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10:25:49 AM PST  Wed, Nov 20th 2013 

Dear all,
I've again a problem with the OCCUP keyword:
I want to do a rtTDDFT calculation for an excited molecule. Therefore I use the following (shortened) inputfile:
title "Cu oxo TDB3LYP excitation"
echo
scratch_dir /tmp/Nwchem
memory total 2500 mb
start Cu_oxo
geometry "system" units angstroms nocenter noautoz noautosym
Cu 1.37626700 0.00002100 0.00022800
[...]
H 2.85367600 1.70711100 1.06158200
end
basis
* library ccpvdz file /pc2work/anlu/nwchem6.3src.20130528/src/basis/libraries/
end
charge 2
dplot
TITLE CU
vectors "CU_ground.movecs"
LimitXYZ
8.0 8.0 100
8.0 8.0 100
8.0 8.0 100
spin total
gaussian
output Dichte_ref_groundstate.cube
end
dft
odft
xc b3lyp
mult 1
maxiter 400
vectors input atomic output "CU_ground.movecs"
end
## Compute ground state of the system
task dft energy
task dplot
unset dft:*
OCCUP
72 72
1.0 1.0 #Orbital 1
1.0 1.0
1.0 1.0
1.0 1.0
1.0 1.0 #Orbital 5
[...]
1.0 1.0 #Orbital 60
1.0 1.0
1.0 1.0
0.070086937 1.0
1.0 1.0
1.0 1.0 # 65
1.0 1.0
1.0 1.0
0.940028887 1.0
1.0 1.0
1.0 1.0 #Orbital 70
0.929913062 0.0
0.062511272 0.0
end
dft
odft
xc b3lyp
mult 1
maxiter 400
vectors input "CU_ground.movecs" output "Cu_oxo.movecs"
noscf
end
task dft energy
unset dplot:*
dplot
TITLE CU
LimitXYZ
8.0 8.0 100
8.0 8.0 100
8.0 8.0 100
spin total
gaussian
end
rt_tddft
tmax 300.0
dt 0.2
load vectors "Cu_oxo.movecs"
print *
visualization
tstart 0.0 # start visualization at this time
tend 299.8 # stop visualization at this time
dplot # postprocess density matrices into cube files after propagation
end
end
task dft rt_tddft
(The basic idea is to calculate the groundstate and occupy higher orbitals with the OCCUPkeyword afterwards. This is done in a noSCF calculation. The output for the rtTDDFT calculation is then:
Open shell propagation

Initial state: Imported open shell MO eigenvectors

Vector Occupation Eigenvalue [au]

1 1.00 3.23392348E+02
2 1.00 3.23392345E+02
[...]
63 0.07 6.22068371E01
64 1.00 6.06523644E01
65 1.00 6.06305144E01
66 1.00 5.77292864E01
67 1.00 5.76451052E01
68 0.94 5.55072444E01
69 1.00 5.52763761E01
70 1.00 5.23793842E01
71 0.93 4.04032406E01
72 0.06 3.96755861E01
73 0.00 2.56850444E01
[...]
Vector Occupation Eigenvalue [au]

1 1.00 3.23392348E+02
2 1.00 3.23392345E+02
[...]
Integral file = /tmp/Nwchem/Cu_oxo.aoints.0
Record size in doubles = 65536 No. of integs per rec = 32766
Max. records in memory = 0 Max. records in file = 2526
No. of bits per label = 16 No. of bits per value = 64
#quartets = 2.284D+07 #integrals = 5.884D+08 #direct = 1.1% #cached = 98.9%
Grid_pts file = /tmp/Nwchem/Cu_oxo.gridpts.0
Record size in doubles = 12289 No. of grid_pts per rec = 3070
Max. records in memory = 39 Max. recs in file = 2219
<rt_tddft>: 0.00000 ### Propagation started ###
<rt_tddft>: 0.00000 ### Checks passed ###
<rt_tddft>: 0.00000 ### Saved density matrix snapshot ###
<rt_tddft>: 0.00000 2.587733604000E+003 # CPU time
<rt_tddft>: 0.00000 1.597777275029E+003 # Enuc
<rt_tddft>: 0.00000 8.437766477621E+003 # Ecore
<rt_tddft>: 0.00000 3.233989488196E+003 # Ecoul
<rt_tddft>: 0.00000 2.062673754170E+002 # Exc(1)
<rt_tddft>: 0.00000 0.000000000000E+000 # Exc(2)
<rt_tddft>: 0.00000 3.812267089813E+003 # Etot
<rt_tddft>: 0.00000 1.615626388229E008 # Eadded
<rt_tddft>: 0.00000 7.000000000000E+001 # Charge [system] (alpha spin)
<rt_tddft>: 0.00000 7.000000000000E+001 # Charge [system] (beta spin)
<rt_tddft>: 0.00000 1.400000000000E+002 # Charge [system] (total spin)
<rt_tddft>: 0.00000 [...] all lower Orbitals nearly 1.0, Orbital 70: 9.999999551251E001
Orbital 71: 1.603641419205E007
# MO Occupations (alpha spin)
[...]
I'm focusing on the occupation of the 71th orbital: rtTDDFT seems to read the correct occupation (0.93) from the file. I expect to have nearly the same occupation for the timestep t=0. But as you can see in the output the occupation decreased from 0.93 to 1.603641419205E007  why? Furthermore if I subtract the written charge density for the timestep t=0 from the charge density of the groundstate there are NO differences in the cubefiles (not even in the last digit).
Can you tell me what I did wrong? Or is rtTDDFT not able to work together with the OCCUPkeyword?
Thank you very much for help :)
Andreas




