Hi Sean,
Thanks for the reply!
About the convergence issue, I found the following.
Here is the output from the convergence (in smd=water) and the MO energies reported by the RT-TDDFT module:
...
NWChem DFT Module
-----------------
H2O
Summary of "ao basis" -> "ao basis" (cartesian)
------------------------------------------------------------------------------
Tag Description Shells Functions and Types
---------------- ------------------------------ ------ ---------------------
O 6-31G* 6 15 3s2p1d
H 6-31G* 2 2 2s
solvent parameters
solvname_short: h2o
solvname_long: water
dielec: 78.4000
dielecinf: 1.7769
aqueous SMD model solvent descriptors
dielec: 78.4000
sola: 0.8200
---------------
-cosmo- solvent
---------------
Cosmo: York-Karplus, doi: 10.1021/jp992097l
dielectric constant -eps- = 78.40
screen = (eps-1)/(eps ) = 0.98724
surface charge correction = lagrangian
-lineq- algorithm = 0
-bem- low level = 3
-bem- from -octahedral-
gaussian surface charge width = 0.98000
degree of switching = 1.00000
switching function tolerance = 0.00010
atomic radii =
--------------
1 8.000 1.520
2 1.000 1.200
3 1.000 1.200
solvent accessible surface
--------------------------
---------- ATOMIC COORDINATES (A.U.) ------------ VDWR(ANG.) --
1 -0.00000000 -0.22817117 0.00000000 1.520
2 -1.43912872 0.90343169 0.00000000 1.200
3 1.43912872 0.90343169 0.00000000 1.200
number of segments per atom = 128
number of points per atom = 128
atom ( nspa, nppa )
----------------------
1 ( 84, 0 ) 0
2 ( 72, 0 ) 0
3 ( 72, 0 ) 0
number of -cosmo- surface points = 228
molecular surface = 36.049 angstrom**2
molecular volume = 16.286 angstrom**3
...... end of -cosmo- initialization ......
G(SMD-CDS) energy (kcal/mol) = 1.451
SMD-CDS SASA (angstrom**2) = 55.867
Caching 1-el integrals
General Information
-------------------
SCF calculation type: DFT
Wavefunction type: closed shell.
No. of atoms : 3
No. of electrons : 10
Alpha electrons : 5
Beta electrons : 5
Charge : 0
Spin multiplicity: 1
Use of symmetry is: off; symmetry adaption is: off
Maximum number of iterations: 100
This is a Direct SCF calculation.
AO basis - number of functions: 19
number of shells: 10
Convergence on energy requested: 1.00D-06
Convergence on density requested: 1.00D-05
Convergence on gradient requested: 5.00D-04
XC Information
--------------
B3LYP Method XC Potential
Hartree-Fock (Exact) Exchange 0.200
Slater Exchange Functional 0.800 local
Becke 1988 Exchange Functional 0.720 non-local
Lee-Yang-Parr Correlation Functional 0.810
VWN I RPA Correlation Functional 0.190 local
Grid Information
----------------
Grid used for XC integration: fine
Radial quadrature: Mura-Knowles
Angular quadrature: Lebedev.
Tag B.-S. Rad. Rad. Pts. Rad. Cut. Ang. Pts.
--- ---------- --------- --------- ---------
O 0.60 70 5.0 590
H 0.35 60 6.0 590
Grid pruning is: on
Number of quadrature shells: 190
Spatial weights used: Erf1
Convergence Information
-----------------------
Convergence aids based upon iterative change in
total energy or number of iterations.
Levelshifting, if invoked, occurs when the
HOMO/LUMO gap drops below (HL_TOL): 1.00D-02
DIIS, if invoked, will attempt to extrapolate
using up to (NFOCK): 10 stored Fock matrices.
