[molpro-user] Problems with CASSCF calculations of plutonyl (PuO_2)^{+2} in C1 symmetry
Robert Polly
polly at kit.edu
Wed Apr 15 07:18:11 BST 2015
Dear MOLPRO users,
I am engaged in CASSCF calculations on uranyl (UO_2)^{+2}, neptunyl
(NpO_2)^{+2}
and plutonyl (PuO_2)^{+2}.
In order to use the Natural Bond Orbital analysis program (NBO)
we had to reduce the symmetry from D2h -> C2v -> C2 -> C1.
Molpro Version: molpro.2012.1.21
In all three MCSCF calculations the input looks like (only differing in
the wf card):
(for the complete input&output see attachement)
*******************************************
ANGSTROM
geometry={
Pu,, 0.0000000, 0.0000000, 0.0000000
O,, 0.0000000, 0.0000000, -1.6846957580
O,, 0.0000000, 0.0000000, 1.6846957580
}
{multi
occ, 16,10,10,3,12,5,5,2;
closed,14, 7, 7,3, 9,3,3,1;
wf,108,6,2;state,1;
wf,108,7,2;state,1;
print,civector;
orbprint,2;
start,2145.2;
orbital,2145.2;
expec2,lzz}
ANGSTROM
symmetry,x,y
geometry={
Pu,, 0.0000000, 0.0000000, 0.0000000
O,, 0.0000000, 0.0000000, -1.6846957580
O,, 0.0000000, 0.0000000, 1.6846957580
}
{multi
occ, 28,15,15,5;
closed,23,10,10,4;
wf,108,2,2;state,1;
wf,108,3,2;state,1;
print,civector;
start,2145.2;
orbital,2146.2;
expec2,lzz}
pop
individual
ANGSTROM
symmetry,xy
geometry={
Pu,, 0.0000000, 0.0000000, 0.0000000
O,, 0.0000000, 0.0000000, -1.6846957580
O,, 0.0000000, 0.0000000, 1.6846957580
}
{multi
occ, 33,30;
closed,27,20;
wf,108,2,2;state,2;
print,civector;
start,2146.2;
orbital,2147.2;
expec2,lzz}
pop
individual
ANGSTROM
symmetry,nosym
geometry={
Pu,, 0.0000000, 0.0000000, 0.0000000
O,, 0.0000000, 0.0000000, -1.6846957580
O,, 0.0000000, 0.0000000, 1.6846957580
}
{multi
occ, 63;
closed,47;
wf,108,1,2;state,2;
maxiter,1;
print,civector;
start,2147.2;
orbital,2148.2;
expec2,lzz}
{pop; individual}
{nbo,level=1;density,2148.2}
*******************************************
This works fine for (UO_2)^{+2} and neptunyl (NpO_2)^{+2}!
But for plutonyl (PuO_2)^{+2} I get the following error message in
the MCSCF for the calculation in C1 symmetry (see attached output)
*******************************************
......
Wavefunction dump at record 2148.2
Convergence thresholds 0.10E-01 (gradient) 0.22E-05 (energy)
0.10E-02 (step length)
Weight factors for state symmetry 1: 0.50000 0.50000
Number of orbital rotations: 10139 ( 752 Core/Active 7003
Core/Virtual 0 Active/Active 2384 Active/Virtual)
Total number of variables: 206136059
ITER. MIC NCI NEG ENERGY(VAR) ENERGY(PROJ) ENERGY
CHANGE GRAD(0) GRAD(ORB) GRAD(CI) STEP TIME
? Error
? Infinite loop
? The problem occurs in muwvfc:ci2
*******************************************
The same error occurs for (UO_2)^{0}. Hence, it works for N=106
((UO_2)^{+2}) and N=107 ((NpO_2)^{+2}) electrons,
but breaks for N=108 electrons ((PuO_2)^{+2} and (UO_2)^{0}).
