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<div class="moz-cite-prefix">Hi,<br>
<br>
The error seem to be numerical, probably due to small symmetry
problem in orbitals/integrals; but might be a bug as well. Before
looking in detail, could you please try the same calculation with
much tighter thresholds for integrals, orbitals, and CI
coefficients?<br>
<br>
Best,<br>
<br>
Alexander<br>
<br>
Le 26/11/2015 02:49, ZOUWL a écrit :<br>
</div>
<blockquote
cite="mid:CAFumqg_QDAu0gVek8NnSQ0o==WYeJZe7Fpxa2cWNCx2zdbcWcw@mail.gmail.com"
type="cite">
<div dir="ltr">
<div>Dear developers,</div>
<div><br>
</div>
<div>There may be a bug in the following spin-orbit calculation.
The low-lying 1D, 3P, 3F, and 5F states of Ta+ are calculated
at the CASSCF(4,6) level, where the 5d6s orbitals are active.
Group symmery used here is Ci, but the results and errors are
the same if D2h is used. All the calculations are performed
using the 2010 version. Input:</div>
<div><br>
</div>
<div>***,Ta+, SOC with ECP</div>
<div>memory,100,m</div>
<div><br>
</div>
<div>symmetry,xyz</div>
<div><br>
</div>
<div>geometry={Ta}</div>
<div><br>
</div>
<div>basis=vtz-pp</div>
<div><br>
</div>
<div>{multi;natorb,ci;</div>
<div>frozen,0;closed,1,3;occ,7,3;</div>
<div>wf,12,1,0;state,5; ! 1D</div>
<div>wf,12,1,2;state,10; ! 3P, 3F</div>
<div>wf,12,1,4;state,7; ! 5F</div>
<div>}</div>
<div><br>
</div>
<div>{ci;noexc;wf,12,1,0;state,5;</div>
<div>save,4201.3;}</div>
<div>{ci;noexc;wf,12,1,2;state,10;</div>
<div>save,4221.3;}</div>
<div>{ci;noexc;wf,12,1,4;state,7;</div>
<div>save,4241.3;}</div>
<div><br>
</div>
<div>! SOC: singlet and triplet states</div>
<div>{ci;hlsmat,ecpls,4201.3,4221.3;}</div>
<div>! SOC: triplet and quintet states</div>
<div>{ci;hlsmat,ecpls,4221.3,4241.3;}</div>
<div>! SOC: singlet and quintet states</div>
<div>{ci;hlsmat,ecpls,4201.3,4241.3;}</div>
<div>---</div>
<div><br>
</div>
<div>The CASSCF energies of L-S states are degenerate (normal):</div>
<div>1D: -56.47502225 (x 5)</div>
<div>3P: -56.49919112 (x 3)</div>
<div>3F: -56.48533379 (x 7)</div>
<div>5F: -56.52492675 (x 7)</div>
<div><br>
</div>
<div>In the first (singlet + triplet) and the third (singlet +
quintet) SOC calculations, the energies of atomic J terms are
degenerate (normal):</div>
<div><br>
</div>
<div> Nr Sym E E-E0 E-E0
E-E(1) E-E(1) E-E(1)</div>
<div> (au) (au) (cm-1)
(au) (cm-1) (eV)</div>
<div> 1 1 -56.51000193 -0.01081081 -2372.70
0.00000000 0.00 0.0000</div>
<div> 2 1 -56.50459652 -0.00540540 -1186.35
0.00540540 1186.35 0.1471</div>
<div> 3 1 -56.50459652 -0.00540540 -1186.35
0.00540540 1186.35 0.1471</div>
<div> 4 1 -56.50459652 -0.00540540 -1186.35
0.00540540 1186.35 0.1471</div>
<div> 5 1 -56.50158234 -0.00239123 -524.81
0.00841958 1847.88 0.2291</div>
<div> 6 1 -56.50158234 -0.00239123 -524.81
0.00841958 1847.88 0.2291</div>
<div> 7 1 -56.50158234 -0.00239123 -524.81
0.00841958 1847.88 0.2291</div>
<div> 8 1 -56.50158234 -0.00239123 -524.81
0.00841958 1847.88 0.2291</div>
<div> 9 1 -56.50158234 -0.00239123 -524.81
0.00841958 1847.88 0.2291</div>
<div> 10 1 -56.49671921 0.00247191 542.52
0.01328272 2915.22 0.3614</div>
<div> 11 1 -56.49671921 0.00247191 542.52
0.01328272 2915.22 0.3614</div>
<div> 12 1 -56.49671921 0.00247191 542.52
0.01328272 2915.22 0.3614</div>
<div> 13 1 -56.49671921 0.00247191 542.52
0.01328272 2915.22 0.3614</div>
<div> 14 1 -56.49671921 0.00247191 542.52
0.01328272 2915.22 0.3614</div>
<div>...</div>
<div> Nr E E-E0 E-E0
E-E(1) E-E(1) E-E(1)</div>
<div> (au) (au) (cm-1)
(au) (cm-1) (eV)</div>
<div> 1 -56.54141852 -0.01649177 -3619.53
0.00000000 0.00 0.0000</div>
<div> 2 -56.54141852 -0.01649177 -3619.53
0.00000000 0.00 0.0000</div>
<div> 3 -56.54141852 -0.01649177 -3619.53
0.00000000 0.00 0.0000</div>
<div> 4 -56.53729558 -0.01236883 -2714.64
0.00412294 904.88 0.1122</div>
<div> 5 -56.53729558 -0.01236883 -2714.64
0.00412294 904.88 0.1122</div>
