[molpro-user] Internal and explicit initial guessing

[Andy May]

Andrew,

This is due to the atomic density guess, see:

http://www.molpro.net/info/current/doc/update.pdf

'Improvements to the Hartree-Fock program'

If you modify your explicit input by setting hf option 'guess_basis' to
'none', i.e.:

hf,guess_basis=none

You should get agreement.

Best wishes,

Andy

On 29/06/10 20:10, Taube, Andrew wrote:
> I am having a weird result when comparing results for basis sets from
> the internal basis set library and from explicitly including the same
> basis set in the input file. While the results converge to the same
> value of RHF energy, the initial guess is different.
>  
> For example, for F- in a cc-pVDZ basis including the basis set explicitly:
> ***,F- cc-pVDZ explicitly
> memory,400,M
> basis={
> s, F , 14710.0000000, 2207.0000000, 502.8000000, 142.6000000,
> 46.4700000, 16.7000000, 6.3560000, 1.3160000, 0.3897000
> c, 1.9, 0.0007210, 0.0055530, 0.0282670, 0.1064440, 0.2868140,
> 0.4486410, 0.2647610, 0.0153330, -0.002332
> c, 1.9, -0.0001650, -0.0013080, -0.0064950, -0.0266910, -0.0736900,
> -0.1707760, -0.1123270, 0.5628140, 0.568778
> c, 9.9, 1
> p, F , 22.6700000, 4.9770000, 1.3470000, 0.3471000
> c, 1.4, 0.0448780, 0.2357180, 0.5085210, 0.45812
> c, 4.4, 1
> d, F , 1.6400000
> c, 1.1, 1
> }
> thrdscf=1e-12,thrdscf_max=1e-9
> gthresh,throvl=1e-9,throrth=1e-7
> gdirect
> geometry={f;
> }
> charge=-1
> hf
>  
> has the following set of iterations:
> ITERATION   DDIFF            GRAD            ENERGY       
> 2-EL.EN.            DIPOLE MOMENTS         DIIS   CPU(IT)  CPU(TOT)
>     1      0.000D+00      0.000D+00       -99.29578519     95.175396  
> 0.000000   0.000000   0.000000    0      5.7      9.2   diag
>     2      0.000D+00      0.131D+00       -99.34548119     88.831609  
> 0.000000   0.000000   0.000000    1      3.0     12.2   diag
>     3      0.206D+00      0.728D-01       -99.36598299     91.014455  
> 0.000000   0.000000   0.000000    2      3.1     15.2   diag
>     4      0.688D-01      0.506D-03       -99.36598357     91.025429  
> 0.000000   0.000000   0.000000    3      3.0     18.2   diag
>     5      0.401D-03      0.113D-04       -99.36598357     91.025398  
> 0.000000   0.000000   0.000000    3      3.0     21.2   diag
>     6      0.184D-04      0.259D-05       -99.36598357     91.025417  
> 0.000000   0.000000   0.000000    3      2.0     23.2   diag
>     7      0.558D-05      0.141D-06       -99.36598357     91.025424  
> 0.000000   0.000000   0.000000    0      2.0     25.1   orth
>  
> While calling the same basis set from the internal library,
> ***,F- cc-pVDZ implicitly
> memory,400,M
> basis={
> f=cc-pVDZ
> }
> thrdscf=1e-12,thrdscf_max=1e-9
> gthresh,throvl=1e-9,throrth=1e-7
> gdirect
> geometry={f;
> }
> charge=-1
> hf
>  
> has the following iteration set:
> ITERATION   DDIFF            GRAD            ENERGY       
> 2-EL.EN.            DIPOLE MOMENTS         DIIS   CPU(IT)  CPU(TOT)
>     1      0.000D+00      0.000D+00       -99.29785341     95.113039  
> 0.000000   0.000000   0.000000    0      5.4      7.5   diag
>     2      0.000D+00      0.129D+00       -99.34608743     88.864010  
> 0.000000   0.000000   0.000000    1      2.9     10.3   diag
>     3      0.202D+00      0.717D-01       -99.36598302     91.014701  
> 0.000000   0.000000   0.000000    2      2.8     13.1   diag
>     4      0.678D-01      0.494D-03       -99.36598357     91.025427  
> 0.000000   0.000000   0.000000    3      3.1     16.2   diag
>     5      0.392D-03      0.110D-04       -99.36598357     91.025398  
> 0.000000   0.000000   0.000000    3      3.1     19.3   diag
>     6      0.179D-04      0.252D-05       -99.36598357     91.025417  
> 0.000000   0.000000   0.000000    3      3.1     22.4   diag
>     7      0.542D-05      0.138D-06       -99.36598357     91.025424  
> 0.000000   0.000000   0.000000    0      3.0     25.4   orth
>  
> Looking at the first iteration there is a difference of 2 mH. In this
> case, that isn’t a big deal, however, I have added basis sets to the
> basis set library and for some larger basis sets, the resultant
> iterations converge to different states. I can send those examples as
> desired. Can someone explain why this behavior is occurring and how to
> control it?
>  
> These calculations were run with molpro version 2009.1, patch level 29.
>  
> Thanks,
> Andrew
>  
> ---
> Andrew G. Taube
> D. E. Shaw Research
> email: Andrew.Taube at DEShawResearch.com
> Tel: +1-212-478-0118
> Fax: +1-212-845-1118
>  
>  
>  
> 
> 
> 
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