[molpro-user] Illegal ECP center

Jing Yang yang15 at sas.upenn.edu
Mon Nov 3 18:59:43 GMT 2014


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
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>>>> 
>> 
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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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