[molpro-user] some questions about cc-pwCV5Z for CoO

Mon Aug 20 16:27:56 BST 2012

Hi,

in your basis input below, the Co basis is contracted, but your O basis set should read:

spdfgh,o,aug-cc-pwCV5Z;c;

To put this into your copy of Molpro, you'll have to convert the format of the Co basis set below to "libmol" format and put it in a file in the /lib subdirectory of your Molpro distribution with file extension .libmol .  Then execute "make" in this directory.  Probably an easier way for your purposes is to just make an include file containing your Co basis set as inputted below.  Then your basis set block could simply be:

basis={
default,aug-cc-pwCV5Z
include,Co_wcv5z.basis
}

where the file Co_wcv5z.basis contains your basis as formatted below.

To improve your RHF convergence, try including explicitly "occ" and "closed" directives to better define your wavefunction.  Having better RHF orbitals as an initial guess to your CASSCF calculation might help your last problem as well.  Also for your last point,  try doing a CASSCF first with fewer states and using that as an initial guess for your calculation that includes many states.

best,

-Kirk

On Aug 20, 2012, at 6:47 AM, 付铭凯 <fumingkai at iccas.ac.cn> wrote:

> 
> Dear colleagues,
>     I apologize in advance for my naive question. I am a new user of molpro. I am having troubles with doing  CASSCF calculation on cobalt Monoxide. From the reference I know that the ground state of CoO is X4Δ. The correlation consistent basis set of quintuple cardinality was used for the Co atom combined with the corresponding augmented basis set for the O atom, aug-cc- pV5Z. To account for the 3s23p6 subvalence core
> electrons of the Co atom, the weighted core cc-pwCV5Z set was employed in the CI calculations. But my local basis library does not have  cc-pwCV5Z  for Co. So I paste corresponding basis for Co from  EMSL website.
> Then I write input file as follows:
> ***,Coo
> memory,384,m;
> gprint,basis,orbital,civector;
> !file,2,Coo-single_point-test.wfu
> 
> basis={
> !
> ! COBALT       (30s,22p,14d,5f,4g,3h,2i) -> [11s,10p,8d,5f,4g,3h,2i]
> ! COBALT       (30s,22p,14d,5f,4g,3h,2i) -> [11s,10p,8d,5f,4g,3h,2i]
> s, CO , 1.61030E+08, 2.87558E+07, 6.42324E+06, 1.72120E+06, 533994.0000000, 186194.0000000, 71201.7000000, 29276.2000000, 12742.3000000, 5800.5100000, 2736.9600000, 1329.9900000, 662.6110000, 337.4150000, 175.2340000, 92.6434000, 49.7576000, 27.0728000, 14.8610000, 8.1812100, 4.4794100, 2.4119100, 1.2584400, 0.6312340, 0.2152970, 0.1185100, 0.0572090, 0.0271660, 7.3346000, 2.6036000
> c, 1.27, 1.005831E-05, 2.418419E-05, 6.846343E-05, 0.000160551, 0.0003573516, 0.0007524535, 0.001557729, 0.003215932, 0.006731782, 0.01430107, 0.03046694, 0.06307436, 0.1211301, 0.2019129, 0.2621166, 0.2203891, 0.09741493, 0.05139403, 0.08720267, 0.07201628, 0.02033519, 0.001482286, -3.935072E-05, -7.063343E-05, -3.872963E-07, 5.656943E-06, 5.765335E-06
> c, 1.27, -5.289415E-06, -1.271923E-05, -3.601347E-05, -8.448201E-05, -0.0001881435, -0.0003965136, -0.0008220461, -0.00170092, -0.003573935, -0.007640675, -0.01646716, -0.03483002, -0.06970371, -0.1257417, -0.1900435, -0.2055906, -0.08810301, 0.1847425, 0.4644587, 0.3893510, 0.1095439, 0.00749383, -0.001499069, -0.0007921508, -6.025659E-05, 6.137086E-05, 1.596147E-05