<div> 6 -56.53729558 -0.01236883 -2714.64
0.00412294 904.88 0.1122</div>
<div> 7 -56.53729558 -0.01236883 -2714.64
0.00412294 904.88 0.1122</div>
<div> 8 -56.53729558 -0.01236883 -2714.64
0.00412294 904.88 0.1122</div>
<div> 9 -56.53111117 -0.00618441 -1357.32
0.01030736 2262.20 0.2805</div>
<div> 10 -56.53111117 -0.00618441 -1357.32
0.01030736 2262.20 0.2805</div>
<div> 11 -56.53111117 -0.00618441 -1357.32
0.01030736 2262.20 0.2805</div>
<div> 12 -56.53111117 -0.00618441 -1357.32
0.01030736 2262.20 0.2805</div>
<div> 13 -56.53111117 -0.00618441 -1357.32
0.01030736 2262.20 0.2805</div>
<div> 14 -56.53111117 -0.00618441 -1357.32
0.01030736 2262.20 0.2805</div>
<div> 15 -56.53111117 -0.00618441 -1357.32
0.01030736 2262.20 0.2805</div>
<div>...</div>
<div><br>
</div>
<div>However, in the second SOC calculation (triplet + quintet),
spherical degeneracy (degeneracy = J * 2 + 1) is broken
because of unknown reasons:</div>
<div><br>
</div>
<div> Nr E E-E0 E-E0
E-E(1) E-E(1) E-E(1)</div>
<div> (au) (au) (cm-1)
(au) (cm-1) (eV)</div>
<div> 1 -56.54145102 -0.01652427 -3626.66
0.00000000 0.00 0.0000</div>
<div> 2 -56.54145075 -0.01652400 -3626.60
0.00000027 0.06 0.0000</div>
<div> 3 -56.54144331 -0.01651655 -3624.96
0.00000771 1.69 0.0002</div>
<div> 4 -56.53734340 -0.01241665 -2725.14
0.00410762 901.52 0.1118</div>
<div> 5 -56.53734093 -0.01241418 -2724.60
0.00411009 902.06 0.1118</div>
<div> 6 -56.53731961 -0.01239286 -2719.92
0.00413141 906.74 0.1124</div>
<div> 7 -56.53730864 -0.01238189 -2717.51
0.00414238 909.15 0.1127</div>
<div> 8 -56.53730809 -0.01238134 -2717.39
0.00414293 909.27 0.1127</div>
<div> 9 -56.53118445 -0.00625770 -1373.41
0.01026657 2253.25 0.2794</div>
<div> 10 -56.53117231 -0.00624555 -1370.74
0.01027871 2255.92 0.2797</div>
<div> 11 -56.53116127 -0.00623451 -1368.32
0.01028975 2258.34 0.2800</div>
<div> 12 -56.53114109 -0.00621434 -1363.89
0.01030993 2262.77 0.2805</div>
<div> 13 -56.53113027 -0.00620352 -1361.52
0.01032075 2265.14 0.2808</div>
<div> 14 -56.53112879 -0.00620203 -1361.19
0.01032223 2265.47 0.2809</div>
<div> 15 -56.53112337 -0.00619661 -1360.00
0.01032765 2266.66 0.2810</div>
<div>...</div>
<div><br>
</div>
<div>There is no such a problem in the following all-electron
calculation, so the error may be related to the ECPLS option.</div>
<div><br>
</div>
<div>***,Ta+, SOC with A.E.</div>
<div>memory,100,m</div>
<div><br>
</div>
<div>symmetry,xyz</div>
<div><br>
</div>
<div>geometry={Ta}</div>
<div><br>
</div>
<div>basis=vtz-dk</div>
<div><br>
</div>
<div>set dkroll=1</div>
<div><br>
</div>
<div>{hf;occ,21,19;wf,80,1,0}</div>
<div><br>
</div>
<div>{multi;natorb,ci;</div>
<div>! 4f5s5p are inactive</div>
<div>frozen,14,9;closed,15,19;occ,21,19;</div>
<div>wf,72,1,0;state,5; ! 1D</div>
<div>wf,72,1,2;state,10; ! 3P, 3F</div>
<div>wf,72,1,4;state,7; ! 5F</div>
<div>}</div>
<div><br>
</div>
<div>{ci;noexc;wf,72,1,0;state,5;</div>
<div>save,4201.3;}</div>
<div>{ci;noexc;wf,72,1,2;state,10;</div>
<div>save,4221.3;}</div>
<div>{ci;noexc;wf,72,1,4;state,7;</div>
<div>save,4241.3;}</div>
<div><br>
</div>
<div>lsint</div>
<div>{ci;hlsmat,ls,4201.3,4221.3;}</div>
<div>{ci;hlsmat,ls,4221.3,4241.3;}</div>
<div>{ci;hlsmat,ls,4201.3,4241.3;}</div>
<div>---</div>
<div><br>
</div>
<div>Best wishes,</div>
<div>Wenli</div>
<div><br>
</div>
</div>
<br>
<fieldset class="mimeAttachmentHeader"></fieldset>
<br>
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</blockquote>
<br>
<br>
<pre class="moz-signature" cols="72">--
Dr. Alexander Mitrushchenkov, IGR
Laboratoire de Modélisation et Simulation Multi Echelle
UMR 8208 CNRS
Université Paris-Est Marne-la-Vallée
5 Bd Descartes
77454 Marne la Vallée, Cedex 2, France
Phone: +33(0)160957316
Fax: +33(0)160957320
e-mail: <a class="moz-txt-link-abbreviated" href="mailto:Alexander.Mitrushchenkov@u-pem.fr">Alexander.Mitrushchenkov@u-pem.fr</a></pre>
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