juanes
February 5, 2024, 3:38pm
#1
I am attempting an optimization between the closed-shell singlet surface and the lowest TDDFT triplet with wB97M-V/pcseg-1.
Calculation hangs when attempting to carry out finite difference gradient evaluation for state 0 (closed-shell singlet). (No, not using solvent).
While I dont know what the situations is for gradients for wB97M-V TDDFT, there are analytic gradients for DFT. Why is it attempting a finite difference gradient evaluation for this?
I can do this same computation with CCSD / EOM-CCSD no problem with the X_OPT rems.
I’ll post the input / point of failure briefly.
juanes
February 5, 2024, 3:41pm
#2
$comment
Plain old SCF on the ground state.
$end
$molecule
0 1
Fe
C 1 rFeC_Head
C 1 rFeC_Tail 2 a_CH_CT
C 1 rFeC_Legs 2 a_CH_CL 3 d_CL_Fe_CH_CT
C 1 rFeC_Legs 2 a_CH_CL 3 d_nCL_Fe_CH_CT
O 1 rFeO_Head 3 a_OH_CT 4 d_OH_Fe_CT_CL
O 1 rFeO_Tail 2 a_CH_OT 4 d_OT_Fe_CH_CL
O 1 rFeO_Legs 2 a_CH_OL 3 d_OL_Fe_CH_CT
O 1 rFeO_Legs 2 a_CH_OL 3 d_nOL_Fe_CH_CT
rFeC_Head = 1.79725
rFeC_Tail = 1.86590
rFeC_Legs = 1.85594
rFeO_Head = 2.95282
rFeO_Tail = 3.00647
rFeO_Legs = 3.00400
a_CH_CT = 112.34031
a_OH_CT = 111.71415
a_CH_OT = 109.99256
a_CH_CL = 88.57562
a_CH_OL = 88.46352
d_nCL_Fe_CH_CT = -105.30500
d_nOL_Fe_CH_CT = -106.09600
d_CL_Fe_CH_CT = 105.30500
d_OL_Fe_CH_CT = 106.09600
d_OH_Fe_CT_CL = 94.57550
d_OT_Fe_CH_CL = -105.28450
$end
$rem
METHOD wB97M-V
UNRESTRICTED FALSE
BASIS PCSEG-1
SYMMETRY FALSE
SYM_IGNORE TRUE
GEN_SCFMAN TRUE
SCF_ALGORITHM DIIS_GDM
SCF_CONVERGENCE 8
MAX_SCF_CYCLES 200
MEM_TOTAL 16000
MEM_STATIC 1000
THRESH 14
$end
@@@
$comment
Optimization of the S0/T MECP structure at wB97M-V.
$end
$molecule
0 1
Fe
C 1 rFeC_Head
C 1 rFeC_Tail 2 a_CH_CT
C 1 rFeC_Legs 2 a_CH_CL 3 d_CL_Fe_CH_CT
C 1 rFeC_Legs 2 a_CH_CL 3 d_nCL_Fe_CH_CT
O 1 rFeO_Head 3 a_OH_CT 4 d_OH_Fe_CT_CL
O 1 rFeO_Tail 2 a_CH_OT 4 d_OT_Fe_CH_CL
O 1 rFeO_Legs 2 a_CH_OL 3 d_OL_Fe_CH_CT
O 1 rFeO_Legs 2 a_CH_OL 3 d_nOL_Fe_CH_CT
rFeC_Head = 1.79725
rFeC_Tail = 1.86590
rFeC_Legs = 1.85594
rFeO_Head = 2.95282
rFeO_Tail = 3.00647
rFeO_Legs = 3.00400
a_CH_CT = 112.34031
a_OH_CT = 111.71415
a_CH_OT = 109.99256
a_CH_CL = 88.57562
a_CH_OL = 88.46352
d_nCL_Fe_CH_CT = -105.30500
d_nOL_Fe_CH_CT = -106.09600
d_CL_Fe_CH_CT = 105.30500
d_OL_Fe_CH_CT = 106.09600
d_OH_Fe_CT_CL = 94.57550
d_OT_Fe_CH_CL = -105.28450
$end
$rem
JOBTYPE OPT
METHOD wB97M-V
UNRESTRICTED FALSE
BASIS PCSEG-1
SYMMETRY FALSE
SYM_IGNORE TRUE
GEN_SCFMAN TRUE
SCF_GUESS READ
SCF_ALGORITHM GDM
SCF_CONVERGENCE 8
MAX_SCF_CYCLES 200
CIS_N_ROOTS 2
CIS_TRIPLETS TRUE
CIS_SINGLETS FALSE
MECP_OPT TRUE
MECP_METHODS BRANCHING_PLANE
MECP_PROJ_HESS TRUE
GEOM_OPT_COORDS 0
MECP_STATE1 [0,0]
MECP_STATE2 [1,1]
MEM_TOTAL 16000
MEM_STATIC 1000
THRESH 14
$end
juanes
February 5, 2024, 4:38pm
#3
Hangs here:
---------------------------------------------------
TDDFT/TDA Excitation Energies
---------------------------------------------------
Excited state 1: excitation energy (eV) = -0.0580
Total energy for state 1: -1716.63005405 au
Multiplicity: Triplet
Trans. Mom.: 0.0000 X 0.0000 Y 0.0000 Z
Strength : 0.0000000000
D( 40) --> V( 1) amplitude = 0.2424
D( 41) --> V( 1) amplitude = 0.8861
D( 41) --> V( 9) amplitude = -0.2603
Excited state 2: excitation energy (eV) = 0.7314
Total energy for state 2: -1716.60104318 au
Multiplicity: Triplet
Trans. Mom.: 0.0000 X 0.0000 Y 0.0000 Z
Strength : 0.0000000000
D( 40) --> V( 1) amplitude = 0.8611
D( 40) --> V( 9) amplitude = -0.3190
D( 41) --> V( 1) amplitude = -0.2543
Finite difference gradient evaluation for state 0
Ground state energy = -1716.6279215899
I don’t think the TDDFT analytic gradient is implemented for VV10-containing functionals. For other meta-GGAs the gradient was added in Q-Chem v.5.3
The finite difference error may originate in a recently introduced bug, please contact Q-Chem support to see if there is a workaround.