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我在计算一个有机金属配合物催化的反应机理，包含十几步反应，其中一步是光激发反应。我用PBE0-D3(BJ)/6-31G**/SDD优化出了过渡态和中间体，现在用PWPB95-D3(BJ)/def2-TZVP算单点。算激发态的时候ORCA 5.0.1报错，关键词如下：
! PWPB95 D3 def2-TZVP def2/J def2-TZVP/C RIJCOSX tightSCF noautostart miniprint nopop
! SlowConv SCFConvForced NoTRAH
%maxcore 2000
%pal nprocs 16 end
%cpcm
smd true
SMDsolvent "benzene"
end
%tddft
nroots 10
iroot 5
TDA false
end
* xyz 0 2
（原子坐标）
报错发生在mp2结束之后，计算TDDFT的时候。
---------------
TD-DFT XC SETUP
---------------
DFT calculation ... on
Name of the grid file ... bbb.grid_cis.tmp
Exchange functional (TD-DFT) ... PW6
Correlation functional (TD-DFT) ... B95
Hybrid DFT ... on
Exchange mixing (TD-DFT) ... 0.500
GGA exch. scaling (TD-DFT) ... 0.500
GGA corr. scaling (TD-DFT) ... 0.731
Building densities ... done
Calculating rho(r) on the grid ... done
Building xc-kernel on the grid ... [file orca_tools/Tool-Numint/qcfxc.cpp, line 14986, Process 12]: Error: Invalid or unknown value for Exchange in DFT XC-Kernel
[file orca_tools/Tool-Numint/qcfxc.cpp, line 14986, Process 2]: Error: Invalid or unknown value for Exchange in DFT XC-Kernel
[file orca_tools/Tool-Numint/qcfxc.cpp, line 14986, Process 6]: Error: Invalid or unknown value for Exchange in DFT XC-Kernel
--------------------------------------------------------------------------
Primary job terminated normally, but 1 process returned
a non-zero exit code. Per user-direction, the job has been aborted.
--------------------------------------------------------------------------
--------------------------------------------------------------------------
mpirun detected that one or more processes exited with non-zero status, thus causing
the job to be terminated. The first process to do so was:
Process name: [[64167,1],3]
Exit code: 55
--------------------------------------------------------------------------
ORCA finished by error termination in CIS
Calling Command: mpirun -np 16 /opt/soft/orca5.01/orca501/orca_cis_mpi bbb.cisinp.tmp bbb
[file orca_tools/qcmsg.cpp, line 458]:
.... aborting the run
搜索了一下，似乎是说这个泛函的kernel没有内置，需要调用libXC。【However, this specific kernel for that functional is not natively implemented. You should try using LibXC.】
按照ORCA manual所说，用orca -libxcfunctionals 查看了Functionals available via LibXC，其中并没有PWPB95。后来我看到社长的帖子《简谈量子化学计算中DFT泛函的选择》(http://sobereva.com/272)，文中说：“ORCA支持wB2GP-PLYP和DSD-PBEP86算TDDFT。”
我的疑问是：
1. 是不是目前ORCA不支持PWPB95算TDDFT？
2. 多步反应中，能否光激发反应用DSD-PBEP86或PBE0/def2-TZVPP，其他反应步骤用PWPB95/def2-TZVPP？最后将各步的自由能垒和自由能变化量拼合成一个完整的Free energy profile。因为求算自由能垒和自由能变化量时都是同一计算级别下作差，应该是有意义的。但不清楚这样做是否合理，恳请老师指教。
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发表于 Post on 2022-1-14 16:14:06
楼主 Author
发表于 Post on 2022-1-15 07:07:02