Dear all,
I've again a problem with the OCCUP keyword:
I want to do a rt-TDDFT calculation for an excited molecule. Therefore I use the following (shortened) input-file:
title "Cu oxo TD-B3LYP 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 cc-pvdz file /pc2work/anlu/nwchem-6.3-src.2013-05-28/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 # post-process 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 OCCUP-keyword afterwards. This is done in a noSCF calculation. The output for the rt-TDDFT 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 -6.22068371E-01
64 1.00 -6.06523644E-01
65 1.00 -6.06305144E-01
66 1.00 -5.77292864E-01
67 1.00 -5.76451052E-01
68 0.94 -5.55072444E-01
69 1.00 -5.52763761E-01
70 1.00 -5.23793842E-01
71 0.93 -4.04032406E-01
72 0.06 -3.96755861E-01
73 0.00 -2.56850444E-01
[...]
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 1.615626388229E-008 # 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: 9.999999551251E-001
Orbital 71: 1.603641419205E-007
# MO Occupations (alpha spin)
[...]
I'm focusing on the occupation of the 71th orbital: rt-TDDFT 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 1.603641419205E-007 - 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 rt-TDDFT not able to work together with the OCCUP-keyword?
Thank you very much for help :-)
Andreas
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