Dear all,
I have been trying to calculate the excitation energies of small polyaromatic hydrocarbon molecules like naphthalene, pyrene etc using the Tamm-Dancoff approximation via the TD-DFT module.
My first benchmark was with the naphthalene cation, for which I managed to reproduce available TD-DFT data from the literature.
In the case of neutral molecules, all of my attempts failed to compare with any literature data.
My calculation steps are the following:
1. Optimize the geometry of the neutral molecule with tight convergence criteria using odft and mult=1.
2. Retrieve the final geometry and movecs file and use them in a TD-DFT calculation.
This is an example input script:
echo
start pyr_tddft-tda_b3lyp_6-31+gs_spin_1_sym
title "pyr_tddft-tda_b3lyp_6-31+gs_spin_1_sym"
charge 0
geometry noautoz nocenter
load preview_pyr_b3lyp_6-31+gs_spin_1_sym-008.xyz
end
basis
* library "6-31+g*"
end
dft
direct
vectors input pyr_b3lyp_6-31+gs_spin_1_sym.movecs output tddft.movecs
xc b3lyp
grid fine
odft
mult 1
end
tddft
cis
nroots 20
end
task tddft energy
According to https://doi.org/10.1016/S0166-1280(02)00787-X, I should get
b2u 3.66
b1u 3.73
b3g 4.29 Forbidden
b3g 4.57 Forbidden
b2u 4.59
What NWCHEM 6.5 gives me is the following:
Ground state ag -615.792027823211 a.u.
<S2> = -0.0000
----------------------------------------------------------------------------
Root 1 b2u 0.087699603 a.u. 2.3864 eV
<S2> = 2.0000
----------------------------------------------------------------------------
Transition Moments X -0.00000 Y -0.00000 Z -0.00000
Transition Moments XX 0.00000 XY -0.00000 XZ 0.00000
Transition Moments YY -0.00000 YZ 0.00000 ZZ 0.00000
Dipole Oscillator Strength 0.00000
Occ. 50 alpha au --- Virt. 57 alpha b2g -0.07693
Occ. 51 alpha b1u --- Virt. 56 alpha b3g 0.08126
Occ. 52 alpha b3g --- Virt. 55 alpha b1u 0.07214
Occ. 53 alpha b2g --- Virt. 54 alpha au -0.68843
Occ. 50 beta au --- Virt. 57 beta b2g 0.07693
Occ. 51 beta b1u --- Virt. 56 beta b3g -0.08126
Occ. 52 beta b3g --- Virt. 55 beta b1u -0.07214
Occ. 53 beta b2g --- Virt. 54 beta au 0.68843
----------------------------------------------------------------------------
Root 2 b3u 0.126585552 a.u. 3.4446 eV
<S2> = 2.0000
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y -0.00000 Z -0.00000
Transition Moments XX 0.00000 XY -0.00000 XZ 0.00000
Transition Moments YY -0.00000 YZ 0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.00000
Occ. 52 alpha b3g --- Virt. 54 alpha au -0.41733
Occ. 53 alpha b2g --- Virt. 55 alpha b1u 0.56371
Occ. 52 beta b3g --- Virt. 54 beta au 0.41733
Occ. 53 beta b2g --- Virt. 55 beta b1u -0.56371
----------------------------------------------------------------------------
Root 3 b3u 0.132444477 a.u. 3.6040 eV
<S2> = 2.0000
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y 0.00000 Z -0.00000
Transition Moments XX 0.00000 XY 0.00000 XZ 0.00000
Transition Moments YY -0.00000 YZ 0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.00000
Occ. 52 alpha b3g --- Virt. 54 alpha au 0.56526
Occ. 53 alpha b2g --- Virt. 55 alpha b1u 0.41969
Occ. 52 beta b3g --- Virt. 54 beta au -0.56526
Occ. 53 beta b2g --- Virt. 55 beta b1u -0.41969
----------------------------------------------------------------------------
Root 4 b1g 0.134861874 a.u. 3.6698 eV
<S2> = 2.0000
----------------------------------------------------------------------------
Transition Moments X -0.00000 Y 0.00000 Z -0.00000
Transition Moments XX 0.00000 XY -0.00000 XZ 0.00000
Transition Moments YY -0.00000 YZ -0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.00000
Occ. 46 alpha b2g --- Virt. 56 alpha b3g 0.08504
Occ. 49 alpha b1u --- Virt. 54 alpha au 0.06845
Occ. 51 alpha b1u --- Virt. 54 alpha au 0.41875
Occ. 51 alpha b1u --- Virt. 68 alpha au -0.05867
Occ. 53 alpha b2g --- Virt. 56 alpha b3g -0.53956
Occ. 53 alpha b2g --- Virt. 63 alpha b3g -0.05984
Occ. 46 beta b2g --- Virt. 56 beta b3g -0.08504
Occ. 49 beta b1u --- Virt. 54 beta au -0.06845
Occ. 51 beta b1u --- Virt. 54 beta au -0.41875
Occ. 51 beta b1u --- Virt. 68 beta au 0.05867
Occ. 53 beta b2g --- Virt. 56 beta b3g 0.53956
Occ. 53 beta b2g --- Virt. 63 beta b3g 0.05984
----------------------------------------------------------------------------
Root 5 b3u 0.137760609 a.u. 3.7487 eV
<S2> = 0.0000
----------------------------------------------------------------------------
Transition Moments X 0.05596 Y 0.00000 Z 0.00000
Transition Moments XX 0.00000 XY 0.00000 XZ -0.00000