> c, 1.27, 1.229605E-06, 2.957032E-06, 8.373552E-06, 1.964835E-05, 4.377266E-05, 9.232007E-05, 0.000191559, 0.0003971299, 0.0008362892, 0.001797242, 0.003901641, 0.008385303, 0.01722495, 0.03269722, 0.05361657, 0.06544278, 0.02877317, -0.09285749, -0.3037701, -0.3649679, -0.01614853, 0.4594886, 0.5645161, 0.2219477, 0.01341422, -0.002819425, 0.002850658
> c, 1.27, -2.623766E-07, -6.309811E-07, -1.786773E-06, -4.192681E-06, -9.340377E-06, -1.970036E-05, -4.087664E-05, -8.474813E-05, -0.000178474, -0.0003835678, -0.0008329223, -0.001790232, -0.003680833, -0.006991583, -0.0114996, -0.01407429, -0.006263082, 0.02044358, 0.06899805, 0.08679416, -0.0002481641, -0.1278762, -0.2042779, -0.1679982, 0.09731253, 0.4059191, 0.4984338
> c, 1.27, -5.219106E-07, -1.254702E-06, -3.555186E-06, -8.332619E-06, -1.860578E-05, -3.90719E-05, -8.171241E-05, -0.0001672056, -0.0003592347, -0.0007508135, -0.001690506, -0.003475677, -0.007545748, -0.01340552, -0.02418218, -0.0253850, -0.01864738, 0.0535809, 0.1194320, 0.2332153, -0.08449372, -0.2635046, -0.7020055, 0.2829039, 1.2814760, 0.08269332, -0.5151596
> c, 1.27, -8.836608E-07, -2.124067E-06, -6.020144E-06, -1.410295E-05, -3.152172E-05, -6.60715E-05, -0.0001386482, -0.0002821319, -0.0006113458, -0.001262795, -0.002887387, -0.005828135, -0.01295023, -0.02239885, -0.04203284, -0.04150388, -0.03625394, 0.1006906, 0.2013184, 0.4996169, -0.2741211, -0.9585018, -0.9159533, 2.3009600, 0.4067037, -2.0722390, 0.2039038
> c, 1.27, 1.083962E-06, 2.608069E-06, 7.378921E-06, 1.734385E-05, 3.851368E-05, 8.174321E-05, 0.0001677276, 0.0003543362, 0.0007253799, 0.001622418, 0.003348887, 0.007673761, 0.01464827, 0.03072353, 0.0447970, 0.06813346, 0.01080639, -0.05323183, -0.4188921, -0.6190722, 0.5395570, 2.8852480, -3.2281870, -0.5981499, 4.2621970, -3.1973340, -0.9026527
> c, 1.27, 1.244828E-06, 2.992113E-06, 8.480955E-06, 1.986664E-05, 4.44134E-05, 9.306556E-05, 0.0001954644, 0.0003972354, 0.0008630873, 0.001777112, 0.004087733, 0.008208135, 0.01845557, 0.0317399, 0.06108727, 0.05970255, 0.05810058, -0.1582299, -0.3738525, -1.5325190, 3.3585990, 1.1755130, -7.4023150, 7.1300430, -3.6484700, -0.3800983, 3.3503540
> c, 28.28, 1
> c, 29.29, 1
> c, 30.30, 1
> p, CO , 97512.6000000, 23815.1000000, 7540.4300000, 2854.0800000, 1217.6900000, 562.5150000, 274.2740000, 139.1140000, 72.8598000, 39.2448000, 21.6430000, 12.1149000, 6.7691200, 3.7052800, 1.9790100, 1.0312700, 0.5136090, 0.2044820, 0.0838700, 0.0341020, 11.2264000, 3.6309000
> c, 1.19, 0.0000220, 0.0000660, 0.0002520, 0.0008480, 0.0028130, 0.0086460, 0.0244890, 0.0618950, 0.1332890, 0.2296000, 0.3028860, 0.2711760, 0.1320160, 0.0248220, -0.0009360, -0.0020170, -0.0008300, -0.0000530, -0.0000020
> c, 1.19, -0.0000080, -0.0000230, -0.0000900, -0.0003030, -0.0010070, -0.0031120, -0.0089090, -0.0229590, -0.0509740, -0.0910870, -0.1264160, -0.1093480, 0.0360560, 0.2668180, 0.4018200, 0.3216300, 0.1188690, 0.0106110, -0.0002040
> c, 1.19, 0.0000020, 0.0000050, 0.0000200, 0.0000660, 0.0002230, 0.0006820, 0.0019780, 0.0050420, 0.0113810, 0.0200420, 0.0287430, 0.0236180, -0.0094800, -0.0734850, -0.1067580, -0.1068070, 0.0419610, 0.3566630, 0.5236540
