手册原文如下
Sometimes you will like to change the ordering of the starting orbitals to obtain a different electronic state inthe SCF calculation. For example, if we take the last input and want to converge to a ligand field excitedstate this can be achieved by:
! UHF HF SV
%basis newGTO Cl "Dunning-DZP" end #注意，这里的Dunning-DZP基组并不能被orca 4.2.0识别，被我改成了cc-pVDZ
end
%scf rotate {48, 49, 90, 1, 1} end #注，这里括号中的两个1依据小*虫马甲小卒的意思大概代表β轨道
end
* xyz -2 2
Cu 0 0 0 newGTO "TZVPP" end
Cl 2.25 0 0
Cl -2.25 0 0
Cl 0 2.25 0
Cl 0 -2.25 0
*
In the present case, MO 48 is the spin-down HOMO and MO49 the spin-down LUMO. Since we do acalculation on a Cu(II) complex (d9electron configuration) the beta LUMO corresponds with the “SOMO”.Thus, by changing the SOMO we proceed to a different electronic state (in this case the one with the “hole”in the “dxy” orbital instead of the “dx2−y2 ” orbital). The interchange of the initial guess MOs is achieved bythe command rotate {48, 49, 90, 1, 1} end. What this does is the following: take the initial guess MOs48 and 49 and rotate them by an angle of 90 degree (this just interchanges them). The two last numbersmean that both orbitals are from the spin-down set. For RHF or ROHF calculations the operator would be 0.In general you would probably first take a look at the initial guess orbitals before changing them