From owner-chemistry@ccl.net Wed Jan  6 01:12:00 2010
From: "xunlei ding dingxunlei###gmail.com" <owner-chemistry|a|server.ccl.net>
To: CCL
Subject: CCL:G: SCF converge problem for ROHF calculation in G03 /09
Message-Id: <-41002-100105225657-13373-DO3EN61pPIw8MoA1NreuPA|a|server.ccl.net>
X-Original-From: xunlei ding <dingxunlei],[gmail.com>
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Date: Wed, 6 Jan 2010 10:56:28 +0800
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Sent to CCL by: xunlei ding [dingxunlei|a|gmail.com]
Dear All,

We know that the SCF converge problem for RHF or UHF calculations can
be solved by "qc" and many other ways.

But the keywords "qc" and "fermi" can not be used in G03/09 for
restrict open shell calculations (such as ROHF).

In G09, it is said in the manual that "For difficult-to-converge ROHF
wavefunctions, where QC cannot be used, add Use=3DL506 to the route
section." But it seems not work in my test.

Then, how to solve the SCF converge problem for ROHF calculation?

Thanks you for your consideration!

--=20
------------------------------------------------------
Xun-Lei Ding (=B6=A1=D1=B8=C0=D7)
Associate Research Professor of Physical Chemistry, Ph.D
State Key Lab for Struct. Chem. of Unstable and Stable Species
Institute of Chemistry, Chinese Academy of Sciences
Zhongguancun North First Street 2=A3=AC
Beijing 100190, P. R. China
Phone 86-10-62568330
Fax   86-10-62559373


From owner-chemistry@ccl.net Wed Jan  6 04:36:01 2010
From: "=?ISO-8859-1?Q?Ulf_Ekstr=F6m?= uekstrom() gmail.com" <owner-chemistry(0)server.ccl.net>
To: CCL
Subject: CCL: Isolated molecules & unoccupied orbitals: does the basis set matter?
Message-Id: <-41003-100106043258-19749-PRGlrnRImjidWUpgwB8aBQ(0)server.ccl.net>
X-Original-From: =?ISO-8859-1?Q?Ulf_Ekstr=F6m?= <uekstrom : gmail.com>
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Date: Wed, 6 Jan 2010 10:32:37 +0100
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Sent to CCL by: =?ISO-8859-1?Q?Ulf_Ekstr=F6m?= [uekstrom() gmail.com]
Dear  Zhongyun,

> At your suggestion, we have increased the basis set to aug-cc-PVTZ (and
> more)
> in Turbomole, and obtained the same virtual states with VASP, being in go=
od
> agreement with your judgement "the plane wave code is right". Thanks!

Good!

> "It can happen that your state that is too high with the small basis will
> come
> down in energy with a more appropriate basis." Could you please share me =
a
> reasoning or even a reference for this knowledge? It's new to me.

Yes, this is actually very easy to see. The virtual orbitals energies are t=
he
eigenvalues of the Kohn-Sham Hamiltonian H. When you have a finite
basis you are actually looking at H projected on this basis. This projected
Hamiltonian has eigenvalues that are upper bounds to the exact eigenvalues
(they are also lower bounds to the largest eigenvalues of H, so the stateme=
nt
is symmetrical).
This is called McDonald's theorem by P.=C5. Malmqvist in ESQC (european
summer school in quantum chemistry) book I,
but you should be able to find it in any linear algebra text. For the lowes=
t
eigenvector I think everyone knows this fact, but it's true also for the hi=
gher
states.

Sincerely,
Ulf


From owner-chemistry@ccl.net Wed Jan  6 09:12:00 2010
From: "Jozsef Csontos jcsontos.lists{:}gmail.com" <owner-chemistry_-_server.ccl.net>
To: CCL
Subject: CCL: extrapolating to the complete basis set limit
Message-Id: <-41004-100105091151-29205-KTWeCEcyTYKQHmSNpsfPnA_-_server.ccl.net>
X-Original-From: Jozsef Csontos <jcsontos.lists!A!gmail.com>
Content-Type: multipart/alternative;
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Date: Tue, 05 Jan 2010 14:18:42 +0100
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Sent to CCL by: Jozsef Csontos [jcsontos.lists:-:gmail.com]

This is a multi-part message in MIME format.
--------------060303010705060601030008
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Hi Pedro,

I think you've already answered to your own question :)

It's not possible to use Pople's basis sets for such task.