Lopata Forum:Admin, Forum:Mod, bureaucrat, sysop


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6:28:24 PM PST  Wed, Nov 27th 2013 

Hi Andreas,
RTTDDFT has not been tested to use occup, but it *might* work.
After doing a noscf occup, and using these vectors to start propagation (with no external electric field), you should see a strange strongly oscillating dipole moment, as you slingshot away from the nonground state initial condition. If you don't use occup (or alternatively just fill up as in the ground state) you should see no dipole oscillations. This tells you that you are indeed pulling in the manually occup'd movecs. Whether or not the resulting dynamics are what you think is something else.
I suspect that the printed movecs might also be incorrect as they are projected onto the initial condition rather than the true ground state.
Email me and we can do some simple tests: klopata AT lsu DOT edu
Ken




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8:13:48 AM PDT  Tue, Mar 17th 2015 

Dear all,
I'm having the same problem (I'm using NWChem 6.3), that is: after a dft calculation I would like to change the occupation of some molecular orbitals and to start a realtime tddft run from the new density matrix "prepared" by changing the occupations.
Is this problem solved in the latest version of NWChem?
I'm copying below my input file.
Thanks for helping,
Silvio Pipolo
memory total 60000 mb
title "glycine oscillations "
echo
scratch_dir ./scratch
permanent_dir ./perm
start glycine
geometry "system" units angstroms nocenter noautoz noautosym
N 1.42928993 0.53588866 0.16209488
C 0.00942352 0.36933896 0.35615339
C 0.63280074 0.51910412 0.70437903
O 0.17821196 1.55581092 1.03380996
O 1.73878613 0.37908690 1.17319014
H 0.30721968 2.07822587 1.69971857
H 0.30592455 0.06898761 1.32949131
H 0.50584431 1.34035573 0.28276602
H 1.88943346 0.37006702 0.21938048
H 1.80706357 1.10969910 0.91321162
end
set geometry "system"
basis
* library 631G*
end
dft
xc b3lyp
vectors output "gly.movecs"
end
task dft energy
OCCUP
21
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.0
1.0
end
dft
xc b3lyp
noscf # do not relax the electron density
vectors input "gly.movecs" output "glymod.movecs"
end
task dft energy
rt_tddft
tmax 2000.0
dt 0.2
print dipole field energy convergence moocc
load vectors "glymod.movecs"
end
task dft rt_tddft




Niri Forum:Admin, Forum:Mod, NWChemDeveloper, bureaucrat, sysop


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10:53:08 AM PDT  Tue, Mar 17th 2015 

Hi Silvio,
This should work. Here's a small closed shell example that works:
echo
start water
geometry "system" units angstroms nocenter noautoz noautosym
O 0.00000000 0.00001441 0.34824012
H 0.00000000 0.76001092 0.93285191
H 0.00000000 0.75999650 0.93290797
end
set geometry "system"
basis
* library 631G
end
occup
6 0
2.0
2.0
2.0
2.0
1.0
1.0
end
dft
xc b3lyp
vectors output occup1.mos
end
task dft
dft
xc b3lyp
vectors input occup1.mos
noscf
end
task dft
unset rt_tddft:*
rt_tddft
load vectors occup1.mos
tmax 200.0
dt 0.2
nrestarts 0
tag "kickx"
print dipole
field "kick"
type delta
polarization x
max 0.001
end
excite "system" with "kick"
end
task dft rt_tddft
Here's an occup example for an open shell:
occup
6 6
1 1
1 1
1 1
1 1
1 0
0 1
end
Let us know or email me directly at niri.govind@pnnl.gov if there are any issues.
Best,
Niri Govind




Niri Forum:Admin, Forum:Mod, NWChemDeveloper, bureaucrat, sysop


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11:11:13 AM PDT  Tue, Mar 17th 2015 

Hi Silvio,
I think the problem in your case is in your occup block. See my example.
Best,
Niri




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8:56:42 AM PDT  Mon, Jun 22nd 2015 

Hi,
sorry to interrupt.But I want to ask if your dplot is working in RT_TDDFT?
Mine do not read dplot block for rt_tddft calculation.
Thanks



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