Symmetry breaking in ZORA-NMR calculations
Clicked A Few Times
7:40:38 AM PST - Tue, Dec 6th 2016
Dear NWChem friends

I calculated NMR in [PtCl4]2- by ZORA in NWChem6.3. [PtCl4]2- has D4h symmetry. The calculated isotropic shielding constants of Cl atoms are 1159.6608, 1175.3171, 1162.2551, and 1148.9335 ppm. These are significantly different to each other, that is, symmetry breaking occurs. I want to know why it happens.
In addition, isotropic shielding constant of Pt is -1140.1492 ppm.

Best regards,

Input file is as follows
ECHO
START
TITLE "[PtCl4]-2"
CHARGE -2
BASIS SPHERICAL
 Pt library sarc-zora

 Cl library 6-31G*
END
memory 500 mb
DFT
 XC pbe0

 direct 

 ITERATIONS 150
END
RELATIVISTIC 
 ZORA

 CLIGHT 137.0359895
END
COSMO
dielec 78.4

rsolv   0.5

ificos  1

lineq   0

do_gasphase false
END
PROPERTY
 MULLIKEN

 DIPOLE

 SHIELDING
END
GEOMETRY
symmetry D4h
Pt 0.0000 0.0000 0.0000
Cl 2.3040 0.0000 0.0000
END
TASK DFT energy
TASK DFT property

Clicked A Few Times
12:30:21 AM PST - Tue, Dec 27th 2016
Symmetry breaking in ZORA-NMR calculations(2)
Dear All,

I add one more example for the symmetry breaking in NMR calculation
by ZORA(NWChem6.3). The diagonal elements of magnetic shielding constant
tensor for 195Pt in [PtCl6]2- with Oh symmetry should be equal to each
other. However, the calculated results of the elements (especially,
paramagnetic term) are significantly different from each other,
as wrritten below.
I want you to tell me why this happens. Is this because of a bug in
NWChem?

Calc. par tensor-> zora
     Atom:    1  Pt

       Diamagnetic

  9278.1230     -2.9024     -2.8115

    -2.9024   9277.9979     -2.3996

    -2.8115     -2.3996   9278.3548



       Paramagnetic

-11384.4764  -2084.0343  -1434.2302

 -2084.0343 -11050.6536  -1455.2491

 -1434.2302  -1455.2491 -12550.7520



       Total Shielding Tensor

 -2106.3533  -2086.9367  -1437.0416

 -2086.9367  -1772.6557  -1457.6487

 -1437.0416  -1457.6487  -3272.3972



          isotropic =   -2383.8021

         anisotropy =   -5023.9663



         Principal Components and Axis System

                1           2           3

           -5733.1130  -1576.1875    157.8942



     1         0.5579     -0.4985     -0.6635

     2         0.5292     -0.4022      0.7471

     3         0.6393      0.7679     -0.0395


Input file:
ECHO

START

TITLE "[PtCl6]-2"

CHARGE -2

BASIS SPHERICAL
 Pt library sarc-zora

 Cl library 6-31G*
END
memory 500 mb
DFT
 XC pbe0

 direct 

 ITERATIONS 150
END
RELATIVISTIC 
 ZORA

 CLIGHT 137.0359895
END
COSMO
dielec 78.4

rsolv   0.5

ificos   1

lineq   0

do_gasphase false
END
PROPERTY
 MULLIKEN

 DIPOLE

 SHIELDING
END
GEOMETRY
symmetry Oh
Pt 0.000000 0.00000 0.00000
Cl 2.322460 0.00000 0.00000
END

TASK DFT energy

TASK DFT property

Clicked A Few Times
12:30:40 AM PST - Tue, Dec 27th 2016
Symmetry breaking in ZORA-NMR calculations(2)
Dear All,

I add one more example for the symmetry breaking in NMR calculation
by ZORA(NWChem6.3). The diagonal elements of magnetic shielding constant
tensor for 195Pt in [PtCl6]2- with Oh symmetry should be equal to each
other. However, the calculated results of the elements (especially,
paramagnetic term) are significantly different from each other,
as wrritten below.
I want you to tell me why this happens. Is this because of a bug in
NWChem?

Calc. par tensor-> zora
     Atom:    1  Pt

       Diamagnetic

  9278.1230     -2.9024     -2.8115

    -2.9024   9277.9979     -2.3996

    -2.8115     -2.3996   9278.3548



       Paramagnetic

-11384.4764  -2084.0343  -1434.2302

 -2084.0343 -11050.6536  -1455.2491

 -1434.2302  -1455.2491 -12550.7520



       Total Shielding Tensor

 -2106.3533  -2086.9367  -1437.0416

 -2086.9367  -1772.6557  -1457.6487

 -1437.0416  -1457.6487  -3272.3972



          isotropic =   -2383.8021

         anisotropy =   -5023.9663



         Principal Components and Axis System

                1           2           3

           -5733.1130  -1576.1875    157.8942



     1         0.5579     -0.4985     -0.6635

     2         0.5292     -0.4022      0.7471

     3         0.6393      0.7679     -0.0395


Input file:
ECHO

START

TITLE "[PtCl6]-2"

CHARGE -2

BASIS SPHERICAL
 Pt library sarc-zora

 Cl library 6-31G*
END
memory 500 mb
DFT
 XC pbe0

 direct 

 ITERATIONS 150
END
RELATIVISTIC 
 ZORA

 CLIGHT 137.0359895
END
COSMO
dielec 78.4

rsolv   0.5

ificos   1

lineq   0

do_gasphase false
END
PROPERTY
 MULLIKEN

 DIPOLE

 SHIELDING
END
GEOMETRY
symmetry Oh
Pt 0.000000 0.00000 0.00000
Cl 2.322460 0.00000 0.00000
END

TASK DFT energy

TASK DFT property


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