Subject: SUMMARY: Excited State Reviews

From: Wibke Sudholt <[email-masked]>
Date: Fri, 17 Nov 2000 10:19:02 +0100

Hello CCLers,

I was asked to provide a summary of the answers to my question regarding
reviews of excited electronic state calculations. So, here it is!

I have to thank very much (in alphabetical order; hopefully, I did not forget
to mention anybody) ...

Jerome Baudry <[email-masked]>
Adolfas Gaigalas <[email-masked]>
Tapas Kar <[email-masked]>
Sergiusz Kwasniewski <[email-masked]>
E. Lewars <[email-masked]>
Kenny Lipkowitz <[email-masked]>
Michael Towler <[email-masked]>
... for sending answers to my question!

Stefan Grimme <[email-masked]>
... for sharing some private information!

Jose Luis Garcia de Paz <[email-masked]>
Ioannis Kerkines <[email-masked]>
Kiniu Wong Kin-Yiu <[email-masked]>
Qadir K. Timerghazin <[email-masked]>
... for their interest in a summary!

I was also asked about the references for DFT/SCI and DFT/MRCI:
S. Grimme, Density functional calculations with configuration interaction for
the excited states of molecules, Chem. Phys. Lett., 259, (1996), 128
S. Grimme und M. Waletzke, A Combination of Kohn-Sham Density Functional
Theory and Multi-Reference Configuration Interaction Methods, J. Chem. Phys.,
111, (1999), 5645
In addition, please take a look at:
http://www.uni-muenster.de/Chemie/OC/research/grimme/1publ.html

Best regards

Wibke Sudholt
Institute of Theoretical Chemistry
Heinrich-Heine-University
Duesseldorf, Germany
[email-masked]

***** Original Question *****

Dear CCLers,

I'm looking for review papers and/or key articles and/or web pages about the
quantum chemical calculation of electronically excited states (especially
singlet excited states). I'm interested in organic molecules with about 10
heavy atoms (about 20 atoms in total).

The question I would like to answer is: Which semiempirical/ab initio/density
functional methods are known for this purpose? How expensive and accurate are
they?

I'm aware of the CASSCF/CASPT2 articles of Roos et al. and also of some papers
about CIS, TDDFT, DFT/SCI and DFT/MRCI.

Thank you very much in advance!

Best regards

Wibke Sudholt
Institute of Theoretical Chemistry
Heinrich-Heine-University
Duesseldorf, Germany
[email-masked]

***** Answers *****

Dear Wibke

You can have a look at:

Characterization of a Conical Intersection between the Ground and First
Excited State for a Retinal Analog.
Ferenc Molnar, Michal Ben-Nun, Todd J. Martínez, and Klaus Schulten.
Journal of Molecular Structure (THEOCHEM), WATOC special issue,
506:169--178, 2000.

abstract visible at:
http://www.ks.uiuc.edu/Publications/Papers/abstract.cgi?tbcode=MOLN2000A

Hope it helps,
Cheers

*****************************************
Jerome Baudry, Ph.D.
Research Scientist, Computational Chemistry
TransTech Pharma, Inc.
4170 Mendenhall Oaks Pwky, Suite 110
High Point, NC, 27265
http://www.ttpharma.com

[email-masked]
tel: (336) 841-0300  #120
fax: (336) 841-0310

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

Dear Dr. Sudholt,
We( at NIST,USA) are also interested in calculating excited S states of
organic molecules(e.g. fluorescein). Arvydas Tamulis has been trying to do
these calculations for us. He may be able to tell you about his experience.
Below is his address.

[email-masked]
Arvydas Tamulis 
Institute of Theoretical Physics and Astronomy,
Theoretical Molecular Electronics Research Group,
A. Gostauto 12, Vilnius 2600, Lithuania
e-mail: [email-masked]; WEBsite: http://www.itpa.lt/~tamulis/
fax: +(370-2)-225361  or  +(370-2)-224694
Phone: +(370-2)-620861 
< some private information cuted out >

Please keep me informed about  your efforts. My understanding is that these
calculations are difficult and on the forefront of what is possible.

