[adf-list]冻结核心zora / qz4p计算

Mikael Johansson. Mikael.Johansson在Iki.fi.
星期五2014年5月16日15:10:49

Dear Erik and All,

Thanks for the explanations, and the basis set. The new QZ4P/Au.4f basis 
set seems to lack quite much of the freedom compared to the all-electron 
QZ4P, and the dummy, full-valence version of the Au.4f, though.

I tested it on the energy difference between the 2D and 3D structures of 
the Au12- anion (http://dx.doi.org/10.1103/PhysRevA.77.053202), with the 
following resulting energy differences (at PBEsol/ZORA/scalar level); the 
HOMO/LUMO energies of the 2D structure are also listed:

          QZ4P   QZ.4f(dummy) QZ.4f(EvL) QZ.4f(trimmed)
E(3D-2D) -19.1    -19.2        -5.0      -18.9  kJ/mol
HOMO      -1.708   -1.713      -1.679     -1.709 eV
LUMO      -1.545   -1.550      -1.514     -1.545


So the new QZ4P/Au.4f gives very different relative energies compared to 
the all-electron basis set. I trimmed away functions from the "dummy" FC 
basis set, leaving all that had a notable effect on the relative energy, 
the result is again pasted below (and the energies in the last column).

In any case, I think this shows that the 60 core electrons do not 
contribute to the binding energy between the gold atoms, at scalar 
relativistic level. The HOMO/LUMO energies are also very similar

With spin-orbit coupling included, the results are a bit different, but 
I'm not sure if this is because the core electrons contribute to the 
binding, or if it's an indirect artefact coming from the effect of SO on 
the orbital energies. It would be nice to have an SO core available. 
Especially as the SO calc with the QZ4P.4f below is more than a factor of 
four faster :-)

          QZ4P   QZ.4f(dummy) QZ.4f(EvL) QZ.4f(trimmed)
E(3D-2D)  -7.60    -2.32       +4.10      -2.96  kJ/mol
HOMO      -1.794   -1.883      -1.699     -1.844
LUMO      -1.655   -1.754      -1.555     -1.711

Cheers,
     Mikael


Gold (QZ4P, 4f frozen (60 e core), trimmed, MPJ 05/2014)

BASIS
         1S  270.000
         2S   42.800
         3S   22.950
         4S   11.900
         2P   78.350
         3P   37.400
         4P   16.650
         3D   31.300
         4D   14.300
         4F    7.300

         1S 2180.000
         1S  695.000
         1S  125.000
         1S   85.450
         2S   35.850
         3S   18.400
         4S    9.200
         5S    7.150
         5S    5.150
         5S    3.850
         6S    3.350
         6S    2.350
         6S    1.600
         6S    1.070
         2P   44.050
         2P   34.150
         3P   21.850
         3P   17.100
         4P   11.150
         4P    8.300
         5P    6.500
         5P    4.500
         5P    3.150
         6P    2.500
         6P    1.700
         6P    1.100
         3D   20.900
         3D   15.600
         4D    9.650
         4D    6.850
         5D    4.900
         5D    3.050
         5D    1.900
         5D    1.200
         4F    4.350
         5F    2.700
         5F    1.350
END

CORE    4  3  2  1
         1S  760.000
         1S  184.000
         1S   87.700
         2S   99.400
         2S   38.300
         3S   48.700
         3S   20.750
         4S   12.700
         4S    9.000
         5S    7.000
         5S    4.600
         6S    3.150
         6S    1.950
         6S    1.210
         2P   65.900
         2P   36.600
         3P   20.800
         3P   15.300
         4P   13.550
         4P    9.250
         5P    6.000
         5P    3.700
         3D   28.000
         3D   17.900
         4D   12.200
         4D    7.800
         5D    5.050
         5D    2.800
         5D    1.500
         4F   16.150
         4F    8.900
         4F    4.900
END

DESCRIPTION
     .22018617895738584744E-01   .14116974977423085713E+00
     .87207693657938767373E+00   .77680889589463730793E-02
    -.25221315127642383869E-01   .22058018545083320910E-01
     .85474922905381706291E-03  -.61155453930447493168E-03
     .56849729991794632853E-03  -.30032240792580685088E-03
     .13360337039928301024E-03  -.53805316319825778441E-04
     .25808355788516243944E-04  -.89712035329347714497E-05

