Subject: Mo DFT/ECP Summary

From: [email-masked] (Larry Cuffe)
Date: Fri, 27 Nov 1998 16:43:12 +0000 (GMT)

Original question:
I'm trying to study complexes of Mo. using DFT. Does it make sense
to use an ECP basis set with DFT (b3lyp) and if so has anyone any sugestions
for basis set of about 6-311G* quality
larry

Executive Summary:
its ok.
Summary:
Question 1:
 It seems o.k. to do so there is some concern about using ECP's and basis sets optimized for 
HF with DFT. The principal cause for concern seems to be problems with BSSE using this sort
of system.  Results are likely to be no worse than HF and may well be better.
Question 2:
 Try the stuttgart group: for ECP's
http://www.theochem.uni-stuttgart.de/ 
or use jaguar which has ECP basis sets built in.
or download from the EMSL basis set library:
http://www.emsl.pnl.gov:2080/docs/ecce/sets/sets.html

Thanks to everyone who replied.

Other references I've uncovered are:
Kaupp, n. Malkin, V. G., Malkina O. L., and Et Salahub, D. R. 
J A C S oct 1994 looks at DFT with ECP's for calculation O NMR shifts for transistion metals.
and a Summary on DFT with ECP's in the CCL archives for 1996.

Below is the slightly edidted text of the replies I recieved.

Dear Larry,

yes, I think you should use an ECP basis set to get the major relativistic
effects. In particular, you will probably get a sizable bond contraction
due to relativity.

   There are a few, not many, papers that study the transferability of
Hartree-Fock derived ECPs into DFT, and it seems that one can do it. The
references are:

C. van W=FCllen Int. J. Quant. Chem., 1996, 58, 147.
T. V. Russo, R. L. Martin, P. J. Hay J. Phys. Chem. 1995, 99, 17085.

Best regards, Georg

--
=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=

Dr. Georg Schreckenbach           Tel:     (USA)-505-667 7605
Theoretical Chemistry T-12        FAX:     (USA)-505-665 3909
M.S. B268, Los Alamos National      E-mail:  [email-masked]
Laboratory, Los Alamos, New Mexico, 87545, USA
Internet:    http://www.t12.lanl.gov/~schrecke/
=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=3D=
***********************************   
I've had good results using the SBK ECPs for Os; it seems to work
just fine with B3LYP and has the three d functions you are looking for.

    Refs would be:

          W.J.Stevens, H.Basch, M.Krauss
                  J.Chem.Phys. 81, 6026-6033 (1984)
          W.J.Stevens, H.Basch, M.Krauss, P.Jasien
                  Can.J.Chem, 70, 612-630 (1992)
          T.R.Cundari, W.J.Stevens  
                  J.Chem.Phys. 98, 5555-5565(1993)
 
    Personally, I don't bother with ECPs for the 3d transition metals as
it doesn't remove that many basis functions and the codes I use can't
compute analytical hessians when ECPs are present.  With the 4d and 5d
metals and the f block metals I use ECPs routinely, to incorporate the
relativistic effects that make the s-p splitting different from what is
found in the non-relativistic equivalent.

					Mark

  To reply, replace the danish robersen with the scottish roberson.

**********************************************************************

We study Ti clusters and TiO2 surfaces using the LACVP** basis of the Jaguar package 
(Schroedinger, Inc.) This basis uses ECPs on the transition-metal atoms and 6-31G** 
basis on others. Ref.for this basis is: P.J.Hay & W.R.Wadt, J.Chem.Phys.82, 299(1985)
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
/  Dr. N. SUKUMAR             /  Tel (O): (414)288-6753  /
/  Department of Chemistry    /      (R): (414)244-2786  /
/  Marquette University       /  Fax  :   (414)288-7066  /
/  P.O.Box 1881               ~~~~~~~~~~~~~~~~~~~~~~~~~~~/
/  Milwaukee, WI 53201-1881                              /
/  Email : [email-masked]                    /
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~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~

Oh yes, we use DFT with B3LYP. Manuscripts in preparation:

\title{Adsorption of O$_2$ on TiO$_2$(110):  A theoretical study}
\author{C.Shu, N.Sukumar & Charles P.Ursenbach;

\title{Theoretical study of adsorption of O$_2$ and CO on TiO$_2$(110)}
\author{N.Sukumar and C.P.Ursenbach}

~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
/  Dr. N. SUKUMAR             /  Tel (O): (414)288-6753  /
/  Department of Chemistry    /      (R): (414)244-2786  /
/  Marquette University       /  Fax  :   (414)288-7066  /
/  P.O.Box 1881               ~~~~~~~~~~~~~~~~~~~~~~~~~~~/
/  Milwaukee, WI 53201-1881                              /
/  Email : [email-masked]                    /
/  http://www.thch.uni-bonn.de/tc/sukumar.html           /
~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
**************************************************************************

Hi Larry,

I just happened to do some B3PW91 calculations on some pretty large
Pt-complexes ( Pt(PMe3)2(i-Pr)(MeCN)+ ). We used an ECP on Pt there and
all things worked out just fine. I don't know however, if it's
theoretically justified.
Anyway, if you get some answers, I'd like to receive a summary (probably
you might summarize to the list anyway?)

Best Regards,

Steven

--------------------------------------------------------------------------
Steven Creve                       [email-masked]
Labo Quantumchemie
Celestijnenlaan 200F
3001-HEVERLEE                      tel: (32) (16) 32 73 93
BELGIUM                            fax: (32) (16) 32 79 92
***************************************************************************

Hi, Larry. I have computed Mo hydrides (H...H bonded complexes) with
DFT. B3PW91/LanLDZ gave reasonable results.   Orlova, G.; Scheiner, S.
J. Phys. Chem.A, 102, 260-269.  
-- 
Galina Orlova
Vis. Res. Professor
[email-masked]
Department of Chemistry and Biochemistry
University of Guelph
Guelph, ON, N1G 2W1, Canada

ph. (519) 824 4120 ext 3061
Fax (519) 766-1499
***************************************************************************

Hi Larry,

there seems to be consensus that ECPs for wavefunction-based methods are =
usable for DFT calculations, too. I do not know if there are any =
ECPs/valence basis sets optimized for DFT. Have a look at the web page =
of the Stuttgart group:
http://www.theochem.uni-stuttgart.de/
They have lots of ECPs and many of them in a format suitable for G9x. =
The others can be converted quite easyly. The ECP of choice would be =
Mo-ECP28MWB (multi electron fit; Wood-Boring, i.e. quasirelativistic).=20

Another place is the EMSL basis set library:
http://www.emsl.pnl.gov:2080/docs/ecce/sets/sets.html
http://www.emsl.pnl.gov:2080/forms/basisform.html
or its european mirror:
http://wserv1.dl.ac.uk:800/emsl_pnl/basisform.html

Concerning the polarization functions: Some people take them from =
comparable basis sets in the literature (e.g. from Huzinagas Handbook of =
Gaussian Basis Sets) others optimize them for a specific valence basis =
set (see e.g. Frenking et al. in Chem. Phys. Lett. 208 (1993) 111). =
There are other methods of optimizing polarization functions, but I =
don't have references at hand.

___________________________________
Dr. Stefan Fau
Fachbereich Chemie, AK Frenking
Philipps-Universit=E4t Marburg
35032 Marburg, Germany
[email-masked]

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Requests for summaries were also received from:
Adel El-Azhary and Patricia L. M. Plummer