From owner-chemistry {*at*} ccl.net Sun Feb 7 20:38:01 2010 From: "Jamin Krinsky jamink^^^berkeley.edu" To: CCL Subject: CCL:G: G09 problem with large-core SD ECP (MWB53 for Gd) Message-Id: <-41206-100207201624-23340-3w4cZmIhVF5B+uY+2WxrbA~!~server.ccl.net> X-Original-From: Jamin Krinsky Content-Type: multipart/alternative; boundary=00151750e6e0f1a884047f0c8bed Date: Sun, 7 Feb 2010 17:16:11 -0800 MIME-Version: 1.0 Sent to CCL by: Jamin Krinsky [jamink]_[berkeley.edu] --00151750e6e0f1a884047f0c8bed Content-Type: text/plain; charset=ISO-8859-1 Content-Transfer-Encoding: quoted-printable Hi S. Bill, In the context of real electron configurations Gd3+ cannot be a singlet, bu= t these ECPs put those seven unpaired "electrons" in the core, as part of the potential felt by the explicit valence electrons (only the core 5s/5p electrons in this basis when considering the free trication). So those 7 4f electrons don't contribute to the multiplicity in the calculation, the calculation only uses electrons that actually exist (and have basis functions). I guess the result could be considered similar to the way ADF calculates closed-shell atom fragments using fractional occupations: maybe it's OK to think of it as 3.5 alpha and 3.5 beta f electrons in the core bu= t I don't think this is anywhere near rigorously correct. The physical meanin= g of this is dubious, which is probably the reason for this debate. However, the simplification makes calculations on large lanthanide complexes much more doable, and lots of properties that don't depend much on the electronics of the metal are reproduced pretty well. Jamin On Sun, Feb 7, 2010 at 5:07 AM, s. Bill s_bill36],[yahoo.co.uk < owner-chemistry(a)ccl.net> wrote: > 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 G= d3+ > 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 ccl.net>* wrote: > > > From: Jamin Krinsky jamink(a)berkeley.edu > Subject: CCL:G: G09 problem with large-core SD ECP (MWB53 for Gd) > To: "Bill, S. H. " > 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 o= f > 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=3Dcore", > instead of the default (Harris), when having an odd number of core > electrons. Note also that, at each geometry optimization step, the initia= l > 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=3Dcore" at e= ach > geometry optimization step with: > > guess=3D(core,always) > > Another possibility could be to use "guess=3Dcore" for a single point > calculation and force the program to always read the guess from the > checkpoint file ("IOp(4/5=3D1)"). For instance: > > %chk=3Dgd.chk > #p scf=3Dtight b3lyp/genecp guess=3Dcore > > Title Card Required > > 3 1 > > > 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=3Dgd.chk > #p opt b3lyp checkbas geom=3Dcheck iop(4/5=3D1) > > 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 > > 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=3D2) (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=3Dultrafinegrid". >> >> 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 >> : >> > 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 j= ob >> > will be completed without any complains. >> > Sincerely; >> > M. Ibrahim >> > >> > On Fri, Feb 5, 2010 at 10:33 AM, Jamin Krinsky jamink++berkeley.edu >> > 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=3Dread int=3Dultrafinegrid >> >> >> >> 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 >> >> >> >> >> >> >> >> -=3D This is automatically added to each message by the mailing scrip= t =3D- >> >> E-mail to subscribers: CHEMISTRY*ccl.net or use:>> >> >> >> E-mail to administrators: CHEMISTRY-REQUEST*ccl.net or use>> >> >> >> > >> > >> > >> > -- >> > Mahmoud A. A. Ibrahim >> > Current Address >> > 7.05, School of Chemistry, >> > The University of Manchester, >> > Oxford Road, Manchester, M13 9PL, >> > United Kingdom. >> > >> > Home Address >> > Chemistry Department, >> > Faculty of Science, >> > Minia University, >> > Minia 61519, >> > Egypt. >> > >> > Contact Information >> > Email: m.ibrahim*compchem.net >> > Website: www.compchem.net >> > Fax No.: +20862342601 >> > >> >> >> >> -- >> Dimitri de Pinho Cavalcanti >> Departamento de Qu=EDmica Fundamental - UFPE - Br >> +55 81 2126-8447 >> >> >> >> - This is automatically added to each message by the mailing script - >> >> E-mail to subscribers: CHEMISTRY%ccl.netor use:>> >> E-mail to administrators: CHEMISTRY-REQUEST%ccl.netor use>> >> >> > > > -- > 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 > > > --=20 Jamin L Krinsky, Ph.D. Molecular Graphics and Computation Facility 175 Tan Hall, University of California, Berkeley, CA 94720 jamink(a)berkeley.edu, 510-643-0616 http://glab.cchem.berkeley.edu --00151750e6e0f1a884047f0c8bed Content-Type: text/html; charset=ISO-8859-1 Content-Transfer-Encoding: quoted-printable Hi S. Bill,
In the context of real electron configurations Gd3+ cannot b= e a singlet, but these ECPs put those seven unpaired "electrons" = in the core, as part of the potential felt by the explicit valence electron= s (only the core 5s/5p electrons in this basis when considering the free tr= ication). So those 7 4f electrons don't contribute to the multiplicity = in the calculation, the calculation only uses electrons that actually exist= (and have basis functions). I guess the result could be considered similar= to the way ADF calculates closed-shell atom fragments using fractional occ= upations: maybe it's OK to think of it as 3.5 alpha and 3.5 beta f elec= trons in=20 the core but I don't think this is anywhere near rigorously correct. Th= e physical meaning of this is dubious, which is probably the reason for thi= s debate. However, the simplification makes calculations on large lanthanid= e complexes much more doable, and lots of properties that don't depend = much on the electronics of the metal are reproduced pretty well.
Jamin