Any help to solve the issue would be greatly appreciated,
cheers,
Robert
--
*********************************************************************
Karlsruher Institut für Technologie (KIT)
Institut fuer Nukleare Entsorgung
Dr. Robert Polly
Quantenchemie
Institut fuer Nukleare Entsorgung (INE), Campus Nord, Gebaeude 712,
Postfach 3640, 76021 Karlsruhe, Germany
0049-(0)721-608-24396
email: polly at kit.edu
www: http://www.fzk.de/ine
KIT - Universität des Landes Baden-Württemberg und
nationales Großforschungszentrum in der Helmholtz-Gemeinschaft
*********************************************************************
-------------- next part --------------
memory,2000,m;
gprint,orbitals,basis
gexpec,lz
file,1,puo2_new_ccsd_ta.int,old
file,2,puo2_new_ccsd_ta.wfu,old
SET,DKROLL=1
basis={o=aug-cc-pVTZ;
!
! PLUTONIUM (26s,23p,17d,13f,5g,3h) -> [12s,10p,9d,8f,5g,3h]
! PLUTONIUM (26s,23p,17d,13f,5g,3h) -> [12s,10p,9d,8f,5g,3h]
s, PU , 54251644.20000000, 13946738.00000000, 4475086.730000000, 1553698.380000000, 574436.7430000000, 221248.9930000000, 88241.3091000000, 36037.0726000000, 14943.6392000000, 6293.2561400000, 2710.7185200000, 1199.6970100000, 543.7359130000, 256.2840680000, 125.0265400000, 62.7882925000, 31.8857192000, 16.0667788000, 8.1327331500, 3.8747232000, 1.8086807000, 0.7658499800, 0.2974020300, 0.1189608100, 0.0475843200, 0.0190337300
c, 1.26, 0.00249294, 0.00235140, 0.00653693, 0.00964595, 0.01907604, 0.03150027, 0.05650682, 0.09609109, 0.16472266, 0.25481578, 0.31761116, 0.23268679, 0.05868708, 0.00040681, 0.00078369, -0.00050984, 0.00028371, -0.00016713, 0.00009959, -0.00005157, 0.00002485, -0.00001116, 0.00000548, -0.00000295, 0.00000137, -0.00000039
c, 1.26, -0.00104488, -0.00098842, -0.00275085, -0.00408162, -0.00812043, -0.01357709, -0.02477954, -0.04344512, -0.07805836, -0.13094872, -0.18173802, -0.11630419, 0.24362767, 0.58611657, 0.30135670, 0.02247790, 0.00195841, -0.00118006, 0.00050312, -0.00024315, 0.00012640, -0.00005516, 0.00002673, -0.00001436, 0.00000659, -0.00000192
c, 1.26, 0.00051143, 0.00048403, 0.00134740, 0.00200109, 0.00398560, 0.00667780, 0.01222662, 0.02154924, 0.03906669, 0.06651635, 0.09441320, 0.05683691, -0.19745038, -0.59242107, -0.27638631, 0.77319659, 0.58522617, 0.04358614, 0.00803096, -0.00413091, 0.00192280, -0.00089581, 0.00044694, -0.00024081, 0.00011341, -0.00003192
c, 1.26, -0.00026669, -0.00025245, -0.00070274, -0.00104402, -0.00207968, -0.00348709, -0.00638752, -0.01127942, -0.02047705, -0.03504993, -0.04990052, -0.02981435, 0.11772265, 0.37227366, 0.18646367, -0.87528722, -0.81793898, 0.89759732, 0.75604534, 0.03181824, 0.00827614, -0.00369577, 0.00179336, -0.00099711, 0.00047579, -0.00013268
c, 1.26, 0.00013346, 0.00012634, 0.00035170, 0.00052250, 0.00104099, 0.00174550, 0.00319870, 0.00564882, 0.01026592, 0.01757925, 0.02509460, 0.01485819, -0.06086874, -0.19689085, -0.09935204, 0.54026292, 0.55804184, -0.91800234, -1.13490552, 1.06396183, 0.72715003, -0.00432805, 0.01431025, -0.00752537, 0.00400267, -0.00097007
