I am trying to do some DFT calculations involving a tungsten complex, specifically the addition to H2 to trans-(iPr3P)2W(CO)3 – this is reaction #7 in the MOR41 database of Dohm et al. (JCTC, 2018, 14, 2596 - for which I have prepared a PSI4 database). I would like to be using some of the newer functionals available through libxc.
I am using Psi4 version 1.2.1 installed though miniconda.
I started with B3LYP for testing purposes. With the def2-SVP basis set I get reasonable results (see Table below). When I switch to the larger def2-TZVP basis set, the error is quite significant and repulsive, and with def2-TZVPP the error is completely ridiculous. I double-checked the basis set included against that in the EMSL basis set exchange and confirmed that they are the same. I did notice that Gaussian16 has a different ECP (notably lmax=5 instead of lmax=3 in PSI4) but using this ECP in PSI4 (I edited the basis set file) with the def2-TZVP basis set did not help. I also tried using Hartree-Fock but got the same problem. To me, this naïvely suggests a problem with the integral code; the problem with HF indicates that this cannot be a grid issue. However, what is weird is that I have only seen this problem with W - MOR41 includes many of the transition metals, but the problem only seems to occur with W.
The energies obtained from the calculations and the corresponding binding energies are:
reactant product H2 ∆E
B3LYP/SVP -1800.179680 -1801.373734 -1.173627 -12.82
B3LYP/TZVP -1802.065479 -1803.088290 -1.179675 98.43
B3LYP/TZVPP -1806.220179 -1805.715773 -1.180027 1057.00
B3LYP/TZVP(run with G16)-1801.629069 -1802.827269 -1.180004 -11.42
B3LYP/TZVP(G16ECP) -1792.608765 -1793.612183 -1.179675 110.60
HF/TZVP -1792.860925 -1793.757451 -1.132519 148.09
HF/SVP -1791.168218 -1792.310048 -1.128942 -8.09
HF/TZVPP -1796.679676 -1796.679676 -1.132944 710.93 0.00
reference (from Dohm et al.) -16.2
Any help on resolving this issue would be appreciated. Attached are my input files (B3LYP/def2-TZVP).
Thanks in advance for your assistance.
Sincerely yours,
Mark.
Input file: reactant
# This is a psi4 input file auto-generated from the database() wrapper.
core.print_out('\n')
p4util.banner(' Database MOR41 Computation: Reagent MOR41-ED07-reagent \n ')
core.print_out('\n')
molecule dbmol {
units Angstrom
no_com
no_reorient
0 1
W 0.090640800000 0.066260000000 -0.088000300000
C 0.106952100000 -1.928814200000 -0.466549400000
O 0.096133700000 -3.065375600000 -0.740415000000
C 0.028274400000 0.379980900000 -1.997828000000
O 0.028029300000 0.578417300000 -3.159275700000
C -0.093307900000 2.080442700000 0.142785900000
O -0.257037700000 3.235495700000 0.206221600000
P -2.383484100000 -0.093746500000 0.193528000000
C -2.920792500000 -0.437281000000 1.956908800000
H -4.016616300000 -0.455293800000 1.975816700000
C -3.316389800000 1.491151500000 -0.179503100000
H -2.732679400000 2.213265400000 0.405760500000
C -3.171527500000 -1.529706200000 -0.720131900000
H -2.611149500000 -2.369346900000 -0.287224300000
C 3.519099200000 -1.266466700000 -0.796919500000
P 2.532536100000 -0.033802100000 0.199724100000
H 3.444524000000 -0.211399300000 2.511588000000
H 3.107501500000 -2.219452200000 -0.441725700000
C 3.585414000000 1.508545400000 0.239418500000
H 4.620761700000 1.185809300000 0.407929600000
C -3.188174200000 1.901699700000 -1.653699400000
H -3.484484300000 2.950588100000 -1.768427500000
H -3.845391300000 1.299978000000 -2.288545900000
H -2.164782300000 1.791235700000 -2.018112000000
C -4.776111600000 1.586022800000 0.287039300000
H -5.430390800000 0.926602700000 -0.288175000000
H -5.131429100000 2.613182000000 0.138362200000
H -4.897503100000 1.346733800000 1.347270300000
C -4.665911000000 -1.776671700000 -0.470122300000
H -4.929291900000 -1.762487500000 0.591439900000
H -4.941115900000 -2.760855300000 -0.868429500000
H -5.281061700000 -1.033761700000 -0.985240800000