There may exist some work where parametrized formulas were developed for
some properties (similarly to the G1, G2, etc. methods) but anyway,
these basis set were not designed to extrapolate, whatever properties,
you're interested in, to the one electron basis set limit.

Best,
Jozsef


On 01/05/2010 12:09 PM, Pedro Silva pedros#ufp.edu.pt wrote:
> Sent to CCL by: Pedro Silva [pedros||ufp.edu.pt]
> Dear Computational Chemists,
>
> I am aware of a variety of schemes (by Truhlar, Dunning, and others)
> that can be used to extrapolate MP2 (or CCSD) results from cc-pVDZ and
> cc-pVTZ basis sets to the complete basis set limit. I have not been
> able to find similar extrapolating schemes for Pople basis sets (apart
>   
>> from the obvious incremental increase of the basis set until finding
>>     
> an assymptotic energy result).  Can any one point me to a few papers
> on that? I have been searching the Web of Science without much success
> (either due to a poor choice of query words, ot to the non-existence
> of such references...)
>
>
> Thank you so much!
>
> Pedro
>
> PS: Happy 2010 :-)
>   

--------------060303010705060601030008
Content-Type: text/html; charset=UTF-8
Content-Transfer-Encoding: 7bit

<!DOCTYPE HTML PUBLIC "-//W3C//DTD HTML 4.01 Transitional//EN">
<html>
<head>
  <meta content="text/html; charset=UTF-8" http-equiv="Content-Type">
  <title></title>
</head>
<body text="#000000" bgcolor="#ffffff">
<font size="+1">Hi Pedro,<br>
<br>
I think you've already answered to your own question :)<br>
<br>
It's not possible to use Pople's basis sets for such task. <br>
<br>
There may exist some work where parametrized formulas were developed
for some properties (similarly to the G1, G2, etc. methods) but anyway,
these basis set were not designed to extrapolate, whatever properties,
you're interested in, to the one electron basis set limit. <br>
<br>
Best,<br>
Jozsef<br>
<br>
</font><br>
On 01/05/2010 12:09 PM, Pedro Silva pedros#ufp.edu.pt wrote:
<blockquote
 cite="mid:-id%234e9-40999-100105060913-14743-sKFt%2FHgs6iQYNm6ZnvScbw(!)server.ccl.net"
 type="cite">
  <pre wrap="">
Sent to CCL by: Pedro Silva [pedros||ufp.edu.pt]
Dear Computational Chemists,

I am aware of a variety of schemes (by Truhlar, Dunning, and others)
that can be used to extrapolate MP2 (or CCSD) results from cc-pVDZ and
cc-pVTZ basis sets to the complete basis set limit. I have not been
able to find similar extrapolating schemes for Pople basis sets (apart
  </pre>
  <blockquote type="cite">
    <pre wrap="">from the obvious incremental increase of the basis set until finding
    </pre>
  </blockquote>
  <pre wrap="">an assymptotic energy result).  Can any one point me to a few papers
on that? I have been searching the Web of Science without much success
(either due to a poor choice of query words, ot to the non-existence
of such references...)


Thank you so much!

Pedro

PS: Happy 2010 :-)
  </pre>
</blockquote>
</body>
</html>

--------------060303010705060601030008--


From owner-chemistry@ccl.net Wed Jan  6 09:46:01 2010
From: "John McKelvey jmmckel%x%gmail.com" <owner-chemistry_-_server.ccl.net>
To: CCL
Subject: CCL:G: SCF converge problem for ROHF calculation in G03 /09
Message-Id: <-41005-100106090815-9566-dlZC5trj9bUDp7oyYPRYmA_-_server.ccl.net>
X-Original-From: John McKelvey <jmmckel!=!gmail.com>
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Date: Wed, 6 Jan 2010 09:08:03 -0500
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Sent to CCL by: John McKelvey [jmmckel**gmail.com]
It is not stated what basis was used.  On the assumption that as basis
sets get larger convergence difficulties may increase, there is always
the possibility that starting with smaller basis sets where
convergence occurs and then slowly increase the size of the basis set
while using the "guess=3Dread" option, which will pick up the previous
SCF vectors as a starting guess.


