RT-TDDFT with water (based on a tutorial) not working

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Clicked A Few Times
Threads 4
Posts 13
3:08:11 PM PST - Tue, Nov 29th 2016
Hi,

I am having trouble in running a RT-TDDFT calculation with water.
This is based on a tutorial found at [1].
Here is the input:

echo
start water
title "H2O"
geometry "system" units angstroms print xyz autosym
  O        0.00000       -0.39574        0.00000
  H       -0.76347        0.20098        0.00000
  H        0.76347        0.20098        0.00000
end
set geometry "system"
memory 2000 mb
dft
 maxiter 100
 grid fine
 direct
end
# Absorption spectrum with Real-Time TDDFT
# using B3LYP/6-31G*/smd=water//B3LYP/6-31G*
# (see DOI: 10.1021/ct200137z and DOI: 10.1021/acs.jpclett.6b00282).
#
# We compute x, y, and z kick simulations with the following parameters:
#      total time:     500.0 au =   12.095 fs
#       time step:       0.2 au = 0.004838 fs
#  field strength:    0.0001 au = 0.05142 V/nm
basis
 * library 6-31G*
end
driver
 maxiter 50
end
dft
 xc B3LYP
end
task dft optimize
# task dft frequencies
cosmo
 do_cosmo_smd true
 solvent water
end
task dft energy
# task dft frequencies
unset rt_tddft:*
rt_tddft
 tmax 500.0
 dt 0.2
 tag "kick_x"
 field "kick"
  type delta
  polarization x
  max 0.0001
 end
 excite "system" with "kick"
end
task dft rt_tddft
unset rt_tddft:*
rt_tddft
 tmax 500.0
 dt 0.2
 tag "kick_y"
 field "kick"
  type delta
  polarization y
  max 0.0001
 end
 excite "system" with "kick"
end
task dft rt_tddft
unset rt_tddft:*
rt_tddft
 tmax 500.0
 dt 0.2
 tag "kick_z"
 field "kick"
  type delta
  polarization z
  max 0.0001
 end
 excite "system" with "kick"
end
task dft rt_tddft


Everything works smoothly until the first 
task dft rt_tddft
.
Here is the output from RT-TDDFT:

 *************************
 * 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      0.00     -0.02
=============== 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 = ( 0.0000E+00,  0.0000E+00, -1.0153E-01)
     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] = 5.0919E-01
     norm[Q_xz] = 1.3002E+00
     norm[Q_yy] = 1.5501E+00
     norm[Q_yz] = 4.6295E-01
     norm[Q_zz] = 2.8298E+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       -3.83853656E-01
         5        2.00       -3.02592866E-01
         6        0.00        8.54131625E-02
         7        0.00        1.72049059E-01
         8        0.00        7.74796640E-01
         9        0.00        8.50198696E-01
        10        0.00        8.74323469E-01
        11        0.00        8.89001705E-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
 ------------------------------------------------------------------------
 zfock_cs_build: not working with symmetry                   0
 ------------------------------------------------------------------------
 zfock_cs_build: not working with symmetry                   0
 ------------------------------------------------------------------------
 zfock_cs_build: not working with symmetry                   0
 ------------------------------------------------------------------------
 ------------------------------------------------------------------------
 zfock_cs_build: not working with symmetry                   0
 ------------------------------------------------------------------------
 zfock_cs_build: not working with symmetry                   0
 ------------------------------------------------------------------------
 ------------------------------------------------------------------------
 zfock_cs_build: not working with symmetry                   0
 zfock_cs_build: not working with symmetry                   0
 ------------------------------------------------------------------------
 ------------------------------------------------------------------------
  current input line : 
 zfock_cs_build: not working with symmetry                   0
 ------------------------------------------------------------------------
 ------------------------------------------------------------------------
  current input line : 
     0: 
 ------------------------------------------------------------------------
 ------------------------------------------------------------------------
 This error has not yet been assigned to a category
 ------------------------------------------------------------------------
 For more information see the NWChem manual at http://www.nwchem-sw.org/index.php/NWChem_Documentation
 ------------------------------------------------------------------------
  current input line : 
    74: task dft rt_tddft
 ------------------------------------------------------------------------
 ------------------------------------------------------------------------
 This error has not yet been assigned to a category
 ------------------------------------------------------------------------
 For more information see the NWChem manual at http://www.nwchem-sw.org/index.php/NWChem_Documentation
 ------------------------------------------------------------------------
  current input line : 
     0: 
 ------------------------------------------------------------------------
 ------------------------------------------------------------------------
 This error has not yet been assigned to a category
 ------------------------------------------------------------------------
 For more information see the NWChem manual at http://www.nwchem-sw.org/index.php/NWChem_Documentation
  current input line : 
     0: 
 ------------------------------------------------------------------------
 ------------------------------------------------------------------------
 This error has not yet been assigned to a category
 ------------------------------------------------------------------------
 For more information see the NWChem manual at http://www.nwchem-sw.org/index.php/NWChem_Documentation
 ------------------------------------------------------------------------
  current input line : 
     0: 
 ------------------------------------------------------------------------
 ------------------------------------------------------------------------
 This error has not yet been assigned to a category
 ------------------------------------------------------------------------
 For more information see the NWChem manual at http://www.nwchem-sw.org/index.php/NWChem_Documentation
  current input line : 
     0: 
 ------------------------------------------------------------------------
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 This error has not yet been assigned to a category
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 For more information see the NWChem manual at http://www.nwchem-sw.org/index.php/NWChem_Documentation
     0: 
 ------------------------------------------------------------------------
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 This error has not yet been assigned to a category
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 For more information see the NWChem manual at http://www.nwchem-sw.org/index.php/NWChem_Documentation
 For further details see manual section: No section for this category                                                                                                                                                                                                                                   
 For further details see manual section: No section for this category                                                                                                                                                                                                                                   
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  current input line : 
     0: 
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 This error has not yet been assigned to a category
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 For more information see the NWChem manual at http://www.nwchem-sw.org/index.php/NWChem_Documentation
 For further details see manual section: No section for this category


