[molpro-user] Illegal ECP center
Tatiana Korona
tania at tiger.chem.uw.edu.pl
Tue Nov 4 17:29:00 GMT 2014
Dear Jing,
Ad 2
For MP2 properties orbital relaxation can be quite substantial. Molpro does not
print these contributions separately for the 2nd order proprties, but for the
first order you can compare e.g. the total electron correlation part of the MP2
dipole moment (subtract MP2 from HF:-) with the MP2 "Orbital relaxation
contribution:"
Ad 4
{hf,thrcphf=1.e-10
polarizability,dm,qm
}
{mp2
core,0
polari,dm,qm
cphf,accu=1.d-10
}
will change convergence thresholds for the CPHF equations on the HF and MP2
levels.
Best wishes,
Tatiana
On Mon, 3 Nov 2014, Jing Yang wrote:
> Dear Peter,
> Thank you for your reply on my message. It is very helpful. I used your input and found out the result is better (even though it still says “No convergence of CPHF ….”). Here are some further questions I would like you to help me answer:
> 1. Which basis set are you using?
> 2. Does the CPHF matter a lot when calculating the polarizabability?
> 3. Can you tell me the reason why you put the obital symmetry in 3,1,1,1,1,1,1? Where does the 3 come from? How can I relate term symbols to the orbital symmetry here?
> 4. I am wondering if you know how to change the cphf default values from input file? I tried the ways in the manual, it looks it does not do anything….
>
> Again, I appreciate your help a lot from previous. I hope you could spend some time to take a look at this email and help me figure out the puzzles eventually. Thank you very much!!
>
> Thanks,
> Jing
>
>
>> On Nov 3, 2014, at 4:36 AM, Peter Knowles <KnowlesPJ at cardiff.ac.uk> wrote:
>>
>> It seems to me that everything works just fine if you remember to do Hartree-Fock before the MP2 calculation, and if you target the closed-shell singlet S state of Cu+, as in the following input. If you want to do MP2 on an open-shell system, then the directive 'MP2' cannot be used, since this calls the closed-shell program. For the singlet D state it seems unlikely to me that one could use any single-reference method, since the reference function has at least two equally-important determinants.
>> Peter
>>
>> geometry={cu}
>> basis
>> ECP,1,10,3; ! ECP input
>> 1; ! NO LOCAL POTENTIAL
>> 2,1.,0.;
>> 2; ! S POTENTIAL
>> 2,30.22,355.770158;2,13.19,70.865357;
>> 2; ! P POTENTIAL
>> 2,33.13,233.891976;2,13.22,53.947299;
>> 2; ! D POTENTIAL
>> 2,38.42,-31.272165;2,13.26,-2.741104;
>> ! (8s7p6d)/[6s5p3d] BASIS SET
>> s,1,27.69632,13.50535,8.815355,2.380805,.952616,.112662,.040486,.01;
>> c,1.3,.231132,-.656811,-.545875;
>> p,1,93.504327,16.285464,5.994236,2.536875,.897934,.131729,.030878;
>> c,1.2,.022829,-1.009513;C,3.4,.24645,.792024;
>> d,1,41.225006,12.34325,4.20192,1.379825,.383453,.1;
>> c,1.4,.044694,.212106,.453423,.533465;
>> end
>> rhf;
>> geometry={cu}
>> basis
>> ECP,1,10,3; ! ECP input
>> 1; ! NO LOCAL POTENTIAL
>> 2,1.,0.;
>> 2; ! S POTENTIAL
>> 2,30.22,355.770158;2,13.19,70.865357;
>> 2; ! P POTENTIAL
>> 2,33.13,233.891976;2,13.22,53.947299;
>> 2; ! D POTENTIAL
>> 2,38.42,-31.272165;2,13.26,-2.741104;
>> ! (8s7p6d)/[6s5p3d] BASIS SET
>> s,1,27.69632,13.50535,8.815355,2.380805,.952616,.112662,.040486,.01;
>> c,1.3,.231132,-.656811,-.545875;
>> p,1,93.504327,16.285464,5.994236,2.536875,.897934,.131729,.030878;
>> c,1.2,.022829,-1.009513;C,3.4,.24645,.792024;
>> d,1,41.225006,12.34325,4.20192,1.379825,.383453,.1;
>> c,1.4,.044694,.212106,.453423,.533465;
>> end
>> core,0
>> {rhf;occ,3,1,1,1,1,1,1;close,3,1,1,1,1,1,1;wf,18,1,0;polari,dm,sm}
>> {mp2;occ,3,1,1,1,1,1,1;close,3,1,1,1,1,1,1;wf,18,1,0;polari,dm,sm}
>>> On 31 Oct 2014, at 14:02, Jing At Penn <yang15 at sas.upenn.edu> wrote:
>>>
>>> Dear Andy,
>>> I am still trying to tackle the quadruple polarizability does not give value problem. You said before because it is a bug. The key problem for quadruple polarizability with MP2 method is that the CPHF doesn't converge for perturbation calculation. To me, I find out the quadruple polarizability works for some cases but not for others. I would rather think it is a basis set problem (close shell has been defined). The reason I would like to put the basis set by hand is to understand how the basis set works in molpro so that I could modify it by myself.
>>> Can you comment on fixing the CPHF convergence error? I think in this way I may figure out how to circumvent the quadruple polarizability calculations problem by using the current version.
>>>
>>> Thanks,
>>> Jing
>>>
>>>> On Oct 31, 2014, at 6:59 AM, Andy May <MayAJ1 at cardiff.ac.uk> wrote:
>>>>
>>>> Jing,
>>>>
>>>> The basis input seems to be in libmol ('MolproInt' from EMSL) format, when it should be in 'Molpro' format.
