CCL:G: G09 problem with large-core SD ECP (MWB53 for Gd)

Dear Dimitri, Ibrahim and Jamin
I haven't worked before on Gadolinium, but according to the electronic configuration of Gd ([Xe] 4f7 5d1 6S2), the electronic configuration of Gd3+ is [Xe] 4f7 [NOT 4p 4s as Dimitri suggested) (Reference: The physics of metals and metallography Vol. 102 Suppl. 1 2006).
So, Ibrahim suggestion about the multiplicity of Gd3+ couldn't be singlet is correct.
May I be confused, so any declaration would be appreciated.
S. Bill

--- On Sat, 6/2/10, Jamin Krinsky jamink(a)berkeley.edu <owner-chemistry%%ccl.net> wrote:

From: Jamin Krinsky jamink(a)berkeley.edu <owner-chemistry%%ccl.net>
Subject: CCL:G: G09 problem with large-core SD ECP (MWB53 for Gd)
To: "Bill, S. H. " <s_bill36%%yahoo.co.uk>
Date: Saturday, 6 February, 2010, 21:26

Dear Dimitri and Ibrahim,

Dimitri is correct in that with these ECPs the trivalent ion is a singlet. Gaussian help got back to me and it turns out that, for G09 at least, the problem is with the Harris guess not being able to handle an odd number of core electrons (why it works with Nd I still don't know. Below is the explanation and work-around proposed by Fernando:

If you proceed with this ECP then you will need to use "guess=core", instead of the default (Harris), when having an odd number of core electrons. Note also that, at each geometry optimization step, the initial guess for the wavefunction is generated using a combination of the SCF solution in previous optimization step with a guess from the Harris functional. If find the same problem in a geometry optimization when it reaches the second step, then try to force the use of "guess=core" at each geometry optimization step with:

guess=(core,always)

Another possibility could be to use "guess=core" for a single point calculation and force the program to always read the guess from the checkpoint file ("IOp(4/5=1)"). For instance:

%chk=gd.chk
#p scf=tight b3lyp/genecp guess=core

Title Card Required

3 1
<Geometry specification>

H C O S 0
6-31g        <-- Basis set specification for other elements
****
Gd 0
mwb53        <-- Basis set specification for Gd
****

Gd 0
mwb53        <-- ECP specification for Gd

--link1--
%chk=gd.chk
#p opt b3lyp checkbas geom=check iop(4/5=1)

Title Card Required

3 1

Thanks much for your input.

Jamin


On Sat, Feb 6, 2010 at 6:29 AM, Dimitri Cavalcanti dimitricavalcanti^-^gmail.com <owner-chemistry%ccl.net> wrote:

Sent to CCL by: Dimitri Cavalcanti [dimitricavalcanti#%#gmail.com]
Dear Jamin and Ibrahim

   I don't know if the behave is the same, but when i try to use the
large core pseudo potentials for actinides 3+ ions in gaussian03 the
calculations don't go because the odd number of electrons in the ECP,
so i think that happens the same for the lanthanides. In the
gaussian's manual is said that since the rev C.01 the use of this ECPs
is possible, but i can't use it without the keyword iop(4/5=2) (a
bypass that makes gaussian ignore the odd number and runs the
calculation, but takes much more time).

  About the multiplicity, there is no problem with that, using the
53MWB for the 3+ oxidation states the valence electrons will be the 4s
and 4p orbtials, that are closed shell.  And about the gaussian 09 i
can't help, i don't use it yet, but the link401 is the one who
generate the initial MOs, so i think that you have problems with the
basis set, try put the basis set explicity, and the ECP and see what
happens, or remove the keyword "int=ultrafinegrid".

Good luck and have a nice weekend.

The use of the 53MWB pseudopotential for gadolinium in gaussian03

2010/2/5 Mahmoud A. A. Ibrahim m.ibrahim]^[compchem.net
<owner-chemistry**ccl.net>:
> Dear Jamin
> The problem backs to the multiplicity of your ion. The Gd3+ ion CAN'T be
> singlet.
> If you run the same job with 3 as charge and 2 as multiplicity, your job
> will be completed without any complains.
> Sincerely;
> M. Ibrahim
>
> On Fri, Feb 5, 2010 at 10:33 AM, Jamin Krinsky jamink++http://berkeley.edu">berkeley.edu
> <owner-chemistry*ccl.net> wrote:
>>
>> Sent to CCL by: "Jamin  Krinsky" [jamink _ berkeley.edu]
>> I'm trying to use the large core MWB53 ECP and accompanying basis for
>> Gd(+3) in Gaussian 09 and I'm getting the following error during initial
>> guess generation (and the job dies):
>>
>> Fell through 30 in IdenVS.
>>  Error termination via Lnk1e in /usr/software/gaussian/g09.revA02/l401.exe
>> at Sun Jan 31 16:13:55 2010
>>
>> I have never come across this error nor can I find any online info on it,
>> so I cannot figure out how to diagnose it. The analogous ECPs for Nd, Eu, Tb
>> and Dy (all trivalent) work just fine, and I get the same error using G09's
>> built-in ECP or pasting it in directly from the Stuttgart web site.
>>
>> Trying it on G03 (revE) results in this error:
>>
>> Odd number of core electrons in MinBas.
>>  Error termination via Lnk1e in
>> /usr/software/gaussian/g03_64.RevE01/g03/l401.exe at Sun Jan 31 17:11:44
>> 2010
>>
>> Which is obvious but not very informative.
>>
>> Representative simple input:
>>
>> #p b3lyp/gen nosymm pseudo=read int=ultrafinegrid
>>
>> large core gaussian built-in
>>
>> 3 1
>> Gd  0.0 0.0 0.0
>>
>> Gd 0
>> MWB53
>> ****
>>
>> Gd 0
>> MWB53
>>
>> Any info anyone might have on this would be greatly appreciated.
>>
>> Best regards,
>> Jamin
>>
>> Jamin L Krinsky, Ph.D.
>> Molecular Graphics and Computation Facility
>> 175 Tan Hall, University of California, Berkeley, CA 94720
>> jamink::berkeley.edu, 510-643-0616
>> http://glab.cchem.berkeley.edu
>>
>>
>>
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>
>
> --
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--
Dimitri de Pinho Cavalcanti
Departamento de Química Fundamental - UFPE - Br
+55 81 2126-8447



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--
Jamin L Krinsky, Ph.D.
Molecular Graphics and Computation Facility
175 Tan Hall, University of California, Berkeley, CA 94720
jamink%berkeley.edu, 510-643-0616
http://glab.cchem.berkeley.edu