Transition Moments YY 0.00000 YZ -0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.00029
Occ. 52 alpha b3g --- Virt. 54 alpha au 0.47892
Occ. 53 alpha b2g --- Virt. 55 alpha b1u 0.51818
Occ. 52 beta b3g --- Virt. 54 beta au 0.47892
Occ. 53 beta b2g --- Virt. 55 beta b1u 0.51818
----------------------------------------------------------------------------
Root 6 b2u 0.141722835 a.u. 3.8565 eV
<S2> = 0.0000
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y -1.85003 Z -0.00000
Transition Moments XX 0.00000 XY 0.00000 XZ -0.00000
Transition Moments YY -0.00000 YZ -0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.32337
Occ. 51 alpha b1u --- Virt. 56 alpha b3g -0.09828
Occ. 52 alpha b3g --- Virt. 55 alpha b1u 0.27567
Occ. 53 alpha b2g --- Virt. 54 alpha au -0.63499
Occ. 51 beta b1u --- Virt. 56 beta b3g -0.09828
Occ. 52 beta b3g --- Virt. 55 beta b1u 0.27567
Occ. 53 beta b2g --- Virt. 54 beta au -0.63499
----------------------------------------------------------------------------
Root 7 ag 0.147505603 a.u. 4.0138 eV
<S2> = 2.0000
----------------------------------------------------------------------------
Transition Moments X -0.00000 Y 0.00000 Z 0.00000
Transition Moments XX -0.00000 XY -0.00000 XZ -0.00000
Transition Moments YY 0.00000 YZ 0.00000 ZZ 0.00000
Dipole Oscillator Strength 0.00000
Occ. 49 alpha b1u --- Virt. 55 alpha b1u 0.06661
Occ. 50 alpha au --- Virt. 54 alpha au 0.45020
Occ. 51 alpha b1u --- Virt. 55 alpha b1u -0.10890
Occ. 52 alpha b3g --- Virt. 56 alpha b3g -0.12598
Occ. 52 alpha b3g --- Virt. 63 alpha b3g 0.05204
Occ. 53 alpha b2g --- Virt. 57 alpha b2g 0.49427
Occ. 53 alpha b2g --- Virt. 71 alpha b2g -0.07603
Occ. 49 beta b1u --- Virt. 55 beta b1u -0.06661
Occ. 50 beta au --- Virt. 54 beta au -0.45020
Occ. 51 beta b1u --- Virt. 55 beta b1u 0.10890
Occ. 52 beta b3g --- Virt. 56 beta b3g 0.12598
Occ. 52 beta b3g --- Virt. 63 beta b3g -0.05204
Occ. 53 beta b2g --- Virt. 57 beta b2g -0.49427
Occ. 53 beta b2g --- Virt. 71 beta b2g 0.07603
----------------------------------------------------------------------------
Root 8 b2u 0.147646939 a.u. 4.0177 eV
<S2> = 2.0000
----------------------------------------------------------------------------
Transition Moments X -0.00000 Y 0.00000 Z -0.00000
Transition Moments XX -0.00000 XY 0.00000 XZ 0.00000
Transition Moments YY 0.00000 YZ -0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.00000
Occ. 49 alpha b1u --- Virt. 56 alpha b3g 0.05034
Occ. 49 alpha b1u --- Virt. 63 alpha b3g -0.09058
Occ. 50 alpha au --- Virt. 57 alpha b2g 0.05667
Occ. 51 alpha b1u --- Virt. 56 alpha b3g -0.10367
Occ. 52 alpha b3g --- Virt. 55 alpha b1u -0.67659
Occ. 53 alpha b2g --- Virt. 54 alpha au -0.09841
Occ. 49 beta b1u --- Virt. 56 beta b3g -0.05034
Occ. 49 beta b1u --- Virt. 63 beta b3g 0.09058
Occ. 50 beta au --- Virt. 57 beta b2g -0.05667
Occ. 51 beta b1u --- Virt. 56 beta b3g 0.10367
Occ. 52 beta b3g --- Virt. 55 beta b1u 0.67659
Occ. 53 beta b2g --- Virt. 54 beta au 0.09841
----------------------------------------------------------------------------
Root 9 b1g 0.158505126 a.u. 4.3131 eV
<S2> = 0.0000
----------------------------------------------------------------------------
Transition Moments X 0.00000 Y 0.00000 Z -0.00000
Transition Moments XX -0.00000 XY 0.08330 XZ 0.00000
Transition Moments YY 0.00000 YZ -0.00000 ZZ 0.00000
Dipole Oscillator Strength 0.00000
Occ. 51 alpha b1u --- Virt. 54 alpha au 0.21703
Occ. 53 alpha b2g --- Virt. 56 alpha b3g 0.67023
Occ. 51 beta b1u --- Virt. 54 beta au 0.21703
Occ. 53 beta b2g --- Virt. 56 beta b3g 0.67023
----------------------------------------------------------------------------
Root 10 b1g 0.160090362 a.u. 4.3563 eV
<S2> = 2.0000
----------------------------------------------------------------------------
Transition Moments X -0.00000 Y -0.00000 Z -0.00000
Transition Moments XX 0.00000 XY 0.00000 XZ 0.00000
Transition Moments YY -0.00000 YZ 0.00000 ZZ -0.00000
Dipole Oscillator Strength 0.00000
Occ. 51 alpha b1u --- Virt. 54 alpha au -0.54604
Occ. 53 alpha b2g --- Virt. 56 alpha b3g -0.43893
Occ. 53 alpha b2g --- Virt. 63 alpha b3g 0.06401
Occ. 51 beta b1u --- Virt. 54 beta au 0.54604
Occ. 53 beta b2g --- Virt. 56 beta b3g 0.43893
Occ. 53 beta b2g --- Virt. 63 beta b3g -0.06401
There seems to be something wrong with the way I am telling NWCHEM to execute my calculations...
I appreciate any input!!
Best regards,
Orestis
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