John McKelvey

2010/1/5 xunlei ding dingxunlei###gmail.com <owner-chemistry._-_.ccl.net>:
>
> Sent to CCL by: xunlei ding [dingxunlei|a|gmail.com]
> Dear All,
>
> We know that the SCF converge problem for RHF or UHF calculations can
> be solved by "qc" and many other ways.
>
> But the keywords "qc" and "fermi" can not be used in G03/09 for
> restrict open shell calculations (such as ROHF).
>
> In G09, it is said in the manual that "For difficult-to-converge ROHF
> wavefunctions, where QC cannot be used, add Use=3DL506 to the route
> section." But it seems not work in my test.
>
> Then, how to solve the SCF converge problem for ROHF calculation?
>
> Thanks you for your consideration!
>
> --
> ------------------------------------------------------
> Xun-Lei Ding (=B6=A1=D1=B8=C0=D7)
> Associate Research Professor of Physical Chemistry, Ph.D
> State Key Lab for Struct. Chem. of Unstable and Stable Species
> Institute of Chemistry, Chinese Academy of Sciences
> Zhongguancun North First Street 2=A3=AC
> Beijing 100190, P. R. China
> Phone 86-10-62568330
> Fax   86-10-62559373
>
>
>
> - This is automatically added to each message by the mailing script ->
>
>



--=20
John McKelvey
10819 Middleford Pl
Ft Wayne, IN 46818
260-489-2160
jmmckel._-_.gmail.com


From owner-chemistry@ccl.net Wed Jan  6 11:32:01 2010
From: "Mariusz Radon mariusz.radon|*|gmail.com" <owner-chemistry%%server.ccl.net>
To: CCL
Subject: CCL:G: SCF converge problem for ROHF calculation in G03 /09
Message-Id: <-41006-100106112714-12046-DWCithSiZVkI/DHRifdtBg%%server.ccl.net>
X-Original-From: Mariusz Radon <mariusz.radon+/-gmail.com>
Content-Transfer-Encoding: quoted-printable
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Date: Wed, 6 Jan 2010 16:56:17 +0100
MIME-Version: 1.0


Sent to CCL by: Mariusz Radon [mariusz.radon::gmail.com]
Hello,

Indeed, (lack of) convergence in ROHF is a problem. I would advice you to t=
ry:

=C2=A0- different (smaller) basis set - than use converged solution as
guess for the larger basis - as was already suggested;
=C2=A0- play a little bit with level shift (vshift);
=C2=A0- if possible, try also a different software, in particular
Schrodinger's Jaguar, esp. if your system is a transition metal
complex.

Are your calculations true ROHF or rather RO-DFT? If DFT, you may try
with a different functional. I have heard that it might be easier to
converge RO-DFT with hybrid than with non-hybrid functional (but I
don't know how much it can be helpful in practice). You may also try
the 100% of the exact exchange i.e. true ROHF calculations. If these
calculations converge, you will be able to provide a better guess to
your favorite functional.