C -2.870200200000 -1.526003600000 -2.225596100000
H -3.144218800000 -2.498142700000 -2.651782600000
H -1.812675800000 -1.348054600000 -2.425012500000
H -3.448170400000 -0.758446700000 -2.747043500000
C -2.408396600000 -1.803345600000 2.432906700000
H -2.872536800000 -2.627943400000 1.884708800000
H -2.631951200000 -1.938346500000 3.497793800000
H -1.323907900000 -1.887034700000 2.300676200000
C -2.438924400000 0.690855900000 2.879924400000
H -1.350131300000 0.797763100000 2.830651500000
H -2.713842600000 0.472510200000 3.918633000000
H -2.876995800000 1.656057300000 2.609917300000
C 5.027356300000 -1.245450500000 -0.518440400000
H 5.252864000000 -1.270709500000 0.553401900000
H 5.493823500000 -0.349511700000 -0.941425500000
H 5.505229900000 -2.115642400000 -0.983606400000
C 3.211772300000 -1.184836700000 -2.299117800000
H 3.611414100000 -0.271091500000 -2.747925100000
C 1.275062600000 -0.181216800000 2.574089300000
H 2.135619700000 -1.206862800000 -2.482717000000
H 3.670616200000 -2.038173500000 -2.812060800000
C 2.705816400000 -2.193295000000 2.086512200000
H 0.415776100000 -0.627664700000 2.006295600000
H 1.117135600000 -0.557046900000 3.593282600000
H 1.188968300000 0.905789500000 2.590191600000
C 2.605867800000 -0.667968300000 1.970815600000
H 2.602648800000 -2.490168400000 3.137199300000
H 3.666061900000 -2.571011900000 1.726042600000
H 1.908387600000 -2.684812300000 1.519271800000
C 3.176687800000 2.445829000000 1.383263000000
H 2.128772900000 2.744492100000 1.290794200000
H 3.786333900000 3.356035300000 1.342193600000
H 3.326985000000 1.990449400000 2.366969500000
C 3.486197100000 2.235599400000 -1.109636000000
H 2.440861800000 2.462784300000 -1.343426600000
H 3.892085500000 1.637683200000 -1.929626800000
H 4.044777600000 3.178009400000 -1.068198700000
}
core.set_memory_bytes(15000000000)
core.set_global_option('BASIS', 'DEF2-TZVP')
core.set_global_option('GUESS', 'GWH')
core.set_global_option('MAXITER', 1000)
core.set_global_option('WRITER_FILE_LABEL', 'MOR41-ED07-reagent')
pickle_kw = ("""(dp0
S'db_func'
p1
cpsi4.driver.driver
energy
p2
sS'db_name'
p3
S'MOR41'
p4
sS'db_mode'
p5
S'sow'
p6
sS'name'
p7
S'B3LYP'
p8
s.""")
kwargs = pickle.loads(pickle_kw)
electronic_energy = energy(**kwargs)
core.print_variables()
core.print_out('\nDATABASE RESULT: computation 11258 for reagent MOR41-ED07-reagent yields electronic energy %20.12f\n' % (electronic_energy))
core.set_variable('NATOM', dbmol.natom())
input file: product
# This is a psi4 input file auto-generated from the database() wrapper.
core.print_out('\n')
p4util.banner(' Database MOR41 Computation: Reagent MOR41-PR07-reagent \n ')
core.print_out('\n')
molecule dbmol {
units Angstrom
no_com
no_reorient
0 1
W -0.000070400000 -0.017989600000 -0.146457100000
C 0.000157200000 1.955377300000 -0.631545200000
O 0.000411800000 3.068043100000 -0.986288700000
C 0.000004600000 0.271128000000 1.825131000000
O 0.000003100000 0.436870000000 2.983755900000
C 0.000079000000 -2.055167300000 -0.056719200000
O 0.000369700000 -3.220382300000 -0.103637600000
H 0.422788400000 -0.287137400000 -1.984721800000
H -0.422970800000 -0.287404200000 -1.985319300000
P -2.498968200000 0.054091800000 -0.052469100000
C -3.398360300000 -0.535031900000 -1.584174500000
H -4.468441100000 -0.526892600000 -1.348265500000
C -3.356878400000 -0.865573300000 1.355714100000
H -3.371868200000 -0.108729700000 2.151443200000
C -3.157712400000 1.802287600000 0.144667000000
H -2.704252500000 2.317272900000 -0.711479200000
C 3.158107500000 1.802481500000 0.146809300000
P 2.499417800000 0.054538100000 -0.052471700000
H 4.468463700000 -0.525230000000 -1.349702400000
H 2.705790900000 2.318402900000 -0.709381300000
C 3.358098800000 -0.866609200000 1.354368100000
H 3.374620800000 -0.110180300000 2.150474500000
C -4.805511900000 -1.297741000000 1.073085200000
H -5.254728700000 -1.674152000000 1.999881200000
