Dear all,
I have recently implemented B97 into ORCA's TDDFT part. For comparison, I chose QCHEM and NWCHEM. For the first few singlet excitations of CH2O, I obtained the following values in eV:
QCHEM NWCHEM
3.9854 4.2181
6.8489 7.0074
8.1122 8.2836
8.1203 8.2844
8.6866 8.7784
9.0941 9.4966
i.e. the numbers differ by tenths of eV. Since I was able to reproduce the QCHEM values with ORCA, I am confident in them.
The NW ground state energy as well as one-electron and core-core-repulsion is fine, as well as the MO energies of the occupied block. A possible explanation are wrong functional derivatives of B97.
Since other functionals like PBE0, HFS, CAM-B3LYP etc. look fine, I am confident in having chosen accurate parameters for each program involved. If someone would like output files or the deviation spreadsheet, I will be happy to provide them.
Full input for NWCHEM follows:
start temp
title "Testing Implementations"
scratch_dir .
permanent_dir .
memory total 1500 stack 200 heap 200 global 1100 MB
geometry units angstroms
symmetry c1
C -0.023503 0.000000 -0.000000
O -1.231109 -0.000000 0.000000
H 0.572248 0.947642 0.000000
H 0.572248 -0.947642 0.000000
end
BASIS spherical
# def2-TZVPD from EMSL
#BASIS SET: (5s,2p) -> [3s,2p]
H S
34.061341000 0.60251978000E-02
5.1235746000 0.45021094000E-01
1.1646626000 0.20189726000
H S
0.32723041000 1.0000000
H S
0.10307241000 1.0000000
H P
0.80000000000 1.0000000
H P
0.95774129632E-01 1.0000000
#BASIS SET: (12s,6p,3d,1f) -> [6s,3p,3d,1f]
C S
13575.3496820 0.22245814352E-03
2035.2333680 0.17232738252E-02
463.22562359 0.89255715314E-02
131.20019598 0.35727984502E-01
42.853015891 0.11076259931
15.584185766 0.24295627626
C S
6.2067138508 0.41440263448
2.5764896527 0.23744968655
C S
0.57696339419 1.0000000
C S
0.22972831358 1.0000000
C S
0.95164440028E-01 1.0000000
C S
0.48475401370E-01 1.0000000
C P
34.697232244 0.53333657805E-02
7.9582622826 0.35864109092E-01
2.3780826883 0.14215873329
0.81433208183 0.34270471845
C P
0.28887547253 1.0000000
C P
0.10056823671 1.0000000
C D
1.0970000000 1.0000000
C D
0.31800000000 1.0000000
C D
0.90985336424E-01 1.0000000
C F
0.76100000000 1.0000000
#BASIS SET: (12s,7p,3d,1f) -> [6s,4p,3d,1f]
O S
27032.3826310 0.21726302465E-03
4052.3871392 0.16838662199E-02
922.32722710 0.87395616265E-02
261.24070989 0.35239968808E-01
85.354641351 0.11153519115
31.035035245 0.25588953961
O S
12.260860728 0.39768730901
4.9987076005 0.24627849430
O S
1.1703108158 1.0000000
O S
0.46474740994 1.0000000
O S
0.18504536357 1.0000000
O S
0.70288026270E-01 1.0000000
O P
63.274954801 0.60685103418E-02
14.627049379 0.41912575824E-01
4.4501223456 0.16153841088
1.5275799647 0.35706951311
O P
0.52935117943 1.0000000
O P
0.17478421270 1.0000000
O P
0.51112745706E-01 1.0000000
O D
2.3140000000 1.0000000
O D
0.64500000000 1.0000000
O D
0.14696477366 1.0000000
O F
1.4280000000 1.0000000
END
scf
thresh 10e-8
end
dft
mult 1
iterations 100
# grid xfine
grid treutler
grid becke
grid lebedev 160 29
tolerances tight # use strict tolerances beginning with first iteration
tolerances accCoul 10
tolerances tol_rho 1e-12
tolerances radius 100.0
convergence energy 1e-8
convergence density 1e-7
convergence gradient 5e-7
xc becke97
decomp
direct
end
tddft
cis
nroots 6
triplet
targetsym none
thresh 1e-6
end
task tddft energy
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