With best regards,
Mariusz Radon

2010/1/6 John McKelvey jmmckel%x%gmail.com <owner-chemistry|,|ccl.net>:
>
> Sent to CCL by: John McKelvey [jmmckel**gmail.com]
> It is not stated what basis was used. =C2=A0On the assumption that as bas=
is
> sets get larger convergence difficulties may increase, there is always
> the possibility that starting with smaller basis sets where
> convergence occurs and then slowly increase the size of the basis set
> while using the "guess=3Dread" option, which will pick up the previous
> SCF vectors as a starting guess.
>
>
> John McKelvey
>
> 2010/1/5 xunlei ding dingxunlei###gmail.com <owner-chemistry.:.ccl.net>:
>>
>> Sent to CCL by: xunlei ding [dingxunlei|a|gmail.com]
>> Dear All,
>>
>> We know that the SCF converge problem for RHF or UHF calculations can
>> be solved by "qc" and many other ways.
>>
>> But the keywords "qc" and "fermi" can not be used in G03/09 for
>> restrict open shell calculations (such as ROHF).
>>
>> In G09, it is said in the manual that "For difficult-to-converge ROHF
>> wavefunctions, where QC cannot be used, add Use=3DL506 to the route
>> section." But it seems not work in my test.
>>
>> Then, how to solve the SCF converge problem for ROHF calculation?
>>
>> Thanks you for your consideration!
>>
>> --
>> ------------------------------------------------------
>> Xun-Lei Ding (=E4=B8=81=E8=BF=85=E9=9B=B7)
>> Associate Research Professor of Physical Chemistry, Ph.D
>> State Key Lab for Struct. Chem. of Unstable and Stable Species
>> Institute of Chemistry, Chinese Academy of Sciences
>> Zhongguancun North First Street 2=EF=BC=8C
>> Beijing 100190, P. R. China
>> Phone 86-10-62568330
>> Fax =C2=A0 86-10-62559373
>>
>>
>>
>> - This is automatically added to each message by the mailing script ->
>>
>>
>
>
>
> --
> John McKelvey
> 10819 Middleford Pl
> Ft Wayne, IN 46818
> 260-489-2160
> jmmckel.:.gmail.com
>
>
>
> - This is automatically added to each message by the mailing script -> =C2=A0 =C2=A0 =C2=A0http://www.ccl.net/cgi-bin/ccl/send_ccl_message> =C2=A0 =C2=A0 =C2=A0http://www.ccl.net/cgi-bin/ccl/send_ccl_message> =C2=A0 =C2=A0 =C2=A0http://www.ccl.net/chemistry/sub_unsub.shtml> =C2=A0 =C2=A0 =C2=A0http://www.ccl.net/spammers.txt>
>
>



--
Mariusz Radon, PhD student
Department of Theoretical Chemistry
Jagiellonian University
http://www.chemia.uj.edu.pl/~mradon
mradon /at/ chemia.uj.edu.pl
(PGP public key available on the website)



--=20
Mariusz Radon, PhD student
Department of Theoretical Chemistry
Jagiellonian University
http://www.chemia.uj.edu.pl/~mradon
mradon /at/ chemia.uj.edu.pl
(PGP public key available on the website)


From owner-chemistry@ccl.net Wed Jan  6 12:20:02 2010
From: "Sanjay Bharathwaj computationalchemist]|[gmail.com" <owner-chemistry#,#server.ccl.net>
To: CCL
Subject: CCL:G: Plane wave basis sets
Message-Id: <-41007-100105142445-15014-Psx34psqwqu1Q4J/i+1Ubg#,#server.ccl.net>
X-Original-From: Sanjay Bharathwaj <computationalchemist__gmail.com>
Content-Type: multipart/alternative; boundary=0015174c0f024016a6047c6ef05b
Date: Tue, 5 Jan 2010 13:23:45 -0500
MIME-Version: 1.0


Sent to CCL by: Sanjay Bharathwaj [computationalchemist++gmail.com]

--0015174c0f024016a6047c6ef05b
Content-Type: text/plain; charset=ISO-8859-1

Dear all,

I have a very preliminary question.

Polarization functions and diffusion functions are added in
the Gaussian basis sets to
better describe the atomic orbitals.

How this kind of functions could be accounted with plane wave basis sets.
Does increasing the the energy cutoff takes care of these functions.
If so what energy cut off level should be used for 4d and 5f orbitals.

Pointing to any papers or webpages is really appreciated

Again sorry if the question is too naive.

Best regards


-- 
Regards,
Dr. Sanjay Bharathwaj Kumar,
Dharmendra Institute of Technology,
Senchillakamani,
India.

