Possible Bug in NWCHEM: TD-B97


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Just Got Here
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