H -4.835629400000 -2.112614900000 0.342511600000
H -5.434310400000 -0.486090300000 0.702882400000
C -2.560531500000 -2.067317500000 1.879344900000
H -3.061648100000 -2.475072300000 2.765696100000
H -1.542735600000 -1.790111500000 2.156345200000
H -2.501752200000 -2.863967000000 1.131819400000
C -4.680578800000 1.979997900000 0.065888300000
H -4.916432600000 3.048909800000 -0.001308900000
H -5.169896500000 1.596146400000 0.966264000000
H -5.123495400000 1.487333900000 -0.804742400000
C -2.618029800000 2.465249900000 1.419594100000
H -2.906610500000 3.522573500000 1.432737600000
H -1.529918400000 2.405362800000 1.476662200000
H -3.033061600000 1.997312800000 2.319029600000
C -3.156120400000 0.402360000000 -2.773590000000
H -3.624805500000 -0.011995200000 -3.673909400000
H -2.084672200000 0.514366300000 -2.975522500000
H -3.570938900000 1.399990900000 -2.605324600000
C -2.983408700000 -1.970962500000 -1.930114600000
H -3.139122600000 -2.660074400000 -1.095275000000
H -1.922494900000 -2.013238900000 -2.196445300000
H -3.565671300000 -2.333115000000 -2.785725800000
C 4.681143700000 1.979452700000 0.069932400000
H 5.169200400000 1.594107000000 0.970364900000
H 4.917733700000 3.048301200000 0.004377900000
H 5.124722600000 1.487610300000 -0.800835900000
C 2.617304900000 2.464485800000 1.421754200000
H 3.030128100000 1.994753700000 2.321273700000
C 2.982560800000 -1.967591100000 -1.933470700000
H 1.529026700000 2.406081300000 1.476946600000
H 2.907394000000 3.521374000000 1.436786500000
C 3.156164200000 0.407188300000 -2.773025600000
H 1.921746200000 -2.008793700000 -2.200354200000
H 3.564969200000 -2.328960800000 -2.789307000000
H 3.137352200000 -2.657957400000 -1.099490900000
C 3.398322700000 -0.532419600000 -1.585326900000
H 3.622375400000 -0.006874700000 -3.674767900000
H 3.573575400000 1.403617700000 -2.603965500000
H 2.084603000000 0.521976000000 -2.972940400000
C 4.806061200000 -1.299837300000 1.069941600000
H 5.255832800000 -1.677434300000 1.995985100000
H 5.435230800000 -0.488422700000 0.699837500000
H 4.834740800000 -2.114113900000 0.338643400000
C 2.561315100000 -2.067960800000 1.878190500000
H 2.501285900000 -2.864212200000 1.130337600000
H 1.543963400000 -1.790105100000 2.156196500000
H 3.062895500000 -2.476510500000 2.763911500000
}
core.set_memory_bytes(15000000000)
core.set_global_option('BASIS', 'DEF2-TZVP')
core.set_global_option('BASIS_GUESS', 'DEF2-SVP')
core.set_global_option('WRITER_FILE_LABEL', 'MOR41-PR07-reagent')
pickle_kw = ("""(dp0
S'db_func'
p1
cpsi4.driver.driver
energy
p2
sS'db_name'
p3
S'MOR41'
p4
sS'db_mode'
p5
S'sow'
p6
sS'name'
p7
S'B3LYP'
p8
s.""")
kwargs = pickle.loads(pickle_kw)
electronic_energy = energy(**kwargs)
core.print_variables()
core.print_out('\nDATABASE RESULT: computation 11258 for reagent MOR41-PR07-reagent yields electronic energy %20.12f\n' % (electronic_energy))
core.set_variable('NATOM', dbmol.natom())
# This is a psi4 input file auto-generated from the database() wrapper.
core.print_out('\n')
p4util.banner(' Database MOR41 Computation: Reagent MOR41-H2-reagent \n ')
core.print_out('\n')
molecule dbmol {
units Angstrom
no_com
no_reorient
0 1
H 0.798743700000 0.046507300000 0.075739400000
H 1.071087200000 0.408924800000 0.665066700000
}
core.set_memory_bytes(15000000000)
core.set_global_option('BASIS', 'DEF2-TZVP')
core.set_global_option('BASIS_GUESS', 'DEF2-SVP')
core.set_global_option('WRITER_FILE_LABEL', 'MOR41-H2-reagent')
pickle_kw = ("""(dp0
S'db_func'
p1
cpsi4.driver.driver
energy
p2
sS'db_name'
p3
S'MOR41'
p4
sS'db_mode'
p5
S'sow'
p6
sS'name'
p7
S'B3LYP'
p8
s.""")
kwargs = pickle.loads(pickle_kw)
electronic_energy = energy(**kwargs)
core.print_variables()
core.print_out('\nDATABASE RESULT: computation 11258 for reagent MOR41-H2-reagent yields electronic energy %20.12f\n' % (electronic_energy))
core.set_variable('NATOM', dbmol.natom())