Damping( 0%) Levelshifting(0.5) DIIS
--------------- ------------------- ---------------
dE on: start ASAP start
dE off: 2 iters 100 iters 100 iters
Screening Tolerance Information
-------------------------------
Density screening/tol_rho: 1.00D-10
AO Gaussian exp screening on grid/accAOfunc: 14
CD Gaussian exp screening on grid/accCDfunc: 20
XC Gaussian exp screening on grid/accXCfunc: 20
Schwarz screening/accCoul: 1.00D-08
Loading old vectors from job with title :
H2O
Time after variat. SCF: 1.9
Time prior to 1st pass: 1.9
Grid_pts file = ./water.gridpts.0
Record size in doubles = 12289 No. of grid_pts per rec = 3070
Max. records in memory = 7 Max. recs in file = 498033
Memory utilization after 1st SCF pass:
Heap Space remaining (MW): 65.45 65447422
Stack Space remaining (MW): 65.54 65535764
convergence iter energy DeltaE RMS-Dens Diis-err time
---------------- ----- ----------------- --------- --------- --------- ------
COSMO gas phase
d= 0,ls=0.0,diis 1 -76.4089539664 -8.55D+01 1.11D-06 5.54D-10 2.1
d= 0,ls=0.0,diis 2 -76.4089539664 -8.16D-12 6.80D-07 4.99D-10 2.1
Memory utilization after 1st SCF pass:
Heap Space remaining (MW): 65.45 65446486
Stack Space remaining (MW): 65.54 65535764
convergence iter energy DeltaE RMS-Dens Diis-err time
---------------- ----- ----------------- --------- --------- --------- ------
COSMO solvation phase
d= 0,ls=0.0,diis 1 -76.4204071046 -1.15D-02 7.84D-03 8.53D-03 2.3
d= 0,ls=0.0,diis 2 -76.4221908241 -1.78D-03 2.00D-03 4.00D-03 2.5
d= 0,ls=0.0,diis 3 -76.4224536808 -2.63D-04 8.78D-04 9.37D-04 2.7
d= 0,ls=0.0,diis 4 -76.4225396238 -8.59D-05 9.25D-05 1.26D-05 2.8
d= 0,ls=0.0,diis 5 -76.4225407800 -1.16D-06 9.09D-06 1.58D-08 3.0
d= 0,ls=0.0,diis 6 -76.4225407834 -3.35D-09 7.78D-07 8.31D-11 3.2
Total DFT energy = -76.422540783370
One electron energy = -123.184436548490
Coulomb energy = 46.888000611769
Exchange-Corr. energy = -9.349755803047
Nuclear repulsion energy = 9.087057941008
COSMO energy = 0.136593015390
Numeric. integr. density = 10.000000401382
Total iterative time = 1.3s
COSMO-SMD solvation results
---------------------------
Reference for the SMD model:
Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378
internal energy in gas <Psi(g)|H|Psi(g)> = -76.4089539664
internal energy in solvent <Psi(s)|H|Psi(s)> = -76.4065098117
delta internal energy = 0.0024441547 ( 1.53 kcal/mol)
total free energy in solvent <Psi(s)|H+V/2|Psi(s)> = -76.4248533812
polarization energy contribution <Psi(s)|V/2|Psi(s)> = -0.0183435695 ( -11.51 kcal/mol)
total free energy in solvent including G(SMD-CDS) = -76.4225407834
G(SMD-CDS) energy contribution = 0.0023125978 ( 1.45 kcal/mol)
1 M fixed-concentration free energy of solvation = -0.0135868169 ( -8.53 kcal/mol)
DFT Final Molecular Orbital Analysis
------------------------------------
Vector 1 Occ=2.000000D+00 E=-1.914063D+01
MO Center= -2.7D-11, -1.2D-01, 2.1D-18, r^2= 1.5D-02
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
1 0.992852 1 O s
Vector 2 Occ=2.000000D+00 E=-9.985629D-01
MO Center= -5.1D-11, 7.1D-02, 1.5D-16, r^2= 5.1D-01
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
2 0.470317 1 O s 6 0.454212 1 O s
1 -0.211394 1 O s
Vector 3 Occ=2.000000D+00 E=-5.148607D-01
MO Center= 1.7D-11, 9.4D-02, 1.3D-18, r^2= 7.7D-01