Adolfas Gaigalas 

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

Hi,

Here is the paper which might be helpful.

Comparison of methods for calculating the properties of intramolecular
hydrogen bonds. excited state proton transfer. T. Kar, S. Scheiner and M,
Cuma, J. Chem. Phys., 111 (1999) 849-858.

Tapas
______________________________________

Tapas Kar, Ph.D
Department of Chemistry & Biochemistry
Utah State University
0300 Old Main Hill
Logan, UT 84322-0300

Voice: 435-797-7230
Fax:   435-797-3390
Email: [email-masked]
       [email-masked]

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

Hi,

A frequently used semiempirical method is Zerners ZINDO/S in combi with CIS.
It provides quite accurate one electron excitation energies for amongst others
organic molecules. All calculated excitations belong to valence transitions
however. If you're planning to include calculation of rydberg states as well
then you should focus on ab initio methods like CASPT2, CCSD(T) and TDDFT.

ref for ZINDO/S:

MC Zerner, GH Loew, RF Kirchner, UT Mueller-Westerhoff, JACS, 1980, 102, 589
GM Pearl, MC Zerner, A Broo, J McKelvey, J Comp Chem, 1998, 19, 781

Hope that this is usefull and that you'll send a summary to CCL.

Bye
Sergiusz

___________________________________________________

 Sergiusz Kwasniewski
 LUC SBG/TS
 Universitaire Campus Gebouw D
 3590 Diepenbeek
 BELGIUM

 tel(direct): 032 (0)11/268315
 fax        : 032 (0)11/268301
 email      : [email-masked]
 http://www.luc.ac.be/Research/TheoChem
___________________________________________________

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

W. Sudholt asked for the calc of electronic excited states:

Hello,

Good results for electronically excited states are often obtained from ZINDO/S, a
semiempirical method (fast), and from time-dependent DFT (DDFT) (much slower).
Another standard method is RCIS. I think ZINDO/S and TDDFT are best. All three are
available in Gaussian 98. I could send you some typical input files.

ZINDO/S is a version of INDO/S (M. Kotzian, N. Rosch, and M. C. Zerner, Theor Chim
Acta, 1992, 81, 201) developed by the group of the late Michael Zerner (hence Z).

TDDFT:

M. E. Casida in "Recent developments and applications of modern density functional
theory", J. M. Seminario, Ed., Elsevier, Amsterdam, 1996 and refs therein.

R. E. Stratmen et al, J Chem Phys, 1998, 109, 8218.

K. B. Wiberg e al, Chem Phys Lett, 1998, 297, 60

RCIS
J. B. Foresman and A. Frisch, "Exploring Chemistry..." Gaussian Inc, Pittsburgh,
PA, 1996, p. 218.

E. Lewars

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

A chapter by Michael Robb (first author) entitled "Computational Strategy for
Organic Photochemistry" has been published in Reviews in Computational
Chemistry, vol. 15, 2000, Wiley VCH Publishers, K. Lipkowitz and D. Boyd,
eds., pp 87-147. This may be of value to you.

Kenny Lipkowitz

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

Hello Wibke,

Quantum Monte Carlo is probably the most accurate ab initio technique
available for molecules of medium size and above. It is capable of
treating excited states. 

For recent applications to molecular excited states, see:

Excitons in small hydrogenated silicon clusters. 
A.R. Porter, M.D. Towler and R.J. Needs

Electronic excited-state wave functions for quantum Monte Carlo:
application to silane and methane 
A.R. Porter, O.K. Al-Mushadani, M.D. Towler and R.J. Needs

These are available in preprint form from :

www.tcm.phy.cam.ac.uk/~mdt26/casino.html

Regards,
Mike Towler

-------------------------------------------------------------------------
Dr. Mike Towler ([email-masked]) Theory of Condensed Matter (Rm 537)
Cavendish Laboratory, University of Cambridge, Cambridge  CB3 0HE, UK
Tel. +44-(0)1223-337359                           Fax. +44-(0)1223-337356
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