c, 1.26, -0.00005862, -0.00005549, -0.00015448, -0.00022949, -0.00045729, -0.00076663, -0.00140547, -0.00248086, -0.00451307, -0.00772019, -0.01105038, -0.00647867, 0.02683852, 0.08798137, 0.04350871, -0.24787974, -0.27082025, 0.49208936, 0.66289203, -0.90451901, -0.87048767, 0.96490379, 0.65220109, -0.04141520, 0.04745318, -0.00440201
c, 1.26, 0.00001848, 0.00001749, 0.00004869, 0.00007233, 0.00014412, 0.00024163, 0.00044293, 0.00078203, 0.00142215, 0.00243426, 0.00348089, 0.00204841, -0.00848849, -0.02773541, -0.01387960, 0.07906794, 0.08580637, -0.15817521, -0.22193071, 0.32117221, 0.32189867, -0.44502810, -0.55146445, 0.27288504, 0.84553192, 0.18245048
c, 1.26, -0.00004516, -0.00004276, -0.00011897, -0.00017689, -0.00035202, -0.00059136, -0.00108062, -0.00191733, -0.00346078, -0.00599501, -0.00838832, -0.00534712, 0.02176959, 0.06543303, 0.04091411, -0.21317116, -0.17884992, 0.34671743, 0.68921453, -1.20360454, -0.43793621, 1.88778147, -0.48383002, -1.40924878, 0.34930435, 0.76857229
c, 1.26, 0.00006327, 0.00005995, 0.00016667, 0.00024808, 0.00049281, 0.00083027, 0.00151028, 0.00269890, 0.00481859, 0.00849306, 0.01151021, 0.00818643, -0.03256682, -0.08680951, -0.07136719, 0.33784373, 0.18580074, -0.39875536, -1.23409432, 2.49916632, -0.50872660, -2.78845238, 3.80109805, -1.83142348, -0.86735339, 1.22410903
!c, 1.26, -0.00008505, -0.00008066, -0.00022387, -0.00033412, -0.00066091, -0.00112108, -0.00201739, -0.00366617, -0.00637950, -0.01170462, -0.01471288, -0.01314229, 0.05014633, 0.10179484, 0.13881894, -0.57700863, -0.04360807, 0.28577711, 2.41518618, -6.11234302, 6.31019519, -2.98600919, -0.88472036, 3.62280626, -3.92780701, 1.87096952
!c, 1.26, 0.00010076, 0.00009531, 0.00026565, 0.00039399, 0.00078723, 0.00131433, 0.00242609, 0.00423970, 0.00783786, 0.01308886, 0.01961329, 0.00949785, -0.04294944, -0.16858767, -0.04709232, 0.44183799, 0.63006181, -1.73371242, -0.70020544, 5.75530280, -8.75554296, 8.57458885, -7.73740670, 6.67681151, -4.49229445, 1.70084867
!c, 1.26, -0.00023239, -0.00021804, -0.00061555, -0.00089566, -0.00184482, -0.00293445, -0.00584677, -0.00905370, -0.02003476, -0.02476955, -0.06047090, 0.02059673, -0.01427971, 0.72411625, -0.71688743, 0.60562270, -5.29737268, 14.48186557, -19.40986429, 16.83755787, -11.03067632, 5.97221631, -3.40091182, 2.10301145, -1.11344409, 0.35961642
p, PU , 26053465.80000000, 5488687.630000000, 1377376.700000000, 387581.7000000000, 119257.3970000000, 39624.1764000000, 14156.7751000000, 5434.8600100000, 2234.3893100000, 975.5529220000, 447.5388250000, 213.6463980000, 103.4895540000, 52.4220770000, 26.5045933000, 13.2414502000, 6.5198106800, 2.9538448100, 1.2734159500, 0.5257129800, 0.2102851900, 0.0841140700, 0.0336456300