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
3 0.524511 1 O px 7 0.291988 1 O px
16 -0.229236 2 H s 18 0.229236 3 H s
Vector 4 Occ=2.000000D+00 E=-3.838537D-01
MO Center= -1.7D-11, -2.1D-01, -1.3D-16, r^2= 6.8D-01
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
4 0.558108 1 O py 8 0.393123 1 O py
6 -0.377756 1 O s 2 -0.155296 1 O s
Vector 5 Occ=2.000000D+00 E=-3.025929D-01
MO Center= -2.8D-11, -1.0D-01, 3.1D-16, r^2= 6.0D-01
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
5 0.638025 1 O pz 9 0.513333 1 O pz
Vector 6 Occ=0.000000D+00 E= 8.541316D-02
MO Center= 2.0D-10, 6.2D-01, 1.7D-16, r^2= 2.4D+00
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
6 1.207119 1 O s 17 -0.958008 2 H s
19 -0.958008 3 H s 8 0.470675 1 O py
4 0.256306 1 O py 2 0.150596 1 O s
Vector 7 Occ=0.000000D+00 E= 1.720491D-01
MO Center= -2.5D-10, 5.7D-01, -1.6D-18, r^2= 2.5D+00
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
17 1.263215 2 H s 19 -1.263215 3 H s
7 0.743009 1 O px 3 0.413619 1 O px
Vector 8 Occ=0.000000D+00 E= 7.747966D-01
MO Center= 4.2D-10, 1.3D-01, 1.1D-16, r^2= 1.6D+00
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
16 0.835065 2 H s 18 -0.835065 3 H s
17 -0.626270 2 H s 19 0.626270 3 H s
7 0.493459 1 O px 11 -0.349141 1 O dxy
Vector 9 Occ=0.000000D+00 E= 8.501987D-01
MO Center= -2.4D-10, -4.3D-01, -6.3D-15, r^2= 1.0D+00
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
4 0.895810 1 O py 6 0.833457 1 O s
8 -0.763309 1 O py 2 -0.422092 1 O s
16 -0.304685 2 H s 18 -0.304685 3 H s
10 -0.242525 1 O dxx 17 0.192916 2 H s
19 0.192916 3 H s 13 -0.182921 1 O dyy
Vector 10 Occ=0.000000D+00 E= 8.743235D-01
MO Center= -2.6D-11, -1.2D-01, 5.5D-15, r^2= 1.1D+00
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
9 -1.035316 1 O pz 5 0.963783 1 O pz
Vector 11 Occ=0.000000D+00 E= 8.890017D-01
MO Center= -2.3D-11, 3.2D-01, -8.6D-17, r^2= 1.6D+00
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
6 1.217961 1 O s 16 0.795751 2 H s
18 0.795751 3 H s 2 -0.746716 1 O s
17 -0.637386 2 H s 19 -0.637386 3 H s
8 -0.435707 1 O py 15 -0.341180 1 O dzz
13 -0.207076 1 O dyy
Vector 12 Occ=0.000000D+00 E= 1.060498D+00
MO Center= -1.2D-10, -6.4D-02, 2.9D-16, r^2= 1.5D+00
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
7 1.612257 1 O px 3 -0.993890 1 O px
17 0.968811 2 H s 19 -0.968811 3 H s
Vector 13 Occ=0.000000D+00 E= 1.196550D+00
MO Center= -5.5D-11, 3.7D-01, 5.8D-16, r^2= 1.4D+00
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
6 3.578158 1 O s 2 -1.448156 1 O s
8 1.123420 1 O py 17 -0.788134 2 H s
19 -0.788134 3 H s 10 -0.650623 1 O dxx
4 -0.422192 1 O py 13 -0.397494 1 O dyy
16 -0.335015 2 H s 18 -0.335015 3 H s
Vector 14 Occ=0.000000D+00 E= 1.717409D+00
MO Center= -2.5D-11, -1.6D-01, -1.0D-16, r^2= 6.2D-01
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
13 1.006688 1 O dyy 10 -0.599722 1 O dxx
15 -0.342551 1 O dzz 6 -0.234714 1 O s
Vector 15 Occ=0.000000D+00 E= 1.735678D+00
MO Center= -2.3D-11, -1.2D-01, -1.1D-15, r^2= 6.1D-01
Bfn. Coefficient Atom+Function Bfn. Coefficient Atom+Function
----- ------------ --------------- ----- ------------ ---------------
12 1.732051 1 O dxz
center of mass
--------------
x = -0.00000000 y = -0.10152795 z = 0.00000000
moments of inertia (a.u.)
