number of occupied orbitals < number of electrons

xujroman leit... at matcalc.de
Thu Oct 27 08:16:53 UTC 2011


Hello,

I am trying to perform a spin relaxation of an iorn-oxide surface
using the keyword RELAX_MULTIPLICITY. However, during the geometry
optimization I got starnge results:

The number of electrons in the second spin channel was some tomes
larger than the number of occupied orbitals. How can this be and where
are the missing electrons?


Here is my input file:

 &GLOBAL
   PRINT_LEVEL  MEDIUM
   PROJECT_NAME VW-HDI
   RUN_TYPE  GEO_OPT
   TRACE_MASTER  T
 &END GLOBAL
 &MOTION
   &GEO_OPT
     OPTIMIZER  CG
     MAX_ITER            2000
     MAX_FORCE     1.0000000000000001E-03
     RMS_FORCE 5.0E-04
     STEP_START_VAL             220
     &CG
       &LINE_SEARCH
         TYPE  2PNT
       &END LINE_SEARCH
     &END CG
   &END GEO_OPT
 &END MOTION
 &FORCE_EVAL
   METHOD  QS
   &DFT
     UKS  T
     RELAX_MULTIPLICITY
     MULTIPLICITY 5
     &SCF
       CHOLESKY INVERSE
       ADDED_MOS 120 120
       &DIAGONALIZATION on
         ALGORITHM standard
       &END DIAGONALIZATION
       MAX_SCF             500
       SCF_GUESS  RESTART
       &SMEAR on
         METHOD energy_window
         WINDOW_SIZE [Ry] 0.0002
       &END SMEAR
       &MIXING  T
         METHOD  BROYDEN_MIXING
         ALPHA     1.0000000000000001E-01
         BETA     1.5000000000000000E+00
         NBUFFER               8
       &END MIXING
     &END SCF
     &QS
       EXTRAPOLATION  PS
       EXTRAPOLATION_ORDER               3
       METHOD  GAPW
     &END QS
     &MGRID
       CUTOFF     2.4000000000000000E+02
     &END MGRID
     &XC
       DENSITY_CUTOFF     1.0000000000000000E-10
       GRADIENT_CUTOFF     1.0000000000000000E-10
       TAU_CUTOFF     1.0000000000000000E-10
       &XC_FUNCTIONAL  NO_SHORTCUT
         &PBE  T
         &END PBE
       &END XC_FUNCTIONAL
     &END XC
     &POISSON
       POISSON_SOLVER  ANALYTIC
       PERIODIC  XY
       &MULTIPOLE
         RCUT     8.0000000000000000E+00
         ANALYTICAL_GTERM  T
       &END MULTIPOLE
     &END POISSON
   &END DFT
   &SUBSYS
     &CELL
       A     1.1520000000000000E+01    0.0000000000000000E+00
0.0000000000000000E+00
       B     0.0000000000000000E+00    1.1520000000000000E+01
0.0000000000000000E+00
       C     0.0000000000000000E+00    0.0000000000000000E+00
2.1000000000000000E+01
       PERIODIC  XY
       MULTIPLE_UNIT_CELL               1              1
1
     &END CELL
     &COORD
O    1.4788279209685332E-01   -6.4079127030438565E-01
8.8325220476786459E+00
Fe    2.7690016478320506E-01   -8.8915274592209970E-01
6.8850929290175822E+00
Fe    8.7976400000000012E+00   -8.1269000000000002E-01
2.3749000000000007E+00
Fe    3.0397300000000000E+00    4.9492500000000001E+00
2.3281299999999998E+00
Fe    3.0415199999999998E+00   -8.0908999999999998E-01
2.3671099999999998E+00
Fe    8.8016500000000022E+00    4.9505000000000017E+00
2.3718499999999998E+00
Cr    1.5265445268577713E-01    5.8547325880567636E-01
3.4448478005617953E+00
Fe    5.9218683378316381E+00    6.3491609715429966E+00
3.5120592438162541E+00
Fe    5.9128074354347282E+00   -1.0007845151664561E+00
6.6748887610404619E+00
Fe    1.4801933747518614E-01    4.8422040959602102E+00
6.6830146057510671E+00
Fe    1.6518698341045117E+00    3.4577332222971751E+00
4.3921260516205685E+00
Fe    7.4147254803784044E+00    9.2345216383798157E+00
4.3381068302596599E+00
Fe    1.0400877636239809E+01    3.4838451416053879E+00
4.6874611836597584E+00
Fe    4.4095248778956488E+00    9.2352850403451114E+00
4.3428553231525111E+00
Fe    1.7781202502280388E-01    2.0005025322446044E+00
6.6470490850910524E+00
Fe    5.9249948780883646E+00    7.8362809136553038E+00
6.5642930381252169E+00
O    2.7181562422782773E-01    2.0649141134020774E+00
4.6331220353614135E+00
O    5.9582322107966172E+00    7.8914440031415687E+00
4.5520067821988919E+00
O    1.5768800000000005E+00    6.2200000000000011E-01
2.0271200000000000E+00
