[molpro-user] different results segmented<->general contractions
Steven L. Mielke
slmielke at gmail.com
Thu Oct 29 10:52:27 GMT 2009
Hi Tanja,
I believe Kirk's response would be true assuming that your mcscf
convergence was well behaved. Yours isn't; however, one can, for
instance, get essentially the same answers (and essentially equivalent
to those listed first below) for both basis input schemes if you do an
initial mcscf calculation with the closed orbitals replaced with
frozen ones and then a second calculation with these orbitals unfrozen
that uses the earlier orbitals to start. There are probably even
slicker ways....
Steven Mielke
On Oct 28, 2009, at 6:51 PM, Kirk Peterson wrote:
> 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
>>
>> _______________________________________________
>> Molpro-user mailing list
>> Molpro-user at molpro.net
>> http://www.molpro.net/mailman/listinfo/molpro-user
>
> _______________________________________________
> Molpro-user mailing list
> Molpro-user at molpro.net
> http://www.molpro.net/mailman/listinfo/molpro-user
More information about the Molpro-user
mailing list