>>>>
>>>> Best wishes,
>>>>
>>>> Andy
>>>>
>>>>> On 31/10/14 07:51, Jing Yang wrote:
>>>>> Hi,
>>>>> I have some trouble with adding basis set with ECP. The following input is for Ag+ ion. It keeps telling “Illegal ECP ceter 47”. What does that mean?
>>>>> Thanks,
>>>>> Jing
>>>>>
>>>>> **,water cartesian coordinates (XYZ format)
>>>>> memory,100,m
>>>>> basis
>>>>> ECP, 47, 28, 3 ;
>>>>> 5; ! f potential
>>>>> 0,568.7006237,-0.0587930;
>>>>> 1,162.3579066,-20.1145146;
>>>>> 2,51.1025755,-104.2733114;
>>>>> 2,16.9205822,-40.4539787;
>>>>> 2,6.1669596,-3.4420009;
>>>>> 5; ! s-f potential
>>>>> 0,76.0974658,2.9861527;
>>>>> 1,15.3327359,35.1576460;
>>>>> 2,18.7715345,450.1809906;
>>>>> 2,13.3663294,-866.0248308;
>>>>> 2,9.8236948,523.1110176;
>>>>> 5; ! p-f potential
>>>>> 0,56.3318043,4.9640671;
>>>>> 1,69.0609098,21.5028219;
>>>>> 2,19.2717998,546.0275453;
>>>>> 2,12.5770654,-600.3822556;
>>>>> 2,8.7956670,348.2949289;
>>>>> 5; ! d-f potential
>>>>> 0,53.4641078,3.0467486;
>>>>> 1,40.1975457,23.3656705;
>>>>> 2,11.9086073,777.2540117;
>>>>> 2,9.7528183,-1238.8602423;
>>>>> 2,8.1788997,608.0677121;
>>>>>
>>>>> AG S Hay-Wadt MB (n+1) ECP : 5 3 1.3 1.4 5.5
>>>>>
>>>>> 2.9500000 2.1490000 0.6684000 0.0997000 0.0347000
>>>>> -1.7910564 2.0244570 0.6072839 1.0141125 -1.2413971
>>>>> -1.2413971 1.1128375 1.0000000
>>>>> AG P Hay-Wadt MB (n+1) ECP : 6 3 1.3 4.5 6.6
>>>>>
>>>>> 6.5530000 1.5650000 0.5748000 0.9085000 0.0833000
>>>>> 0.0252000 -0.1079117 0.7403645 0.3721008 -0.0418371
>>>>> 1.0087586 1.0000000
>>>>> AG D Hay-Wadt MB (n+1) ECP : 4 2 1.3 4.4
>>>>>
>>>>> 3.3910000 1.5990000 0.6282000 0.2108000 0.1396938
>>>>> 0.4744421 0.5156311 1.0000000
>>>>> end
>>>>> cartesian
>>>>> geomtyp=XYZ
>>>>> geometry={
>>>>> 1
>>>>> METAL CARTESIAN COORDINATES
>>>>> Ag 0.00000000 0.00000000 0.00000000
>>>>> }
>>>>> set,charge=1.0
>>>>> hf
>>>>> {mp2
>>>>> core,0
>>>>> polari,dm,sm,mltp3}
>>>>>
>>>>> Variables initialized (661), CPU time= 0.00 sec
>>>>> Commands initialized (458), CPU time= 0.01 sec, 486 directives.
>>>>> Default parameters read. Elapsed time= 1.57 sec
>>>>>
>>>>> Checking input...
>>>>> Passed
>>>>> 1
>>>>>
>>>>>
>>>>> *** PROGRAM SYSTEM MOLPRO ***
>>>>> Copyright, University College Cardiff Consultants Limited, 2008
>>>>>
>>>>> Version 2010.1 linked May 7 2014 08:43:28
>>>>>
>>>>>
>>>>> **********************************************************************************************************************************
>>>>> LABEL * water cartesian coordinates (XYZ format)
>>>>> Linux-3.0.93-0.8.2_1.0502.8048-cray_ari_c/nid06082(x86_64) 64 bit mpp version DATE: 31-Oct-14 TIME: 00:41:54
>>>>> **********************************************************************************************************************************
>>>>>
>>>>> SHA1: 2458f1e66e4952b685fd9c97d9367cff62d511a6
>>>>> **********************************************************************************************************************************
>>>>>
>>>>> Variable memory set to 100000000 words, buffer space 230000 words
>>>>>
>>>>> SETTING BASIS = USERDEF
>>>>> SETTING GEOMTYP = XYZ
>>>>> SETTING CHARGE = 1.00000000
>>>>>
>>>>>
>>>>> Recomputing integrals since basis changed
>>>>>
>>>>>
>>>>> Using cartesian basis functions
>>>>>
>>>>> Illegal ECP centre: 47
>>>>>
>>>>> GLOBAL ERROR fehler on processor 0
>>>>> _______________________________________________
>>>>> Molpro-user mailing list
>>>>> Molpro-user at molpro.net
>>>>> http://www.molpro.net/mailman/listinfo/molpro-user
>>>>>
>>>
>>> _______________________________________________
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>>
>> --
>> Prof. Peter J. Knowles
>> School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
>> Telephone +44 29 208 79182 Email KnowlesPJ at Cardiff.ac.uk
>> WWW http://www.cardiff.ac.uk/chemy/contactsandpeople/academicstaff/knowles.html
>>
>>
>>
>>
>>
>>
>
>
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Dr. Tatiana Korona http://tiger.chem.uw.edu.pl/staff/tania/index.html
Quantum Chemistry Laboratory, University of Warsaw, Pasteura 1, PL-02-093 Warsaw, POLAND
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