O    7.3381400000000010E+00    6.3885500000000004E+00
2.0141100000000001E+00
O    1.0259890000000000E+01    6.1856000000000000E-01
2.0292300000000001E+00
O    4.4943300000000015E+00    6.3917099999999998E+00
2.0221700000000000E+00
O    2.3431379700941141E-01   -9.2079833437695002E-01
4.5643731467106337E+00
O    5.9915725286798907E+00    4.7625955453337196E+00
4.4997981923690817E+00
Fe    5.9191108455829218E+00    5.8797518939309257E-01
3.5070629942191505E+00
Fe    1.6046413550995117E-01    6.3583955327557842E+00
3.4881603649320079E+00
Fe    6.0313733675113355E+00    4.7406107244663804E+00
6.6720256323340177E+00
Fe    7.5120882865556027E+00    3.4555116330989577E+00
4.2753228501643532E+00
Fe    1.6536729623048274E+00    9.3073495251237315E+00
4.4533705871827580E+00
Cr    4.5354767902471540E+00    3.4733330290391859E+00
4.4492842576590723E+00
Fe    1.0295771610071485E+01    9.2225325279460026E+00
4.7710339650507700E+00
Fe    5.9394068689383159E+00    2.0433397126326480E+00
6.6435001193869283E+00
Fe    1.6028248475490683E-01    7.8288308493322809E+00
6.5802077664031851E+00
O    5.9571179851410045E+00    2.1575479421128634E+00
4.5625120047583181E+00
O    2.8607237010793973E-01    7.9333675176737790E+00
4.5915247215196127E+00
O    7.3586400000000003E+00    6.1438000000000004E-01
2.0099300000000002E+00
O    1.5794400000000000E+00    6.3908199999999997E+00
2.0123000000000002E+00
O    4.4784400000000000E+00    6.1450000000000005E-01
1.9985800000000005E+00
O    1.0250859999999999E+01    6.3854700000000006E+00
2.0150999999999999E+00
O    5.9231999150645613E+00   -9.5218640007183042E-01
4.5028629656638852E+00
O    3.4057444225745115E-01    4.8299851411679642E+00
4.5516050881309491E+00
Fe    3.0312392479226045E+00    3.3739554802915199E+00
7.7231011771401299E+00
Fe    8.7945661402723108E+00    9.2186752738178743E+00
7.9219196076663589E+00
Fe    8.8009800000000027E+00    2.0665300000000002E+00
2.5750899999999999E+00
Fe    3.0400299999999998E+00    7.8256100000000020E+00
2.3696700000000002E+00
Fe    1.0192495624358541E+01    5.9928981524545222E-01
8.6755199380288595E+00
Fe    4.5390742547280922E+00    6.4484765399717956E+00
8.3679159776549419E+00
Fe    7.3088525385393952E+00    6.0636007975618411E-01
8.6371873097259897E+00
Cr    1.6628453717476546E+00    6.3527919280508893E+00
8.6523689407285591E+00
O    8.7566933054942631E+00   -7.0840505098148965E-01
8.8554998850189808E+00
O    3.0919311385251018E+00    5.0490432546348663E+00
8.5449257982097535E+00
O    4.5308817654868001E+00    3.3826942726280640E+00
6.3940443265932334E+00
O    1.0311032878023529E+01    9.2162913616102049E+00
6.7069858180100947E+00
O    1.5747164293729607E+00    3.3634403659245571E+00
6.4132696101822715E+00
O    7.3480730120491531E+00    9.1441625544408023E+00
6.5535113539522527E+00
O    3.0391211460301504E+00    1.8539570794680584E+00
8.8599886437801505E+00
O    8.9014457534890212E+00    7.6283359434903479E+00
8.8760297648623858E+00
Fe    8.8145962782012894E+00    5.8104651410986463E-01
5.6122173579947781E+00
Cr    3.0164134927703801E+00    6.3467827402347163E+00
5.4973775675335457E+00
O    8.8880059205237938E+00   -8.8026576011240665E-01
4.3681378549088681E+00
O    3.0614358984316343E+00    4.8559672707889101E+00
4.3437196538558167E+00
O    7.2051074014582097E+00    5.9315680941952831E-01
6.5849775940394704E+00
O    1.5546905031629858E+00    6.4529316851620822E+00
6.6678916752037898E+00
O    1.0393433535294637E+01    5.8189058137684224E-01
6.6392715569925809E+00
O    4.6011708281178141E+00    6.4382940015005188E+00
6.3558407549187317E+00
O    8.9279377297922196E+00    2.0502945028849977E+00
4.4706732174596624E+00
O    2.9478632460465759E+00    7.8208699168275144E+00
4.3820554775833793E+00
Fe    8.8053292399764036E+00    3.4537137113277883E+00
7.8871133989636455E+00
Fe    3.0412877305603798E+00    9.2369900944983794E+00
7.7218251186956222E+00
Fe    3.0400500000000008E+00    2.0638000000000001E+00
2.3392200000000001E+00
Fe    8.7978500000000004E+00    7.8193900000000021E+00
