Summary:DFT for hydrogen bond
- From: Yubo Fan <yubofan.,at,.mail.chem.tamu.edu>
- Organization: Chemistry Department, Texas A&M University
- Subject: Summary:DFT for hydrogen bond
- Date: Thu, 08 Feb 2001 10:00:45 +0000
I sent a message about hydrogen bond calculation by DFT to CCL several
days ago. I've got many helpful replies. Now I summarize them below.
I know most of DFT methods are not good to the calculation of Hydrogen
Bonding. But a friend of mine told me somebody developed a DFT method
that can be used in HB calculations. What is this method?
Are there some papers using different methods (DFT methods preferred) to
calculate HB and systematically compare them? Any advice is helpful.
Thanks in Advance
Dr. Yubo Fan Email: yubofan.,at,.mail.chem.tamu.edu
Department of Chemistry Tel: 1-979-845-7222
Texas A&M University
College Station, TX 77843
Hello. I had a couple of such publications a few years back. They are as
A. T. Pudzianowski, "A Systematic Appraisal of Density Functional
for Hydrogen Bonding in Binary Ionic Complexes," J. Phys. Chem.
A. T. Pudzianowski, "Current Computational Approaches to The Strong
Bond," Rec. Res. Devel. in Physical Chem. 1, 81-97 (1997).
Both of these deal with the strong H-bond, but there are plenty of
other situations. The latter reference is a review article, so there is
related information. It appears in a volume published in India, so it
hard to find. Let me know if you'd like reprints and I'll send them
Andrew T. Pudzianowski, Ph.D.
Computer-Assisted Drug Design
Bristol-Myers Squibb PRI
Princeton NJ 08543-4000
(609) 252-4248 (office)
(609) 252-6030 (fax)
check B(M)LYP functional which was developed for such calculations
(references in the paper enclosed). It's essentially B3LYP whith HF
increased to 35%. I've tested it on OH- hydration and it performed quite
Prof. Piotr Paneth
temporary address through 5/3/01:
Department of Chemistry, Smith Hall box I11, room 224
University of Minnesota
Minneapolis, MN 55455-0431
207 Pleasant St. SE
phone: (612) 626-0259, fax: (612) 624-9320 or (612) 626-9390
E-mail: paneth.,at,.comp.chem.umn.edu or panet001.,at,.umn.edu
Re: your question to CCL concerning h-bonding and dft.
We have been working on a number of H-bonded clusters involving
water and have found that the (generally popular) B3LYP method
and others give too high "binding".
It is suggested that the HTCH functional could be good - this is
probably the one you are thinking of. A ref you might find useful is:
Tuma, Christian; Daniel Boese, A.; Handy, Nicholas C..
Predicting the binding energies of H-bonded complexes: A
comparative DFT study. Phys. Chem. Chem. Phys. (1999),
1(17), 3939-3947. CODEN: PPCPFQ ISSN:1463-9076. CAN
131:342144 AN 1999:538455 CAPLUS
and other papers by Handy describing the development of new
I would be grateful if you summarize or email me any interesting
information you get.
Department of Chemistry
University of Otago
tel 64 3 479 7929
fax 64 3 479 7906
actually some of the hybrid DFT does pretty well
for H-bonds. Something like B3LYP/6-31+G* gets the
water dimer interaction right to about 0.5 kcal/mol.
| Frank Jensen, Department of Chemistry |
| SDU Odense University, DK-5230 Odense, Denmark |
| FAX +45 66 15 87 80 , Voice +45 65 50 25 07 |
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Try the functionals by Nic Handy (there is one in Gaussian) and also the
see www.gaussian.com, DFT methods for details or better consult the
Koch, Holthausen, VCH 2000
take a look at the following papers:
- Kumar et al., Low barrier hydrogen bonds: Ab initio and DFT
Investigations, J. Comp. Chem. 1998, 19, 1345-1352.
- C. Tuma et al., Predicting the binding energies of H-Bonded complexes:
A comparative DFT study, Phys. Chem. Chem. Phys.
(PCCP) 1999, 1, 3939- 3947.
-Novoa & Soso, Evaluation of the Density Functional Approximation on the
Computation of H-Bond Interactions, J. Phys. Chem.
1995, 99, 15837-15845.
- Molecular Dynamics and DFT Studies of Intermolecular Hydrogen Bonds
between Bifunctional Heteroazaaromatic Molecules
and Hydroxylic Solvents, J.P.C. A; 2000; 104(42); 9542-9555.
- Comparative Study of BSSE Correction Methods at DFT and MP2 Levels of
Theory (of Hydrogen-bonded clusters),
J.Comp.Chem. 1998, 69, 575-584 (and references therein).
- Density Functional Theory and Molecular Clusters, J. Comp. Chem. 1995,
- A Systematic Appraisal of Density Functional Methodologies for
Hydrogen Bonding in Binary Ionic Complexes," J. Phys.
Chem. 100, 4781-4789 (1996).
Hopefully you will find something useful.
All the best
I'd say it depends a bit on the system.
If the nature of the hydrogen bond is mainly electrostatic,
then gradient-corrected and hybrid functional do a reasonably good job.
If the nature of the hydrogen bond is mainly
dispersive, then DFT won't work.
Dr. Klaus Stark
Molecular Simulations Inc.
82 008 Unterhaching
Phone : ++49-89-61459-420
Mobile : ++49-172-936-3380
Fax : ++49-89-61459-400
E-Mail : kstark.,at,.msi.de
Web Page : http://www.msi.com
actually, DFT methods are not really bad for hydrogen bonding,
they are just really bad in treating dispersion. They overestimate the
electrostatic attraction in order to compensate for the lack of proper
treatment of electron correlation. For H-bonded systems, using the
B3LYP density functional and the 6-31G(d,p) basis set, you can obtain
with quite reasonable geometries and interaction energies.
Usually H-bonds are about 0.03A shorter than the they would be when
you optimise them with MP2 method and interaction energies are about
Density functional calculations on H-bonded systems have been
carried out in:
M. Meyer, T. Steinke, M. Brandl, J. Sühnel J. Comp. Chem. 2001, 22,
Density Functional Study of Guanine and Uracil Quartets and of
Guanine/Metal Ion Complexes
Dear Yubo Fan:
The following paper might be of interest to you:
J. Spanget-Larsen: "Infrared absorption and Raman scattering of
(Z)-3-hydroxypropenal. A density functional theoretical study",
Chemical Physics 240 (1999) 51-61.
A number of standard DFT procedures (BLYP, BPW91, B3LYP, B3PW91) are
a study of molecular and vibrational structure of 3-hydroxypropenal
(malonaldehyd enol), probably the simplest species with an
JENS SPANGET-LARSEN Phone: +45 4674 2000 (RUC)
Department of Chemistry +45 4674 2710 (direct)
Roskilde University (RUC) Fax: +45 4674 3011
P.O.Box 260 E-Mail: JSL.,at,.virgil.ruc.dk
DK-4000 Roskilde, Denmark http://virgil.ruc.dk/~jsl/