c, 1.23, 0.00005251, 0.00011499, 0.00031926, 0.00080345, 0.00209793, 0.00557067, 0.01516097, 0.04122835, 0.10630969, 0.23479423, 0.37401841, 0.32659545, 0.10335081, 0.00283068, 0.00152398, -0.00094790, 0.00044254, -0.00019825, 0.00010118, -0.00004985, 0.00002535, -0.00001184, 0.00000373
c, 1.23, -0.00002788, -0.00006113, -0.00017001, -0.00042897, -0.00112513, -0.00300531, -0.00826522, -0.02281570, -0.06050789, -0.13896132, -0.23126007, -0.14142712, 0.31411357, 0.58329938, 0.23467235, 0.01421998, 0.00125059, -0.00065839, 0.00025907, -0.00013089, 0.00006648, -0.00003141, 0.00000984
c, 1.23, 0.00001463, 0.00003208, 0.00008925, 0.00022536, 0.00059174, 0.00158287, 0.00436518, 0.01209316, 0.03231526, 0.07495323, 0.12636289, 0.06432538, -0.26974106, -0.51920510, 0.11053400, 0.76929242, 0.31616926, 0.00898156, 0.00224984, -0.00119290, 0.00059681, -0.00027880, 0.00008886
c, 1.23, -0.00000708, -0.00001553, -0.00004320, -0.00010920, -0.00028642, -0.00076811, -0.00211297, -0.00588526, -0.01566569, -0.03672224, -0.06132171, -0.03108522, 0.15131832, 0.27785946, -0.10707164, -0.71846641, -0.00724991, 0.90231025, 0.27893846, -0.00420668, 0.00557816, -0.00247204, 0.00076614
c, 1.23, 0.00000279, 0.00000613, 0.00001705, 0.00004308, 0.00011302, 0.00030301, 0.00083415, 0.00232208, 0.00618980, 0.01449947, 0.02427899, 0.01205014, -0.06107053, -0.11332534, 0.05076615, 0.32234650, -0.02685694, -0.62167485, 0.01000959, 0.76945815, 0.35435053, 0.01073119, 0.00374004
c, 1.23, -0.00000138, -0.00000302, -0.00000841, -0.00002124, -0.00005580, -0.00014926, -0.00041224, -0.00114257, -0.00306357, -0.00712191, -0.01207563, -0.00567641, 0.02961348, 0.05786249, -0.02947232, -0.15624099, 0.00447973, 0.37098565, -0.10770755, -0.54084565, 0.01785314, 0.69719157, 0.39285366
c, 1.23, 0.00000340, 0.00000744, 0.00002074, 0.00005226, 0.00013781, 0.00036659, 0.00102088, 0.00279828, 0.00761389, 0.01736234, 0.03036539, 0.01235590, -0.06953991, -0.15407488, 0.09931449, 0.35909306, 0.03563052, -1.22178254, 1.13584258, 0.64424156, -1.52433262, 0.31522545, 0.56626491
c, 1.23, -0.00000337, -0.00000740, -0.00002059, -0.00005200, -0.00013658, -0.00036562, -0.00100898, -0.00280105, -0.00749848, -0.01749399, -0.02951959, -0.01404071, 0.07535064, 0.14424258, -0.08544105, -0.43186285, 0.12526773, 1.28587584, -2.12792923, 1.30124832, 0.52656027, -1.91037137, 1.42532503
!c, 1.23, 0.00000484, 0.00001068, 0.00002945, 0.00007553, 0.00019348, 0.00053851, 0.00140372, 0.00421037, 0.01017987, 0.02719096, 0.03662073, 0.03611429, -0.15342679, -0.11359106, -0.06031518, 1.07400479, -1.09663305, -0.72103681, 2.76577109, -3.73896598, 3.67939510, -2.76751825, 1.21651001
!c, 1.23, -0.00001018, -0.00002264, -0.00006161, -0.00016142, -0.00039902, -0.00117331, -0.00281919, -0.00942326, -0.01971391, -0.06342165, -0.06018959, -0.12135390, 0.46599808, -0.01899640, 0.51409519, -3.59098064, 6.26032746, -6.09340517, 4.47510011, -2.91201269, 1.80896366, -0.99292568, 0.35027175