------------------
2.292227814855 -0.000000000205 0.000000000000
-0.000000000205 4.174595510957 0.000000000000
0.000000000000 0.000000000000 6.466823325813
Multipole analysis of the density
---------------------------------
L x y z total alpha beta nuclear
- - - - ----- ----- ---- -------
0 0 0 0 -0.000000 -5.000000 -5.000000 10.000000
1 1 0 0 0.000000 0.000000 0.000000 -0.000000
1 0 1 0 0.982358 0.500432 0.500432 -0.018506
1 0 0 1 -0.000000 -0.000000 -0.000000 0.000000
2 2 0 0 -3.001548 -3.571865 -3.571865 4.142183
2 1 1 0 0.000000 -0.000000 -0.000000 0.000000
2 1 0 1 -0.000000 -0.000000 -0.000000 0.000000
2 0 2 0 -4.408450 -3.228662 -3.228662 2.048874
2 0 1 1 0.000000 0.000000 0.000000 0.000000
2 0 0 2 -5.371023 -2.685511 -2.685511 0.000000
Task times cpu: 1.3s wall: 2.8s
NWChem Input Module
-------------------
NWChem Real-Time TDDFT Module
-----------------------------
H2O
Summary of "ao basis" -> "ao basis" (cartesian)
------------------------------------------------------------------------------
Tag Description Shells Functions and Types
---------------- ------------------------------ ------ ---------------------
O 6-31G* 6 15 3s2p1d
H 6-31G* 2 2 2s
solvent parameters
solvname_short: h2o
solvname_long: water
dielec: 78.4000
dielecinf: 1.7769
aqueous SMD model solvent descriptors
dielec: 78.4000
sola: 0.8200
---------------
-cosmo- solvent
---------------
Cosmo: York-Karplus, doi: 10.1021/jp992097l
dielectric constant -eps- = 78.40
screen = (eps-1)/(eps ) = 0.98724
surface charge correction = lagrangian
-lineq- algorithm = 0
-bem- low level = 3
-bem- from -octahedral-
gaussian surface charge width = 0.98000
degree of switching = 1.00000
switching function tolerance = 0.00010
atomic radii =
--------------
1 8.000 1.520
2 1.000 1.200
3 1.000 1.200
solvent accessible surface
--------------------------
---------- ATOMIC COORDINATES (A.U.) ------------ VDWR(ANG.) --
1 -0.00000000 -0.22817117 0.00000000 1.520
2 -1.43912872 0.90343169 0.00000000 1.200
3 1.43912872 0.90343169 0.00000000 1.200
number of segments per atom = 128
number of points per atom = 128
atom ( nspa, nppa )
----------------------
1 ( 84, 0 ) 0
2 ( 72, 0 ) 0
3 ( 72, 0 ) 0
number of -cosmo- surface points = 228
molecular surface = 36.049 angstrom**2
molecular volume = 16.286 angstrom**3
...... end of -cosmo- initialization ......
G(SMD-CDS) energy (kcal/mol) = 1.451
SMD-CDS SASA (angstrom**2) = 55.867
Caching 1-el integrals
General Information
-------------------
SCF calculation type: DFT
Wavefunction type: closed shell.
No. of atoms : 3
No. of electrons : 10
Alpha electrons : 5
Beta electrons : 5
Charge : 0
Spin multiplicity: 1
Use of symmetry is: off; symmetry adaption is: off
Maximum number of iterations: 100
This is a Direct SCF calculation.
AO basis - number of functions: 19
number of shells: 10
Convergence on energy requested: 1.00D-06
Convergence on density requested: 1.00D-05
Convergence on gradient requested: 5.00D-04
XC Information
--------------
B3LYP Method XC Potential
Hartree-Fock (Exact) Exchange 0.200
Slater Exchange Functional 0.800 local
Becke 1988 Exchange Functional 0.720 non-local
Lee-Yang-Parr Correlation Functional 0.810
VWN I RPA Correlation Functional 0.190 local
Grid Information
----------------
Grid used for XC integration: fine
Radial quadrature: Mura-Knowles
Angular quadrature: Lebedev.
Tag B.-S. Rad. Rad. Pts. Rad. Cut. Ang. Pts.
--- ---------- --------- --------- ---------
O 0.60 70 5.0 590
H 0.35 60 6.0 590
Grid pruning is: on
Number of quadrature shells: 190
Spatial weights used: Erf1
Convergence Information
-----------------------
Convergence aids based upon iterative change in
total energy or number of iterations.
Levelshifting, if invoked, occurs when the
HOMO/LUMO gap drops below (HL_TOL): 1.00D-02
DIIS, if invoked, will attempt to extrapolate
using up to (NFOCK): 10 stored Fock matrices.
Damping( 0%) Levelshifting(0.5) DIIS
--------------- ------------------- ---------------
dE on: start ASAP start
dE off: 2 iters 100 iters 100 iters
Screening Tolerance Information
-------------------------------
Density screening/tol_rho: 1.00D-10
AO Gaussian exp screening on grid/accAOfunc: 14
CD Gaussian exp screening on grid/accCDfunc: 20
XC Gaussian exp screening on grid/accXCfunc: 20
Schwarz screening/accCoul: 1.00D-08
*************************
* Closed-shell RT-TDDFT *
*************************
****************************** WARNING ******************************
SCF did not converge previously--it is quite likely that
the starting density is not in the ground state
*********************************************************************
****************************** WARNING ******************************
Schwartz screening tolerance is similar to the Magnus interpolation
tolerance--this may cause problems with convergence. If
so, try loosening tol_interpol.
