[molpro-user] Different ROHF energy on molpro2006 and 2009

Peter Knowles KnowlesPJ at Cardiff.ac.uk
Thu Mar 10 07:57:18 GMT 2011


Hartree-Fock convergence to the global minimum is not always easy to achieve. The algorithm has indeed changed between these two Molpro versions, but if you are curious enough to add
{mcscf;occ,8,2;closed,7,2}
{rhf;start,2140.2}
to the end of your input, you will discover that neither versions (and, therefore, presumably the other codes you quote) deliver the global minimum.
Peter
On 10 Mar 2011, at 00:39, Hao Feng wrote:

> Dear Molpro Users,
> 
> I just tested the ROHF energy of an open shell molecule by using molpro2009. However, I found that it's different from that by PSI3, CFOUR and Gaussian. So I asked my friend in USA to do the computation by molpro2006. It's curious to find that molpro2006 gave the same energy as PSI3, CFOUR and Gaussian did. Of course, the orbital energies are different.
> 
> The input parameters are very simple:
> 
> ***, test
> print,basis,orbitals
> {gthresh,optgrad=1.0d-8,energy=1.d-08}
> geometry={ang
> F
> H 1 RFH
> N 2 RNH1 1 NHF
> H 3 RNH2 2 HNH 1 HNHF1
> H 3 RNH2 2 HNH 1 HNHF2
> }
> RFH  =        1.516342686704521
> RNH1 =        1.045983157323055
> NHF  =      109.819543901404572
> RNH2 =        1.018269885054718
> HNH  =      112.777687641596941
> HNHF1=       64.446118736239796
> HNHF2=      -64.446118736239796
> 
> basis=aug-cc-pVDZ
> 
> {rhf
> wf,     spin=1, symmetry=1
> occ,    8, 2
> closed, 7, 2
>                                                                                !open,   8.1
> }
> ===============================
> 
> 
> Here's ITERATION of molpro 2006:
> 
> ITERATION    DDIFF          GRAD             ENERGY        2-EL.EN.            DIPOLE MOMENTS         DIIS
>   1      0.000D+00      0.000D+00      -155.45562751    192.113134   0.000000   0.198769   2.829883    0
>   2      0.000D+00      0.155D-01      -155.18324665    185.479212   0.000000   0.372252  -1.338398    1
>   3      0.469D-01      0.321D-01      -155.51364091    190.427758   0.000000   0.125240   2.849837    2
>   4      0.404D-01      0.842D-02      -155.48011690    187.667101   0.000000   0.274519   0.924929    1
>   5      0.219D-01      0.137D-01      -155.53847879    189.148906   0.000000   0.204770   1.837293    2
>   6      0.116D-01      0.192D-02      -155.54109836    189.390427   0.000000   0.185367   2.092388    3
>   7      0.323D-02      0.932D-03      -155.54148002    189.448409   0.000000   0.186380   2.118059    4
>   8      0.761D-03      0.752D-03      -155.54171122    189.429110   0.000000   0.187281   2.130760    5
>   9      0.448D-03      0.489D-03      -155.54205321    189.473347   0.000000   0.184940   2.201274    6
>  10      0.862D-03      0.471D-03      -155.54247471    189.518009   0.000000   0.180305   2.314999    7
>  11      0.167D-02      0.217D-03      -155.54250159    189.500748   0.000000   0.180110   2.313510    8
>  12      0.278D-03      0.525D-04      -155.54251625    189.531565   0.000000   0.177308   2.369530    9
>  13      0.735D-03      0.554D-04      -155.54252498    189.512130   0.000000   0.178826   2.341206    9
>  14      0.346D-03      0.156D-04      -155.54252616    189.516344   0.000000   0.178509   2.348071    9
>  15      0.846D-04      0.272D-05      -155.54252618    189.516819   0.000000   0.178504   2.348725    9
>  16      0.867D-05      0.722D-06      -155.54252618    189.516890   0.000000   0.178510   2.348815    9
>  17      0.196D-05      0.226D-06      -155.54252618    189.516964   0.000000   0.178504   2.348965    7
>  18      0.200D-05      0.499D-07      -155.54252618    189.516959   0.000000   0.178505   2.348953    7
>  19      0.203D-06      0.162D-07      -155.54252618    189.516957   0.000000   0.178505   2.348954    0
> 
> and molpro 2009:
> 
> ITERATION    DDIFF          GRAD             ENERGY        2-EL.EN.            DIPOLE MOMENTS         DIIS
>   1      0.000D+00      0.000D+00      -155.45562749    192.113129    0.00000    0.19877    2.82988    0
>   2      0.000D+00      0.155D-01      -155.42112997    186.552535    0.00000    0.31821    0.10373    1
>   3      0.333D-01      0.201D-01      -155.53678475    189.060911    0.00000    0.21312    1.59237    2
>   4      0.187D-01      0.169D-02      -155.53910509    189.125683    0.00000    0.20576    1.63452    3
>   5      0.318D-02      0.524D-03      -155.53947982    189.147665    0.00000    0.20428    1.68098    4
>   6      0.103D-02      0.401D-03      -155.53968813    189.184512    0.00000    0.20437    1.72817    5
>   7      0.506D-03      0.399D-03      -155.53986246    189.211203    0.00000    0.20330    1.77068    6
>   8      0.418D-03      0.432D-03      -155.53951031    189.144956    0.00000    0.20624    1.68025    7
>   9      0.904D-03      0.377D-03      -155.53908373    189.015652    0.00000    0.21428    1.49466    8
>  10      0.181D-02      0.232D-03      -155.53906980    188.975868    0.00000    0.21722    1.44950    9
>  11      0.370D-03      0.635D-04      -155.53905514    188.941258    0.00000    0.21998    1.40235    9
>  12      0.439D-03      0.169D-04      -155.53905563    188.935012    0.00000    0.22073    1.39144    9
>  13      0.135D-03      0.801D-05      -155.53905583    188.935971    0.00000    0.22087    1.39392    9
>  14      0.518D-04      0.102D-04      -155.53905588    188.935579    0.00000    0.22095    1.39309    9
>  15      0.208D-04      0.185D-05      -155.53905589    188.935700    0.00000    0.22098    1.39307    9
>  16      0.422D-05      0.319D-06      -155.53905589    188.935532    0.00000    0.22100    1.39287    9
>  17      0.231D-05      0.106D-06      -155.53905589    188.935568    0.00000    0.22100    1.39291    8
>  18      0.536D-06      0.339D-07      -155.53905589    188.935568    0.00000    0.22100    1.39291    0
> 
> The output files are attached.
> 
> Does anyone have any suggestion?
> 
> Thanks a lot!
> 
> Hao
> 
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--
Prof. Peter J. Knowles             
School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff CF10 3AT, UK
Email KnowlesPJ at Cardiff.ac.uk 
WWW http://www.cardiff.ac.uk/chemy/contactsandpeople/academicstaff/knowles.html
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