    -.74301761942448460441E-02  -.55584553577420862946E-01
    -.27607557570960511439E+00  -.85069418488694703573E-01
     .98473277922767876724E+00   .10980611439562316944E+00
     .36350035199224214541E-02   .88635186836117730094E-03
    -.17929041216155235366E-02   .13928777214444929521E-02
    -.75563740692087598503E-03   .33864950344558931083E-03
    -.16981692269205694358E-03   .60095244924641582674E-04

     .36155958996457898159E-02   .16135758013044225467E-01
     .15781806613780821613E+00  -.79192180749857350730E-02
    -.30880828962613571242E+00  -.37744400432206853813E+00
     .11929913799355595927E+01  -.62861852690925560869E-02
     .72405099200356084696E-02  -.26164496421376653816E-02
     .68207106909025892738E-03  -.14251503497624676601E-03
     .39225324072805088291E-04  -.94110898754734729913E-05

    -.19006718691067976418E-02  -.27927537528881786998E-02
    -.95151375339088767324E-01   .29786589973954117477E-01
     .63260544421577677432E-01   .31623676965735764144E+00
    -.87849784290291010880E+00   .10559412773604577307E+01
     .21914770570424652041E+00  -.11095858047777526836E-01
     .50126428323178711874E-02  -.25447872183713324788E-02
     .13760467616083140851E-02  -.50472702572226942844E-03

     .15128143207712455021E+00   .87214239235873480816E+00
     .13229175940767643610E-01  -.20960022992712542406E-01
     .16133812185068818756E-01  -.66520657387665266605E-02
     .19863381480148575679E-02  -.70243588713429165171E-03

    -.57814562752468760809E-01  -.51067204765293661151E+00
     .97530755301405136493E+00   .22728829123725974304E+00
    -.67054229068071236064E-01   .24485888776444180576E-01
    -.72465894505855943386E-02   .25799466191666411974E-02

     .25287909708401334896E-01   .26589730458413995962E+00
    -.50687020012771810684E+00  -.47721541536086825586E+00
     .93701274548289703592E+00   .52005190668748813021E+00
     .90339002800095321438E-02  -.29097001873307293610E-02

     .37550105477285616873E+00   .66530197545234670553E+00
    -.48982083504430732473E-02   .39286895797436757749E-02
    -.10497093965855495718E-02   .36613946156453309371E-03
    -.11370041091496406861E-03

    -.19911235427959006472E+00  -.34333924066275745002E+00
     .72717859834297116084E+00   .45904078411905252510E+00
    -.33164479837385543032E-02   .23456149893496436483E-02
    -.77427476107391789758E-03

     .28964845446318310263E+00   .62715619383714515944E+00
     .23076743973531274601E+00

0/
END

FIT
  1S  19500.000
  1S  14851.787
  1S  11311.567
  1S   8615.230
  1S   6561.618
  1S   4997.526
  1S   3806.266
  1S   2898.967
  1S   2207.940
  1S   1681.634
  1S   1280.783
  1S    975.483
  1S    742.957
  1S    565.858
  1S    430.975
  1S    328.243
  1S    250.000
  1S    159.630
  2S    188.319
  2S    133.117
  3S    137.777
  3S    102.787
  3S     76.682
  4S     75.490
  4S     58.307
  4S     45.035
  5S     43.257
  5S     34.247
  5S     27.113
  6S     25.689
  6S     20.723
  6S     16.717
  7S     15.711
  7S     12.864
  7S     10.532
  8S      9.848
  8S      8.162
  8S      6.765
  8S      5.606
  9S      5.226
  9S      4.375
  9S      3.663
  9S      3.067
  9S      2.568
  9S      2.150
  9S      1.800
  2P    169.050
  2P    107.804
  3P    101.255
  4P     91.792
  4P     65.682
  5P     58.641
  5P     43.328
  6P     38.413
  6P     29.082
  7P     25.704
  7P     19.839
  8P     17.517
  8P     13.735
  8P     10.769
  9P      9.510
  9P      7.556
  9P      6.003
  9P      4.769
  9P      3.789
  9P      3.010
  9P      2.392
  9P      1.900
  3D    145.900
  3D     93.254
  4D     79.320
  5D     66.913
  6D     56.338
  6D     40.591
  7D     34.205
  7D     25.211
  8D     21.291
  8D     15.987
  8D     12.004
  9D     10.165
  9D      7.752
  9D      5.912
  9D      4.509
  9D      3.439
  9D      2.622
  9D      2.000
  4F    137.300
  5F    108.522
  6F     86.108
  6F     58.597
  7F     46.743
  7F     32.670
  8F     26.211
  8F     18.724
  8F     13.376
  9F     10.793
  9F      7.852
  9F      5.713
  9F      4.156
  9F      3.024
  9F      2.200
  5G     56.350
  6G     43.438
  6G     28.747
  7G     22.327
  7G     15.206
  8G     11.898
  8G      8.296
  9G      6.538
  9G      4.648
  9G      3.305
  9G      2.350
END