On Sun, Feb 7, 2010 at 5:07 AM, s. = Bill s_bill36],[yahoo.co.uk <owner-chemistry(a)ccl.ne= t> wrote:
Dear Dimitri, Ibrahim and Jamin
I=A0haven't=A0worked before on Gado= linium, but according to the electronic configuration of Gd ([Xe] 4f7 5d1 6= S2), the electronic configuration of Gd3+ is [Xe] 4f7 [NOT 4p 4s as Dimitri= suggested) (Reference:=A0The physics of metals and metallography=A0Vol. 10= 2=A0Suppl. 1=A02006).
So, Ibrahim suggestion about the multiplicity of Gd3+ couldn't be = singlet is correct.
May I be confused, so any declaration would b= e appreciated.
S. Bill

--- On Sat, 6/2/10, Jamin Krinsk= y 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. Gaussia= n 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 ele= ctrons (why it works with Nd I still don't know. Below is the explanati= on and work-around proposed by Fernando:

If you proceed with this ECP then you will need to use=20 "guess=3Dcore", instead of the default (Harris), when having an o= dd number of core electrons. Note also that, at each geometry optimization step,=20 the initial guess for the wavefunction is generated using a combination=20 of the SCF solution in previous optimization step with a guess from the=20 Harris functional. If find the same problem in a geometry optimization=20 when it reaches the second step, then try to force the use of=20 "guess=3Dcore" at each geometry optimization step with:

guess=3D(core,always)

Anot= her=20 possibility could be to use "guess=3Dcore" for a single point cal= culation=20 and force the program to always read the guess from the checkpoint file=20 ("IOp(4/5=3D1)"). For instance:

%chk=3Dgd.chk
#p scf=3Dtight b3lyp/genecp=A0guess=3Dcore

Title Card Required

3 1
<Geometry = specification>

H C O S 0
6= -31g =A0 =A0 =A0 =A0<--=A0Basis set specification for other elemen= ts
****=
Gd 0
mwb53<= span style=3D"font-weight: normal;">=A0=A0 =A0 =A0 =A0<--=A0Basis set specification for Gd
****

Gd 0
mwb53=A0=A0 =A0 =A0 =A0<--=A0ECP=20 specification for Gd

--link1--
%= chk=3Dgd.chk
#p opt b= 3lyp checkbas=A0geom=3Dcheck iop(4/5=3D1)

Title Card Required

3 1

Thanks much for your input.

Jamin

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

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

=A0 =A0I don't know if the behave is the same, but when i try to use t= he
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<= br> is possible, but i can't use it without the keyword iop(4/5=3D2) (a
bypass that makes gaussian ignore the odd number and runs the
calculation, but takes much more time).

=A0 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. =A0And 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=3Dultrafinegrid".

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=A0Jamin
> The problem backs to the multiplicity of your ion. The Gd3+ ion CAN= 9;T be
> singlet.
> If you run the same job with 3 as charge and 2 as multiplicity, your j= ob
> will be completed without any complains.
> Sincerely;
> M. Ibrahim
>
> On Fri, Feb 5, 2010 at 10:33 AM, Jamin Krinsky jamink++berkeley.edu
> <owner-chemistry*ccl.net> wrote:
>>
>> Sent to CCL by: "Jamin =A0Krinsky" [jamink _ berkeley.edu] >> I'm trying to use the large core MWB53 ECP and accompanying ba= sis for
>> Gd(+3) in Gaussian 09 and I'm getting the following error duri= ng initial
>> guess generation (and the job dies):
>>
>> Fell through 30 in IdenVS.
>> =A0Error termination via Lnk1e in /usr/software/gaussian/g09.revA0= 2/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 us= ing 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.
>> =A0Error 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=3Dread int=3Dultrafinegrid
>>
>> large core gaussian built-in
>>
>> 3 1
>> Gd =A00.0 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
>>
>>
>>
>> -=3D This is automatically added to each message by the mailing sc= ript =3D-
>> E-mail to subscribers: CHEMISTRY*ccl.net or use:
>> =A0 =A0 =A0http://www.ccl.net/cgi-bin/ccl/send= _ccl_message
>>
>> E-mail to administrators: CHEMISTRY-REQUEST*ccl.net or use
>> =A0 =A0 =A0http://www.ccl.net/cgi-bin/ccl/send= _ccl_message>> =A0 =A0 =A0http://www.ccl.net/che= mistry/sub_unsub.shtml>> =A0 =A0 =A0http://www.ccl.net/spamme= rs.txt>>
>>
>
>
>
> --
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0Mahmoud A. A. Ibrahim
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 Current Address
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 7.05, School of Chemistry,
> =A0 =A0 =A0 =A0 =A0 =A0 =A0The University of Manchester,
> =A0 =A0 =A0 =A0 Oxford Road, Manchester, M13 9PL,
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 United Kingdom.
>
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0Home Address
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0Chemistry Department,
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 Faculty of Science,
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0Minia University,
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 Minia 61519,
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0Egypt.<= br> >
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 Contact Information
> =A0 =A0 =A0 =A0 =A0 Email: m.ibrahim*compchem.net
> =A0 =A0 =A0 =A0 =A0 =A0 =A0Website: www.compchem.net
> =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 =A0 Fax No.: +20862342601
>



--
Dimitri de Pinho Cavalcanti
Departamento de Qu=EDmica Fundamental - UFPE - Br
+55 81 2126-8447



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--
Jamin L Krinsky, Ph.D.<= br>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





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

--00151750e6e0f1a884047f0c8bed--