN "ANT_T1.hess"
DELE 11548
SOCME 0.0, 2.33e-5
END
* XYZFILE 0 1 ANT_T1.xyz
另外手册中说明，ESD模块内SOCME应使用的是原子单位，：
The relevant matrix elements can be calculated from any method available in ORCA and inputed as SOCME Re,Im under %ESD
where Re and Im are its real and imaginary parts (in in atomic units!)
也就是说将上述手册ESD模块中SOCME的值2.33e-5为Eh单位 若转变为cm-1单位就是约为5.11 cm-1
但我实际算的蒽分子的S1到T1\T2d的旋轨耦合几乎为零，差别比较大
请问是我理解的有问题吗，还是我计算的有问题 以下是我的输入文件，请各位批评指正
! B3LYP/G TZVP miniprint tightSCF
%pal
nprocs 64
end
%tddft
nroots 20
dosoc true
tda false
printlevel 10
end
* xyzfile 0 1 anthracene.xyz
同时我把输出文件上传
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发表于 Post on 2022-3-29 13:52:15
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，源代码见
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