FITCOEFFICIENTS
/
END



On Tue, 13 May 2014, Erik van Lenthe (support at scm.com) wrote:

> Dear Mikael,
>
> The frozen core orbital description in the ZORA basis set files are 
> calculated with the LDA functional using a scalar relativistic Hamiltonian.
> If one uses a different functional than LDA this can lead to a small error.
> If one uses frozen core basis sets in spin-orbit coupled calculations this 
> can lead to larger errors, because the core orbitals were calculated with the 
> scalar relativistic Hamiltonian. Especially if one has many core like STO 
> functions in the valence that can describe the (radial) difference between a 
> 2p1/2 spinor and a 2p3/2 spinor, the errors can be larger (variational 
> collapse).
>
> At the end of this mail I pasted an untested ZORA/QZ4P/Au.4f basis set file, 
> which is QZ4P in the valence, but lacks core-like STOs in the core.
>
> Best regards,
> Erik
> SCM
>
> Gold (QZ4P, 4f frozen)
>
> BASIS
> 1S   57.000
> 2S   36.650
> 3S   21.050
> 4S   12.400
> 2P   39.650
> 3P   17.950
> 4P   12.550
> 3D   22.100
> 4D   11.200
> 4F    8.000
>
> 1S  184.000
>         5S    7.150
>         5S    5.150
>         5S    3.850
>         6S    3.350
>         6S    2.350
>         6S    1.600
>         6S    1.070
>         5P    6.500
>         5P    4.500
>         5P    3.150
> 6P    2.500
> 6P    1.700
> 6P    1.100
>         5D    4.900
>         5D    3.050
>         5D    1.900
>         5D    1.200
> 5F    2.700
> 5F    1.350
> END
>
> CORE    4  3  2  1
>         1S  760.000
>         1S  184.000
>         1S   87.700
>         2S   99.400
>         2S   38.300
>         3S   48.700
>         3S   20.750
>         4S   12.700
>         4S    9.000
>         5S    7.000
>         5S    4.600
>         6S    3.150
>         6S    1.950
>         6S    1.210
>         2P   65.900
>         2P   36.600
>         3P   20.800
>         3P   15.300
>         4P   13.550
>         4P    9.250
>         5P    6.000
>         5P    3.700
>         3D   28.000
>         3D   17.900
>         4D   12.200
>         4D    7.800
>         5D    5.050
>         5D    2.800
>         5D    1.500
>         4F   16.150
>         4F    8.900
>         4F    4.900
> END
>
> DESCRIPTION
>     .22018617895738584744E-01   .14116974977423085713E+00
>     .87207693657938767373E+00   .77680889589463730793E-02
>    -.25221315127642383869E-01   .22058018545083320910E-01
>     .85474922905381706291E-03  -.61155453930447493168E-03
>     .56849729991794632853E-03  -.30032240792580685088E-03
>     .13360337039928301024E-03  -.53805316319825778441E-04
>     .25808355788516243944E-04  -.89712035329347714497E-05
>
>    -.74301761942448460441E-02  -.55584553577420862946E-01
>    -.27607557570960511439E+00  -.85069418488694703573E-01
>     .98473277922767876724E+00   .10980611439562316944E+00
>     .36350035199224214541E-02   .88635186836117730094E-03
>    -.17929041216155235366E-02   .13928777214444929521E-02
>    -.75563740692087598503E-03   .33864950344558931083E-03
>    -.16981692269205694358E-03   .60095244924641582674E-04
>
>     .36155958996457898159E-02   .16135758013044225467E-01
>     .15781806613780821613E+00  -.79192180749857350730E-02
>    -.30880828962613571242E+00  -.37744400432206853813E+00
>     .11929913799355595927E+01  -.62861852690925560869E-02
>     .72405099200356084696E-02  -.26164496421376653816E-02
>     .68207106909025892738E-03  -.14251503497624676601E-03
>     .39225324072805088291E-04  -.94110898754734729913E-05
>
>    -.19006718691067976418E-02  -.27927537528881786998E-02