d, PU , 14943.6392000000, 6293.2561400000, 2710.7185200000, 1199.6970100000, 543.7359130000, 256.2840680000, 125.0265400000, 62.7882925000, 31.8857192000, 16.0667788000, 8.1327331500, 3.8747232000, 1.8086807000, 0.7658499800, 0.2974020300, 0.1189608100, 0.0475843200
c, 1.17, 0.00034733, 0.00088222, 0.00424777, 0.01709053, 0.06304124, 0.17940614, 0.34991770, 0.38826691, 0.18690613, 0.02644473, 0.00084591, -0.00009659, 0.00003789, -0.00003095, 0.00001226, -0.00000670, 0.00000205
c, 1.17, -0.00019670, -0.00050043, -0.00242282, -0.00981162, -0.03670615, -0.10632646, -0.20562350, -0.17947282, 0.17717557, 0.53289017, 0.36968470, 0.06342264, -0.00183006, 0.00066393, -0.00037767, 0.00017096, -0.00005814
c, 1.17, 0.00008839, 0.00022116, 0.00109194, 0.00437069, 0.01657582, 0.04776644, 0.09328472, 0.07228543, -0.11766398, -0.32900220, -0.09799202, 0.49942051, 0.53181318, 0.13699443, 0.00047702, 0.00226222, -0.00080259
c, 1.17, -0.00002801, -0.00006961, -0.00034623, -0.00137916, -0.00525368, -0.01509645, -0.02960725, -0.02235643, 0.03901652, 0.10983630, 0.02296622, -0.20801823, -0.21125477, 0.26789836, 0.52755077, 0.35099908, 0.10995684
c, 1.17, 0.00004253, 0.00010726, 0.00052510, 0.00211579, 0.00798551, 0.02313787, 0.04502713, 0.03497790, -0.06110937, -0.16920131, -0.04423844, 0.37936241, 0.33053562, -0.93157433, -0.15682740, 0.64302719, 0.24616825
c, 1.17, -0.00004105, -0.00014075, -0.00049313, -0.00254973, -0.00797901, -0.02731400, -0.04368894, -0.05294665, 0.09812479, 0.12702859, 0.19421836, -0.82289073, 0.24613598, 1.05965025, -1.33884833, 0.29093549, 0.59225414
!c, 1.17, 0.00004427, 0.00020150, 0.00051414, 0.00342545, 0.00899248, 0.03611712, 0.04754558, 0.08191499, -0.16331476, -0.09236319, -0.37871385, 1.61694633, -1.80782934, 0.67144317, 0.63285382, -1.45269443, 1.14975138
!c, 1.17, -0.00007122, -0.00015242, -0.00088754, -0.00316322, -0.01315395, -0.03506659, -0.07653841, -0.05029845, 0.08667269, 0.38037689, -0.03268399, -1.58046420, 2.67474299, -2.58908909, 2.25941876, -1.82801030, 0.93714991
!c, 1.17, 0.00029214, -0.00028376, 0.00395520, 0.00059082, 0.04693903, 0.02263496, 0.31009942, -0.22168543, 0.50600777, -2.79329677, 4.82371694, -4.43275005, 2.79699700, -1.43686590, 0.78477885, -0.44806924, 0.17673949
f, PU , 975.5529220000, 447.5388250000, 213.6463980000, 103.4895540000, 52.4220770000, 26.5045933000, 13.2414502000, 6.5198106800, 2.9538448100, 1.2734159500, 0.5257129800, 0.2102851900, 0.0841140700
c, 1.13, 0.00098630, 0.00395391, 0.02144404, 0.07517896, 0.19477800, 0.34930917, 0.38214148, 0.21513776, 0.04203903, -0.00082314, 0.00092234, -0.00037458, 0.00013777
c, 1.13, -0.00032327, -0.00127220, -0.00703978, -0.02446783, -0.06403178, -0.10736653, -0.09515665, 0.07824573, 0.35025383, 0.44479037, 0.30322031, 0.11469965, 0.00722375