Not only the error intrigues me, but what is the reason for the first and last warnings (repeated below)?

(
****************************** WARNING ******************************
  SCF did not converge previously--it is quite likely that
  the starting density is not in the ground state
*********************************************************************
...
****************************** WARNING ******************************
  Starting movecs not specified--trying SCF output:
   ./water.movecs
*********************************************************************
)

Does anybody know something about it?

All the best,
Felipe

Clicked A Few Times
Threads 4
Posts 13
3:19:40 PM PST - Tue, Nov 29th 2016
It occurred to me that this could be due to symmetry.
Changing 
geometry "system" units angstroms print xyz autosym
to 
geometry "system" units angstroms print xyz noautosym
has "solved" the issue.

But the warnings remain.

Furthermore, does anyone knows why I am having two geometries being propagated? Some output has been gathered below:

Geometry initialization (also appears in the last post):

...
 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
=======================================================
...


(why a geometry called driverinitial with three atoms but no basis function?)

Initial propagation:

...
kick_x      0.00000        ### Propagation started ###
kick_x      0.00000        ### Checks passed ###
kick_x      0.00000   0.000000000000E+000   0.000000000000E+000   0.000000000000E+000     # Applied E-field [driverinitial] (alpha spin)
kick_x      0.00000   0.000000000000E+000   0.000000000000E+000   0.000000000000E+000     # Applied E-field [driverinitial] (beta spin)
kick_x      0.00000   1.000000000000E-004   0.000000000000E+000   0.000000000000E+000     # Applied E-field [system] (alpha spin)
kick_x      0.00000   1.000000000000E-004   0.000000000000E+000   0.000000000000E+000     # Applied E-field [system] (beta spin)
kick_x      0.00000   9.087057941008E+000     # Enuc
kick_x      0.00000  -1.230318047252E+002     # Ecore
kick_x      0.00000   4.688799160678E+001     # Ecoul
kick_x      0.00000  -9.349754548525E+000     # Exc(1)
kick_x      0.00000   0.000000000000E+000     # Exc(2)
kick_x      0.00000  -7.640650972596E+001     # Etot
kick_x      0.00000  -7.105427357601E-014     # Eadded
kick_x      0.00000   0.000000000000E+000   0.000000000000E+000   0.000000000000E+000     # Dipole moment [driverinitial]
kick_x      0.00000   4.723066256210E-011   9.823580546607E-001  -1.338243279755E-015     # Dipole moment [system]
kick_x      0.00000        ### Saved restart point ###
kick_x      0.00000   3.887855970497E-008     # Magnus interpol (matrix 1 of 1)
kick_x      0.00000                     2     # Magnus total interpolations
kick_x      0.20000   0.000000000000E+000   0.000000000000E+000   0.000000000000E+000     # Applied E-field [driverinitial] (alpha spin)
kick_x      0.20000   0.000000000000E+000   0.000000000000E+000   0.000000000000E+000     # Applied E-field [driverinitial] (beta spin)
kick_x      0.20000   0.000000000000E+000   0.000000000000E+000   0.000000000000E+000     # Applied E-field [system] (alpha spin)
kick_x      0.20000   0.000000000000E+000   0.000000000000E+000   0.000000000000E+000     # Applied E-field [system] (beta spin)
kick_x      0.20000   9.087057941008E+000     # Enuc
kick_x      0.20000  -1.230310160680E+002     # Ecore
kick_x      0.20000   4.688722099854E+001     # Ecoul
kick_x      0.20000  -9.349772627629E+000     # Exc(1)