>    -.95151375339088767324E-01   .29786589973954117477E-01
>    .63260544421577677432E-01   .31623676965735764144E+00
>    -.87849784290291010880E+00   .10559412773604577307E+01
>     .21914770570424652041E+00  -.11095858047777526836E-01
>     .50126428323178711874E-02  -.25447872183713324788E-02
>     .13760467616083140851E-02  -.50472702572226942844E-03
>
>     .15128143207712455021E+00   .87214239235873480816E+00
>     .13229175940767643610E-01  -.20960022992712542406E-01
>     .16133812185068818756E-01  -.66520657387665266605E-02
>     .19863381480148575679E-02  -.70243588713429165171E-03
>
>    -.57814562752468760809E-01  -.51067204765293661151E+00
>    .97530755301405136493E+00   .22728829123725974304E+00
>    -.67054229068071236064E-01   .24485888776444180576E-01
>    -.72465894505855943386E-02   .25799466191666411974E-02
>
>    .25287909708401334896E-01   .26589730458413995962E+00
>    -.50687020012771810684E+00  -.47721541536086825586E+00
>     .93701274548289703592E+00   .52005190668748813021E+00
>     .90339002800095321438E-02  -.29097001873307293610E-02
>
>    .37550105477285616873E+00   .66530197545234670553E+00
>    -.48982083504430732473E-02   .39286895797436757749E-02
>    -.10497093965855495718E-02   .36613946156453309371E-03
>    -.11370041091496406861E-03
>
>    -.19911235427959006472E+00  -.34333924066275745002E+00
>    .72717859834297116084E+00   .45904078411905252510E+00
>    -.33164479837385543032E-02   .23456149893496436483E-02
>    -.77427476107391789758E-03
>
>     .28964845446318310263E+00   .62715619383714515944E+00
>     .23076743973531274601E+00
>
> 0/
> END
>
> FIT
>  1S  19500.000
>  1S  14851.787
>  1S  11311.567
>  1S   8615.230
>  1S   6561.618
>  1S   4997.526
>  1S   3806.266
>  1S   2898.967
>  1S   2207.940
>  1S   1681.634
>  1S   1280.783
>  1S    975.483
>  1S    742.957
>  1S    565.858
>  1S    430.975
>  1S    328.243
>  1S    250.000
>  1S    159.630
>  2S    188.319
>  2S    133.117
>  3S    137.777
>  3S    102.787
>  3S     76.682
>  4S     75.490
>  4S     58.307
>  4S     45.035
>  5S     43.257
>  5S     34.247
>  5S     27.113
>  6S     25.689
>  6S     20.723
>  6S     16.717
>  7S     15.711
>  7S     12.864
>  7S     10.532
>  8S      9.848
>  8S      8.162
>  8S      6.765
>  8S      5.606
>  9S      5.226
>  9S      4.375
>  9S      3.663
>  9S      3.067
>  9S      2.568
>  9S      2.150
>  9S      1.800
>  2P    169.050
>  2P    107.804
>  3P    101.255
>  4P     91.792
>  4P     65.682
>  5P     58.641
>  5P     43.328
>  6P     38.413
>  6P     29.082
>  7P     25.704
>  7P     19.839
>  8P     17.517
>  8P     13.735
>  8P     10.769
>  9P      9.510
>  9P      7.556
>  9P      6.003
>  9P      4.769
>  9P      3.789
>  9P      3.010
>  9P      2.392
>  9P      1.900
>  3D    145.900
>  3D     93.254
>  4D     79.320
>  5D     66.913
>  6D     56.338
>  6D     40.591
>  7D     34.205
>  7D     25.211
>  8D     21.291
>  8D     15.987
>  8D     12.004
>  9D     10.165
>  9D      7.752
>  9D      5.912
>  9D      4.509
>  9D      3.439
>  9D      2.622
>  9D      2.000
>  4F    137.300
>  5F    108.522
>  6F     86.108
>  6F     58.597
>  7F     46.743
>  7F     32.670
>  8F     26.211
>  8F     18.724
>  8F     13.376
>  9F     10.793
>  9F      7.852
>  9F      5.713
>  9F      4.156
>  9F      3.024
>  9F      2.200
>  5G     56.350
>  6G     43.438
>  6G     28.747
>  7G     22.327
>  7G     15.206
>  8G     11.898
>  8G      8.296
>  9G      6.538
>  9G      4.648
>  9G      3.305
>  9G      2.350
> END
>
> FITCOEFFICIENTS
> /
> END


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