c, 1.13, 0.00031174, 0.00127842, 0.00684354, 0.02435130, 0.06241178, 0.10496923, 0.07996383, -0.10370734, -0.39608983, -0.21945688, 0.44457029, 0.48217774, 0.17647463
c, 1.13, -0.00031687, -0.00170770, -0.00733922, -0.03038835, -0.06817982, -0.13202341, -0.06244423, 0.10370256, 0.65027309, -0.39461221, -0.65896233, 0.58530794, 0.36632456
!c, 1.13, 0.00031770, 0.00148757, 0.00714246, 0.02721521, 0.06581683, 0.11540390, 0.06107815, -0.15303217, -0.69986781, 1.27952189, -0.70600556, -0.40483158, 0.83617326
!c, 1.13, -0.00082712, -0.00038833, -0.01537388, -0.02273636, -0.13063687, -0.06393799, -0.23497860, 0.70076641, -0.07298899, -0.94966410, 1.53776542, -1.59267115, 1.00293789
!c, 1.13, 0.00173097, 0.00092679, 0.03243714, 0.04966878, 0.27199887, 0.10209887, 0.35434799, -1.83191065, 2.27680972, -1.76952594, 1.20834905, -0.79930440, 0.38772565
!c, 1.13, -0.00101852, 0.02330933, 0.00414378, 0.31254498, 0.09542907, 1.02637746, -2.72191866, 2.64754223, -1.59872212, 0.83538894, -0.43259931, 0.22120878, -0.08712604
g, PU , 3.8747232000, 1.8086807000, 0.7658499800, 0.2974020300, 0.1189608100
c, 1.5, 0.16072694, 0.35222555, 0.55159242, 0.20214081, 0.02965220
c, 1.5, -0.29446996, -0.54384067, 0.25294819, 0.58569922, 0.14386149
!c, 1.5, 0.52339278, 0.19954664, -0.92258772, 0.56371391, 0.38773446
!c, 1.5, -0.87866538, 0.89784187, -0.09398920, -0.71318415, 0.93244402
!c, 1.5, 1.04064838, -1.60170748, 1.43869645, -1.20941211, 0.79133255
h, PU , 0.9190199700, 0.3568824300, 0.1427529700
c, 1.3, 0.94318589, 0.08572380, 0.07194679
!c, 1.3, -0.65865802, 1.06997837, 0.10879984
!c, 1.3, 0.28060996, -0.86510514, 1.19424449
}
ANGSTROM
geometry={
Pu,, 0.0000000, 0.0000000, 0.0000000
O,, 0.0000000, 0.0000000, -1.6846957580
O,, 0.0000000, 0.0000000, 1.6846957580
}
{multi
occ, 16,10,10,3,12,5,5,2;
closed,14, 7, 7,3, 9,3,3,1;
wf,108,6,2;state,1;
wf,108,7,2;state,1;
print,civector;
orbprint,2;
start,2145.2;
orbital,2145.2;
expec2,lzz}
!pop
!individual
ANGSTROM
symmetry,x,y
geometry={
Pu,, 0.0000000, 0.0000000, 0.0000000
O,, 0.0000000, 0.0000000, -1.6846957580
O,, 0.0000000, 0.0000000, 1.6846957580
}
{multi
occ, 28,15,15,5;
closed,23,10,10,4;
wf,108,2,2;state,1;
wf,108,3,2;state,1;
print,civector;
start,2145.2;
orbital,2146.2;
expec2,lzz}
pop
individual
ANGSTROM
symmetry,xy
geometry={
Pu,, 0.0000000, 0.0000000, 0.0000000
O,, 0.0000000, 0.0000000, -1.6846957580
O,, 0.0000000, 0.0000000, 1.6846957580
}
{multi
occ, 33,30;
closed,27,20;
wf,108,2,2;state,2;
print,civector;
start,2146.2;
orbital,2147.2;
expec2,lzz}
pop
individual
ANGSTROM
symmetry,nosym
geometry={
Pu,, 0.0000000, 0.0000000, 0.0000000
O,, 0.0000000, 0.0000000, -1.6846957580
O,, 0.0000000, 0.0000000, 1.6846957580
}
{multi
occ, 63;
closed,47;
wf,108,1,2;state,2;
maxiter,1;
print,civector;
start,2147.2;
orbital,2148.2;
expec2,lzz}
{pop; individual}
{nbo,level=1;density,2148.2}
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