2.3640400000000010E+00
Fe    4.4257642447927852E+00    6.0195656368134476E-01
8.6577593050598178E+00
Fe    1.0305950066956918E+01    6.3502123761872626E+00
8.5713509405273509E+00
Fe    1.5752182036292648E+00    5.7302119627195292E-01
8.6694167170733571E+00
Cr    7.3939463385783259E+00    6.4439327534089950E+00
8.6855222804595851E+00
O    2.9663138436985270E+00   -6.8654382437958850E-01
8.7629109614751712E+00
O    8.8970052202878236E+00    5.1108631889326341E+00
8.7612227304310597E+00
O    1.0304138613149108E+01    3.3756077526847044E+00
6.7215825920588168E+00
O    4.5048561589988623E+00    9.1650449746710869E+00
6.4797901493099719E+00
O    7.3814975329467662E+00    3.3599233672368807E+00
6.5739649415409547E+00
O    1.5600537448159482E+00    9.2196054802508289E+00
6.4639300850957060E+00
O    8.7482771318263008E+00    1.9012231724429036E+00
8.8909801206526140E+00
O    3.1172716046269735E+00    7.6717401283228668E+00
8.6758191359836481E+00
Fe    3.0559696384815691E+00    6.8857767982128493E-01
5.5165703554158254E+00
Fe    8.7990760680349123E+00    6.3636338110116624E+00
5.5140929725419081E+00
O    2.9948817405548431E+00   -8.1533548012990542E-01
4.3701573867948929E+00
O    8.9839266118147538E+00    4.8382740371659549E+00
4.3714458187286267E+00
O    1.5581219359963878E+00    6.5795952903489130E-01
6.6071529828580342E+00
O    7.3089563189106315E+00    6.4037200087949078E+00
6.6865792557479695E+00
O    4.5957544639128365E+00    6.1921592998069430E-01
6.5677568480843664E+00
O    1.0378073116047618E+01    6.3858485639881826E+00
6.5070971313032082E+00
O    3.0791821470400351E+00    2.1485528641150924E+00
4.3000196075025636E+00
O    8.9539615770748355E+00    7.8639524059049419E+00
4.3506689088665365E+00
Fe    1.5961000000000000E-01    3.5531700000000002E+00
1.1639299999999999E+00
Fe    5.9198899999999997E+00    9.2608499999999996E+00
1.1621300000000001E+00
O    2.7394957301408224E-01    1.8795047188287086E+00
8.5587630750989430E+00
O    5.9987714144632482E+00    7.7459236776359104E+00
8.4521605942163927E+00
O    1.0204710000000004E+01    3.5020500000000001E+00
2.1755900000000001E+00
O    4.4483200000000016E+00    9.2569599999999994E+00
2.1716400000000000E+00
O    1.6286100000000003E+00    3.5044400000000002E+00
2.1520000000000001E+00
O    7.3897600000000017E+00    9.2581900000000008E+00
2.1746799999999999E+00
O    5.8250042781611437E+00   -6.1759269671266559E-01
8.6564241533727078E+00
O    2.1971029556070371E-01    5.0912686055461567E+00
8.6683748170059918E+00
Fe    5.9192600000000004E+00    3.5458100000000008E+00
1.1654200000000001E+00
Cr    1.5625000000000006E-01    9.2572500000000009E+00
1.2128700000000003E+00
O    5.7668668675427641E+00    1.9567635660772327E+00
8.4998241889418118E+00
O    1.6007441109371531E-01    7.6099346746351602E+00
8.5179489677548261E+00
O    4.4459499999999998E+00    3.5019000000000000E+00
2.1825600000000009E+00
O    1.0190180000000000E+01    9.2643800000000027E+00
2.1468799999999999E+00
O    7.3915499999999996E+00    3.5034200000000011E+00
2.1600199999999998E+00
O    1.6526600000000005E+00    9.2616800000000037E+00
2.1674799999999999E+00
O    5.9098899051743015E+00    5.1305974936918401E+00
8.5015686773881249E+00
H    1.5768800000000005E+00    6.2200000000000011E-01
1.0271200000000000E+00
H    7.3381400000000010E+00    6.3885500000000004E+00
1.0141100000000001E+00
H    1.0259890000000000E+01    6.1856000000000000E-01
1.0289800000000000E+00
H    4.4943300000000015E+00    6.3917099999999998E+00
1.0221700000000000E+00
H    7.3586400000000003E+00    6.1438000000000004E-01
1.0099300000000000E+00
H    1.5794400000000000E+00    6.3908199999999997E+00
1.0123000000000000E+00
H    4.4784400000000000E+00    6.1450000000000005E-01
9.9858000000000025E-01
H    1.0250859999999999E+01    6.3854700000000006E+00
1.0150999999999999E+00
O    6.8678919584169913E+00    6.3356074702406424E+00
1.0782327801585261E+01
N    4.6238373569297240E+00    6.2509246712226902E+00
1.1368655972158635E+01