--0015174c0f024016a6047c6ef05b
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<span class=3D"Apple-style-span" style=3D"font-family: verdana, tahoma, ari=
al, helvetica, sans-serif; font-size: 11px; -webkit-border-horizontal-spaci=
ng: 2px; -webkit-border-vertical-spacing: 2px; ">Dear all,=A0<br><br>I have=
 a very preliminary question.=A0</span><div>
<font class=3D"Apple-style-span" face=3D"verdana, tahoma, arial, helvetica,=
 sans-serif" size=3D"3"><span class=3D"Apple-style-span" style=3D"font-size=
: 11px; -webkit-border-horizontal-spacing: 2px; -webkit-border-vertical-spa=
cing: 2px;"><br>
</span></font></div><div><font class=3D"Apple-style-span" face=3D"verdana, =
tahoma, arial, helvetica, sans-serif" size=3D"3"><span class=3D"Apple-style=
-span" style=3D"font-size: 11px; -webkit-border-horizontal-spacing: 2px; -w=
ebkit-border-vertical-spacing: 2px;">Polarization functions and diffusion f=
unctions are added in the=A0Gaussian=A0basis sets to=A0</span></font></div>
<div><font class=3D"Apple-style-span" face=3D"verdana, tahoma, arial, helve=
tica, sans-serif" size=3D"3"><span class=3D"Apple-style-span" style=3D"font=
-size: 11px; -webkit-border-horizontal-spacing: 2px; -webkit-border-vertica=
l-spacing: 2px; ">better describe the atomic orbitals.</span></font></div>
<div><font class=3D"Apple-style-span" face=3D"verdana, tahoma, arial, helve=
tica, sans-serif" size=3D"3"><span class=3D"Apple-style-span" style=3D"font=
-size: 11px; -webkit-border-horizontal-spacing: 2px; -webkit-border-vertica=
l-spacing: 2px;"><br>
</span></font></div><div><font class=3D"Apple-style-span" face=3D"verdana, =
tahoma, arial, helvetica, sans-serif" size=3D"3"><span class=3D"Apple-style=
-span" style=3D"font-size: 11px; -webkit-border-horizontal-spacing: 2px; -w=
ebkit-border-vertical-spacing: 2px;">How this kind of functions could be ac=
counted with plane wave basis sets.</span></font></div>
<div><span class=3D"Apple-style-span" style=3D"font-family: verdana, tahoma=
, arial, helvetica, sans-serif; font-size: 11px; -webkit-border-horizontal-=
spacing: 2px; -webkit-border-vertical-spacing: 2px; ">Does increasing the t=
he energy cutoff takes care of these functions.</span></div>
<div><font class=3D"Apple-style-span" face=3D"verdana, tahoma, arial, helve=
tica, sans-serif" size=3D"3"><span class=3D"Apple-style-span" style=3D"font=
-size: 11px; -webkit-border-horizontal-spacing: 2px; -webkit-border-vertica=
l-spacing: 2px;">If so what energy cut off level should be used for 4d and =
5f orbitals.=A0</span></font></div>
<div><font class=3D"Apple-style-span" face=3D"verdana, tahoma, arial, helve=
tica, sans-serif" size=3D"3"><span class=3D"Apple-style-span" style=3D"font=
-size: 11px; -webkit-border-horizontal-spacing: 2px; -webkit-border-vertica=
l-spacing: 2px;"><br>
</span></font></div><div><font class=3D"Apple-style-span" face=3D"verdana, =
tahoma, arial, helvetica, sans-serif" size=3D"3"><span class=3D"Apple-style=
-span" style=3D"font-size: 11px; -webkit-border-horizontal-spacing: 2px; -w=
ebkit-border-vertical-spacing: 2px;">Pointing to any papers or webpages is =
really appreciated</span></font></div>
<div><div><font class=3D"Apple-style-span" face=3D"verdana, tahoma, arial, =
helvetica, sans-serif" size=3D"3"><span class=3D"Apple-style-span" style=3D=
"font-size: 11px; -webkit-border-horizontal-spacing: 2px; -webkit-border-ve=
rtical-spacing: 2px;"><br>
</span></font></div><div><span class=3D"Apple-style-span" style=3D"font-fam=
ily: verdana, tahoma, arial, helvetica, sans-serif; font-size: 11px; -webki=
t-border-horizontal-spacing: 2px; -webkit-border-vertical-spacing: 2px; ">A=
gain sorry if the question is too naive.=A0<br>
<br>Best regards=A0<br><br></span><br>-- <br>Regards,<br>Dr. Sanjay Bharath=
waj Kumar,<br>Dharmendra Institute of Technology,</div><div>Senchillakamani=
,</div><div>India.<br>
</div></div>

--0015174c0f024016a6047c6ef05b--