[molpro-user] Differences between 2010.1 and 2012.1 (UKS)

[Gerald Knizia]

Dear Javier,
I am not sure about UKS itself, but we might have modified some aspects
of the initial guess. Maybe you are dealing with a system with multiple
low-lying states and this time you get a different one. Do other
properties (e.g., dipole moments) agree in both calculations?
-- 
Gerald Knizia

On Fri, 2013-05-31 at 13:55 +0200, Javier Cerezo wrote:
> I just realized that I reported the SCF output wrongly (drawbacks of 
> copy-pasting..). Here are the actual info (DDIF and GRAD for 2012.1 
> updated):
> 
> 2010.1.-
> Last iteration: 46
> DDIF = 0.421D-05
> GRAD=0.788D-06
> Energy change = 1.44E-6
> Energy=-1793.40448762
> 
> 2012.1.-
> Last iteration: 38
> DDIF = 0.318D-05
> GRAD=0.553D-06
> Energy change = 6.80E-7
> Energy=-1793.4037537
> 
> Javier
> 
> El 31/05/13 11:23, Javier Cerezo escribió:
> > Dear Molpro users,
> >
> > I am comparing the performance of versions 2010.1 and 2012.1 by 
> > running the same job with both of them. The computation is a {UKS, 
> > B3LYP3} (I attached the input at the end of the message) which 
> > according to what I understand from the manual, should be using the 
> > same settings (namely, the same grid). As expected, the newer version 
> > performs better by achieving convergence in less SCF cycles and taking 
> > less time for each iteration. However, the final energy is not the 
> > same in both cases, with a difference, E(2012.1)-E(2010.1), of 0.0007 
> > hartrees (~0.46kcal/mol). I understand that it is an small difference 
> > (at least below the "chemical accuracy") but I was wondering why both 
> > versions did not lead to the same results and if there is any change 
> > in settings of thresholds that I am missing.
> >
> > Here you have some info about the SCF in both cases.
> >
> > 2010.1.-
> > Last iteration: 46
> > DDIF = 0.421D-05
> > GRAD=0.788D-06
> > Energy change = 1.44E-6
> > Energy=-1793.40448762
> >
> > 2012.1.-
> > Last iteration: 38
> > DDIF = 0.421D-05
> > GRAD=0.788D-06
> > Energy change = 6.80E-7
> > Energy=-1793.4037537
> >
> >
> > The same input is used, which follows
> >
> > ***
> > ! Set max memory in the cluster (8GB)
> > memory,228,m
> >
> > file,2,wavefunction.wfu
> >
> > basis={
> >  default=cc-pVDZ
> > ! LANL2TZ from BSE for Ni
> > ! NICKEL       (5s,5p,6d) -> [5s,5p,4d]
> > s, NI , 7.6200000, 2.2940000, 0.8760000, 0.1153000, 0.0396000
> > c, 1.1, 1
> > c, 2.2, 1
> > c, 3.3, 1
> > c, 4.4, 1
> > c, 5.5, 1
> > p, NI , 23.6600000, 2.8930000, 0.9435000, 0.0840000, 0.0240000
> > c, 1.1, 1
> > c, 2.2, 1
> > c, 3.3, 1
> > c, 4.4, 1
> > c, 5.5, 1
> > d, NI , 42.7200000, 11.7600000, 3.8170000, 1.1690000, 0.2836000, 
> > 0.0898000
> > c, 1.3, 0.0372699, 0.1956103, 0.4561273
> > c, 4.4, 1
> > c, 5.5, 1
> > c, 6.6, 1
> > ! Effective core Potentials
> > ! -------------------------
> > ECP, ni, 10, 2 ;
> > 3; !  d-ul potential
> > 1,469.9324331,-10.0000000;
> > 2,85.4236411,-69.4084805;
> > 2,21.2674984,-12.0951020;
> > 4; !  s-ul potential
> > 0,162.1686097,3.0000000;
> > 1,176.5333232,22.0253618;
> > 2,68.9562010,443.0181088;
> > 2,13.5792838,145.5696411;
> > 4; !  p-ul potential
> > 0,69.0181506,5.0000000;
> > 1,275.5955596,4.9882824;
> > 2,47.1315453,256.6945853;
> > 2,12.9874075,78.4754450;
> > }
> >
> > ! Read geom from XYZ
> > geomtyp=xyz
> > geometry=lu167s_T_25.xyz
> >
> > !Specify triplet (spin=2)
> > wf,spin=2,charge=0
> >
> > !Activate direct methods
> > gdirect
> >
> > ! Computaion of DFT energy
> > {UKS,B3LYP3}
> > ---
> >
> > Thanks!
> >
> > Javier
> >
> >
>