[molpro-user] different results segmented<->general contractions
Kirk Peterson
kipeters at wsu.edu
Wed Oct 28 23:51:31 GMT 2009
Hi Tanja,
in principle I believe these basis sets should give exactly the same
results since they exactly span the
same function space.
best wishes,
Kirk
On Oct 28, 2009, at 11:28 AM, Tanja van Mourik wrote:
> Dear Molpro users,
>
> One of my students has been doing CASSCF excited-state calculations
> using
> Molpro, and noticed differences in the results if she ticks or not
> ticks the
> "optimized general contractions" box when taking correlation
> consistent basis
> sets from the EMSL basis set site. I know that this option just
> removes from the
> general contractions the primitive that is also used uncontracted,
> to make the
> basis set work more efficiently with programs that support only
> segmented
> contractions. So ticking or not ticking this box should yield the
> same basis
> set, and therefore the results should be the same. Or am I missing
> something?
>
> We get the same results if we just compute the CASSCF ground-state
> energy.
> However, when computing excited states, there are significant
> differences, for
> example, for the input example below, the results are:
>
> "optimized general contractions" unselected:
>
> !MCSCF STATE 1.1 ENERGY -642.134635362437
> !MCSCF STATE 1.1 DIPOLE MOMENT -0.32765294 0.92287005
> 1.17631226
> !MCSCF STATE 2.1 ENERGY -641.868731948405
> !MCSCF STATE 2.1 DIPOLE MOMENT -0.96546607 -0.43965941
> -0.07105395
>
> "optimized general contractions" selected:
> !MCSCF STATE 1.1 ENERGY -642.136366749999
> !MCSCF STATE 1.1 DIPOLE MOMENT -0.32929977 0.81772379
> 1.14350008
> !MCSCF STATE 2.1 ENERGY -641.855949809309
> !MCSCF STATE 2.1 DIPOLE MOMENT -0.80264158 -0.20134531
> -0.18076690
>
> The input for the "optimized general contractions" case is:
> ===================================
> ***,2-keto singlet
> memory,400,m;
>
> geomtyp=xyz
> geometry={
> 8
> posphate group
> P 0.07854900 -0.05791100 -0.10861500
> O 1.03411300 -0.52179800 -1.13286600
> O -0.99689500 -1.16731000 0.32924700
> H -1.66406600 -0.84451300 0.95852600
> O -0.90278800 1.17835500 -0.45177200
> H -0.43421500 1.96143600 -0.78591300
> O 0.77406700 0.47094500 1.26445500
> H 1.65207400 0.07020700 1.38410100
> }
>
> basis={
> !
> ! HYDROGEN (5s,2p) -> [3s,2p]
> ! HYDROGEN (4s,1p) -> [2s,1p]
> ! HYDROGEN (1s,1p)
> s, H , 13.0100000, 1.9620000, 0.4446000, 0.1220000, 0.029740
> c, 1.3, 0.0196850, 0.1379770, 0.4781480
> c, 4.4, 1
> c, 5.5, 1
> p, H , 0.7270000, 0.141000
> c, 1.1, 1
> c, 2.2, 1
> ! OXYGEN (10s,5p,2d) -> [4s,3p,2d]
> ! OXYGEN (9s,4p,1d) -> [3s,2p,1d]
> ! OXYGEN (1s,1p,1d)
> s, O , 11720.0000000, 1759.0000000, 400.8000000, 113.7000000,
> 37.0300000,
> 13.2700000, 5.0250000, 1.0130000, 0.3023000, 0.078960
> c, 1.8, 0.0007100, 0.0054700, 0.0278370, 0.1048000, 0.2830620,
> 0.4487190,
> 0.2709520, 0.0154580
> c, 1.8, -0.0001600, -0.0012630, -0.0062670, -0.0257160, -0.0709240,
> -0.1654110, -0.1169550, 0.5573680
> c, 9.9, 1
> c, 10.10, 1
> p, O , 17.7000000, 3.8540000, 1.0460000, 0.2753000, 0.068560
> c, 1.3, 0.0430180, 0.2289130, 0.5087280
> c, 4.4, 1
> c, 5.5, 1
> d, O , 1.1850000, 0.332000
> c, 1.1, 1
> c, 2.2, 1
> ! PHOSPHOROUS (13s,9p,2d) -> [5s,4p,2d]
> ! PHOSPHOROUS (12s,8p,1d) -> [4s,3p,1d]
> ! PHOSPHOROUS (1s,1p,1d)
> s, P , 94840.0000000, 14220.0000000, 3236.0000000, 917.1000000,
> 299.5000000,
> 108.1000000, 42.1800000, 17.2800000, 4.8580000, 1.8180000, 0.3372000,
> 0.1232000, 0.04170
> c, 1.11, 0.255509D-03, 0.198193D-02, 0.102760D-01, 0.414823D-01,
> 0.131984D+00,
> 0.308662D+00, 0.420647D+00, 0.222878D+00, 0.164035D-01, -0.254255D-02,
> 0.748050D-03
> c, 1.11, -0.696939D-04, -0.535266D-03, -0.283709D-02, -0.113983D-01,
> -0.392929D-01, -0.996364D-01, -0.197983D+00, -0.114860D+00, 0.518595D
> +00,
> 0.601847D+00, 0.368612D-01
> c, 1.11, 0.191199D-04, 0.147223D-03, 0.777912D-03, 0.314546D-02,
> 0.108200D-01,
> 0.279957D-01, 0.563978D-01, 0.358190D-01, -0.193387D+00, -0.372097D
> +00,
> 0.624246D+00 c, 12.12, 1 c, 13.13, 1 p, P , 370.5000000,
> 87.3300000,
> 27.5900000, 10.0000000, 3.8250000, 1.4940000, 0.3921000, 0.1186000,
> 0.03430 c,
> 1.7, 0.395005D-02, 0.302492D-01, 0.129554D+00, 0.327594D+00,
> 0.456992D+00,
> 0.253086D+00, 0.168798D-01 c, 1.7, -0.959832D-03, -0.711177D-02,
> -0.327122D-01, -0.795784D-01, -0.135016D+00, -0.910585D-02, 0.537802D
> +00 c,
> 8.8, 1 c, 9.9, 1 d, P , 0.3730000, 0.11300 c, 1.1, 1 c, 2.2, 1 }
>
> gprint,basis,distance,angle
> gprint,orbital=104
> gexpec,DM
>
> hf
> orbital,2100.2
>
> {casscf;
> occ,28;
> closed,18;
> wf,50,,0;state,2;
> print,orbitals}
> ==============================
>
> The other case can be reproduced by simply using the keyword
> basis=avdz instead
> of the basis set block in the input above.
>
> Could someone help us understand what is going on here? Should we
> get different
> results, and if so, why? Is there another problem?
>
> Best wishes,
>
> Tanja
> --
> =================================================================
> Tanja van Mourik
> Senior Lecturer in Chemistry
> School of Chemistry, University of St. Andrews
> North Haugh, St. Andrews, Fife KY16 9ST, Scotland (UK)
>
> email: tanja.vanmourik at st-andrews.ac.uk
> web: http://chemistry.st-and.ac.uk/staffmember.php?id=tvm
>
> The University of St Andrews is a charity registered
> in Scotland: No SC013532
> =================================================================
>
>
>
>
>
> ------------------------------------------------------------------
> University of St Andrews Webmail: https://webmail.st-andrews.ac.uk
>
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