C    4.6286619829662436E+00    7.7262943711421057E+00
1.1546394752117275E+01
C    3.3497177750538265E+00    5.6427407089151513E+00
1.1299715750261067E+01
O    3.3638356158359848E+00    4.3170189421984526E+00
1.1521278109025321E+01
O    2.3160581699954554E+00    6.2818798504482478E+00
1.1071068776022649E+01
C    2.0711300294364690E+00    3.6358513021966878E+00
1.1364374421650140E+01
C    5.8935246256615432E+00    5.6266068444302713E+00
1.1149510433173196E+01
N    6.0184687233602947E+00    4.3055514226360669E+00
1.1375209893845886E+01
H    4.5339347972334920E+00    7.9554655084721171E+00
1.2614776023395661E+01
H    5.5719755395179948E+00    8.1140816273922223E+00
1.1155299414471827E+01
H    3.7957541790084175E+00    8.1599132592772321E+00
1.0987885221445660E+01
H    1.5000805150428229E+00    3.7565718455485548E+00
1.2291263459104648E+01
H    1.5143905685471859E+00    4.0444664750019195E+00
1.0513345351226949E+01
H    2.3307519863643260E+00    2.5920066673484587E+00
1.1174279180741635E+01
H    5.1673599257168892E+00    3.7538455155112049E+00
1.1464323767024304E+01
H    6.8096668053080478E+00    3.8743183014192488E+00
1.0902166667164790E+01
     &END COORD
     &KIND N
       BASIS_SET DZVP-MOLOPT-SR-GTH
       POTENTIAL GTH-PBE-q5
     &END KIND
     &KIND C
       BASIS_SET DZVP-MOLOPT-SR-GTH
       POTENTIAL GTH-PBE-q4
     &END KIND
     &KIND F
       BASIS_SET DZVP-MOLOPT-SR-GTH
       POTENTIAL GTH-PBE-q7
     &END KIND
     &KIND Fe
       BASIS_SET DZVP-MOLOPT-SR-GTH
       POTENTIAL GTH-PBE-q16
     &END KIND
     &KIND O
       BASIS_SET DZVP-MOLOPT-SR-GTH
       POTENTIAL GTH-PBE-q6
     &END KIND
     &KIND Mo
       BASIS_SET DZVP-MOLOPT-SR-GTH
       POTENTIAL GTH-PBE-q14
     &END KIND
     &KIND Cr
       BASIS_SET DZVP-MOLOPT-SR-GTH
       POTENTIAL GTH-PBE-q14
     &END KIND
     &KIND Si
       BASIS_SET DZVP-MOLOPT-SR-GTH
       POTENTIAL GTH-PBE-q4
     &END KIND
     &KIND H
       BASIS_SET DZVP-MOLOPT-SR-GTH
       POTENTIAL GTH-PBE-q1
     &END KIND
   &END SUBSYS
 &END FORCE_EVAL


I got the following output for the second geometry optimization step:


 DISTRIBUTION OF THE NEIGHBOR LISTS
              Total number of particle
pairs:                              22209
              Total number of matrix
elements:                           7095776
              Average number of particle
pairs:                             1389
              Maximum number of particle
pairs:                             1563
              Average number of matrix
element:                           443486
              Maximum number of matrix
elements:                          492602


 DISTRIBUTION OF THE OVERLAP MATRIX
              Number  of non-zero
blocks:                                   9170
              Percentage non-zero
blocks:                                  97.01
              Average number of blocks per
CPU:                              574
              Maximum number of blocks per
CPU:                              627
              Average number of matrix elements per
CPU:                  160945
              Maximum number of matrix elements per
CPU:                  175454

 Spin 1

 Number of
electrons:                                                        602
 Number of occupied
orbitals:                                                657
 Number of molecular
orbitals:                                               722

 Spin 2

 Number of
electrons:                                                        598
 Number of occupied
orbitals:                                                596
 Number of molecular
orbitals:                                               718

 Number of orbital
functions:                                               2277
 Number of independent orbital
functions:                                   2277

 Extrapolation method: PS Nth order


Can please someone tell me what I have done incorrect.
Thanks in advance,
Roman



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