> c, 1.19, 0.0000030, 0.0000080, 0.0000320, 0.0001050, 0.0003580, 0.0010780, 0.0031740, 0.0079580, 0.0182850, 0.0315250, 0.0468610, 0.0364210, -0.0118170, -0.1276830, -0.1731630, -0.1635510, 0.1536860, 0.6349130, 0.3577730
> c, 1.19, 0.0000060, 0.0000170, 0.0000670, 0.0002110, 0.0007580, 0.0021560, 0.0067440, 0.0158960, 0.0391480, 0.0618960, 0.1055240, 0.0714280, -0.0044130, -0.4223150, -0.4262330, 0.0815560, 1.1466020, -0.1112240, -0.7105390
> c, 1.19, 0.0000070, 0.0000220, 0.0000780, 0.0002990, 0.0008450, 0.0031230, 0.0074230, 0.0233610, 0.0418220, 0.0975620, 0.0946120, 0.2204310, -0.2118190, -0.7588750, -0.4724910, 2.0963660, -0.7589120, -1.1642940, 1.0676890
> c, 1.19, 0.0000100, 0.0000310, 0.0001100, 0.0004180, 0.0011970, 0.0043860, 0.0105980, 0.0331430, 0.0606140, 0.1404950, 0.1393730, 0.4499180, -0.9931010, -1.4130860, 2.9290650, -0.6058880, -1.8335560, 2.0771050, -0.9947610
> c, 20.20, 1
> c, 21.21, 1
> c, 22.22, 1
> d, CO , 545.1100000, 160.5580000, 61.6223000, 26.8224000, 12.4583000, 6.0606600, 2.9951700, 1.4647770, 0.6982420, 0.3200570, 0.1388040, 0.0550170, 8.0293000, 4.9005000
> c, 1.11, 0.0001810, 0.0016350, 0.0089410, 0.0327080, 0.0893220, 0.1819660, 0.2666540, 0.2974140, 0.2620050, 0.1719960, 0.0667780
> c, 1.11, -0.0002090, -0.0019030, -0.0104410, -0.0384790, -0.1079020, -0.2222780, -0.2817040, -0.1294980, 0.2102160, 0.4320100, 0.3313770
> c, 1.11, 0.0002770, 0.0025550, 0.0139620, 0.0525040, 0.1517350, 0.3163190, 0.2342970, -0.3302410, -0.5981010, 0.0737630, 0.5953900
> c, 1.11, -0.0003850, -0.0036800, -0.0196840, -0.0765810, -0.2355780, -0.5047020, 0.2497730, 0.9813720, -0.5418260, -0.7166120, 0.6007770
> c, 1.11, -0.0005830, -0.0042550, -0.0289000, -0.0939660, -0.4172350, -0.4197820, 1.4598530, -0.5170060, -1.1613150, 1.4364000, -0.3666040
> c, 12.12, 1
> c, 13.13, 1
> c, 14.14, 1
> f, CO , 12.5542000, 5.5551000, 2.4581000, 1.0877000, 0.3686000
> c, 1.1, 1
> c, 2.2, 1
> c, 3.3, 1
> c, 4.4, 1
> c, 5.5, 1
> g, CO , 8.7355000, 4.2811000, 2.0981000, 0.7828000
> c, 1.1, 1
> c, 2.2, 1
> c, 3.3, 1
> c, 4.4, 1
> h, CO , 7.8788000, 3.7437000, 1.5288000
> c, 1.1, 1
> c, 2.2, 1
> c, 3.3, 1
> i, CO , 8.0114000, 3.6607000
> c, 1.1, 1
> c, 2.2, 1
> 
> spdfgh,o,aug-cc-pwCV5Z;
> }
> 
> geometry={angstrom;
>           Co;
>           o,Co,1.621}
> {rhf;wf,35,1,5;}
> {casscf;occ,11,4,4,1;closed,7,2,2,0;
> wf,35,1,5;state,5;
> wf,35,2,5;state,4;
> wf,35,3,5;state,4;
> wf,35,4,5;state,4;
> wf,35,1,3;state,5;
> wf,35,2,3;state,4;
> wf,35,3,3;state,4;
> wf,35,4,3;state,4;
> wf,35,1,1;state,5;
> wf,35,2,1;state,4;
> wf,35,3,1;state,4;
> wf,35,4,1;state,4;
> maxiter,20;
> orbprint,4;}
> 
> table,energy;
> 
> 
> Then I have four question as follows:
> 1.If I want use contracted  cc-pwCV5Z  for Co,how should I change my input?
> 2.what should I do if I want to my local basis libary have  cc-pwCV5Z  for Co? Say it in detail if please.
> 3.my RHF calculation always have 60 iteration,so I suspect something is wrong with rhf command block .Maybe the high spin or something else ?how could I change my input?
> 4.when I do casscf program, I always meet "sipn contamination","wrong CI vector",how to deal with them?
>  I would be much much much gragteful for your suggestions.
> 
> 
> 
> 
> 
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