*********************************************************************
Geometry Atoms Basis func. Nuc. charge Nuc. dip. mom.
-----------------------------------------------------------------------------------------
driverinitial 3 (100% ) 0 ( 0% ) 10.00 0.00 0.00 0.00
*system 3 (100% ) 19 (100% ) 10.00 -0.00 -0.02 0.00
=============== Geometry Initialization ===============
Active geometry: "system"
No linear dependencies
Number of atomic orbitals = 19
Number of molecular orbitals = 19
=======================================================
System parameters
-----------------
No. atoms : 3
Wavefunction type : restricted
No. alpha electrons : 5
No. beta electrons : 5
Total no. electrons : 10
System charge : 0
2e integrals
------------
tol2e for real part of Fock matrix: 1.0000E-08
tol2e for imag part of Fock matrix: 1.0000E-10
Propagation parameters
----------------------
End time (tmax) : 5.0000E+02 au = 1.2095E+01 fs
Time step (dt) : 2.0000E-01 au = 4.8378E-03 fs
No. time steps (nt) : 2500
Progagation method : 2nd order Magnus w/ self-consistent interpolation
Exponentiation method : Adaptive contractive power series
Tolerances
----------
Zero / comparison / check tolerance : 1.0000E-08
Series convergence tolerance : 1.0000E-10
Interpolation convergence tolerance : 1.0000E-07
Reqd no. zero terms in series : 3
Reqd no. zero terms in interpolation : 1
Output and checking parameters
------------------------------
Quantites to print : messages, dipole, field, energy, <S^2>
No. print points : 2500 (once every 1 time steps)
No. checks : 10 (once every 250 time steps)
No. restart points : 100 (once every 25 time steps)
Checking level : 1 (checkpoints only)
Profiling : No
Dipole and quadrupole matrices
------------------------------
Center of mass = (-4.1748E-11, -1.0153E-01, 0.0000E+00)
norm[D_x] = 1.4391E+00
norm[D_y] = 1.0184E+00
norm[D_z] = 1.0184E+00
norm[Q_xx] = 3.6212E+00
norm[Q_xy] = 1.3002E+00
norm[Q_xz] = 4.6295E-01
norm[Q_yy] = 2.3663E+00
norm[Q_yz] = 4.6295E-01
norm[Q_zz] = 2.7777E+00
Applied fields
--------------
"kick"
Type : delta
Polarization : x
Field maximum : 1.0000E-04 au = 5.1421E-02 V/nm
Excitation rules
----------------
Excite geometry "system" with "kick"
Closed shell propagation
------------------------
****************************** WARNING ******************************
Starting movecs not specified--trying SCF output:
./water.movecs
*********************************************************************
File name : ./water.movecs
Job title : H2O
Basis set name : ao basis
SCF type : dft
Atomic orbitals : 19
Molecular orbitals : 19
Vector Occupation Eigenvalue [au]
--------------------------------------------
1 2.00 -1.91406328E+01
2 2.00 -9.98562901E-01
3 2.00 -5.14860740E-01
4 2.00 -3.83853655E-01
5 2.00 -3.02592866E-01
6 0.00 8.54131631E-02
7 0.00 1.72049058E-01
8 0.00 7.74796639E-01
9 0.00 8.50198691E-01
10 0.00 8.74323469E-01
11 0.00 8.89001704E-01
12 0.00 1.06049823E+00
13 0.00 1.19655008E+00
14 0.00 1.71740885E+00
15 0.00 1.73567783E+00
16 0.00 1.76590757E+00
17 0.00 2.27515280E+00
18 0.00 2.57191774E+00
19 0.00 3.54163434E+00
Grid_pts file = ./water.gridpts.0
Record size in doubles = 12289 No. of grid_pts per rec = 3070
Max. records in memory = 7 Max. recs in file = 498033
kick_x 0.00000 ### Propagation started ###
kick_x 0.00000 ### Checks passed ###
...
Everything seems converged (DIIS errors are around 1e-10 -- 1e-11, energy deltas are around 1e-9 -- 1e-12, for instance. Those values are for both gas and condensed phases (SMD).), but the output does not say it directly.
MO energies match but RT-TDDFT does not report total energies so I can't compare.
Can this be a bug?
Another question: is it OK to use COSMO/SMD together with RT-TDDFT in NWChem?
Thanks again in advance.
All the best,
Felipe
|