kick_x      0.20000   0.000000000000E+000     # Exc(2)
kick_x      0.20000  -7.640650975607E+001     # Etot
kick_x      0.20000  -3.010447358065E-008     # Eadded
kick_x      0.20000   0.000000000000E+000   0.000000000000E+000   0.000000000000E+000     # Dipole moment [driverinitial]
kick_x      0.20000   8.133903820679E-006   9.776107816813E-001  -1.246510265411E-015     # Dipole moment [system]
kick_x      0.20000   3.902881728912E-008     # Magnus interpol (matrix 1 of 1)
...


Thank you all in advance!

All the best,
Felipe

Gets Around
Threads 1
Posts 165
10:28:02 AM PST - Wed, Nov 30th 2016
You are correct that in the first case symmetry was the problem. The code is currently not set up to use symmetry in the calculation of the Fock matrix, and so symmetry needs to be turned off.

The "SCF did not converge..." warning is triggered by the RT-TDDFT code finding that the dft:converged flag in the RTDB is set to false. If the SCF calculation before the RT-TDDFT calculation did converge, then there is potentially a bug in the code where that flag is not getting set correctly. If the MO energies and total energy at the beginning of the RT-TDDFT calculation match those from the SCF calculation, then this is probably a harmless bug in this circumstance.

The "Starting movecs not specified..." warning is simply telling you that you did not make use of the load keyword in the RT-TDDFT input and the code is going with the default starting point of the output from the previous SCF calculation.

Finally, you do not have two geometries being propagated. Only the system specified by the last set geometry directive is being propagated. However, the RT-TDDFT code is set up to compute properties for any geometry that it finds in the RTDB. This is a convenience for a calculation like the charge transfer example in the RT-TDDFT documentation, but does make for slightly odd looking output in other cases.

Clicked A Few Times
Threads 4
Posts 13
11:37:59 AM PST - Wed, Nov 30th 2016
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
Edited On 11:39:08 AM PST - Wed, Nov 30th 2016 by Dudektria

Gets Around
Threads 1
Posts 165
12:19:16 PM PST - Wed, Nov 30th 2016
It does appear that the RT-TDDFT code is picking up the correct information from the SCF calculation (for the total energy, you can look at the total energy reported at time 0 in the propagation if you are having the code print the energy at every step). There must be a small bug somewhere in which the converged flag is getting set to false during the initialization of the RT-TDDFT calculation when COSMO is active.

From a technical perspective, I do believe the RT-TDDFT calculation will work with COSMO in the sense that the code won't crash. I don't believe that this combination was ever tested thoroughly so I advise testing and carefully checking results against some baseline. Beyond whether the code will run or not though, I strongly advise that you do a literature search on RT-TDDFT combined with implicit solvent models if you have not already done so. There are several aspects that should be considered when combining these methods. For instance, while the ground state was solved using the static dielectric constant of water (~78), it is the optical or high-frequency dielectric constant of water (~2) that would be appropriate when propagating the electronic system.

Clicked A Few Times
Threads 4
Posts 13
2:04:44 PM PST - Wed, Nov 30th 2016
Thanks again for the reply, I will look into that.


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