Subject: Summary of NMR calculaton.

From: [email-masked] (Mori Seiji)
Date: Thu, 7 Dec 1995 13:46:11 +0900

Dear netters,

 Thank you for several replies about my questions for the method of NMR
chemical shift, and so on. 
Replies about  isotropy and anitrosopy which I posted will be sent soon.
I think the reliability of IGAIM , CSGT in G94 packages were not known very
much thus we have to check
these methods comparing with known methods. The systematic review of
solvent effects, 
polarity and coordination with donating solvent such as ether have still be
awaited.

  Sincerely yours,
  Seiji Mori

---my original question---

  Dear everybody,

Recently, many letters about NMR chemical shift calculation were posted,
and I am also 
interested in NMR shifts in organic and organometallic complexes in
solution. I have several questions,

1. How is the reliablities of 
   1.1  methods (GIAO, IGAIM, CSGT, IGLO)
   1.2  theory (HF,DFT,MP2...CC) and basis-sets
   1.3  How is the solvent effect of polarity on the NMR shift, coupling
constant
(I think it is not related calcluation , probably it is a fundamental
question about NMR)?
2. Do you know the program or references which one can calculate not only
chemical shift but also 
the coupling constant 
( for example, 1H-1H and 13C-13C) and NOE in quantum chemistry other than
G94? As to 1H-1H 
coupling constant, 
many programs such as PCMODEL was supported but its calculation  is not QC. 

 If you have comments and indicate the references, would you please send me
? I will summarize
replies.

 Thanks in advance,
 Seiji Mori
-------------
Replies
---1---
Received: by zinc.chem.ucalgary.ca (AIX 3.2/UCB 5.64/4.03)
          id AA10813; Fri, 24 Nov 1995 15:29:30 -0700
From: [email-masked]
Message-Id: <[email-masked]>
Subject: Re: CCL:NMR shift and coupling constant calculation

Hi Seiji,

you have quite a lot of questions in your posting ... I shall try to give
you a few hints, with no intention to be comprehensive.

> 
> 1. How is the reliablities of 
>    1.1  methods (GIAO, IGAIM, CSGT, IGLO)
>    1.2  theory (HF,DFT,MP2...CC) and basis-sets
>    1.3  How is the solvent effect of polarity on the NMR shift, coupling
> constant
> (I think it is not related calcluation , probably it is a fundamental
> question about NMR)?

Good references to start with are three nice reviews, one new, two are older:

D.B.Chesnut:
Annual Reports on NMR Spectroscopy,   published by Academic Press,
Vol.21,1989, p. 51    and ibid, Vol. 29, 1994, p.71.

H.Fukui:
Magn. Res. Rev. 1987, vol. 11, 205

Further, very comprehensive reviews are contained in an annual series, since
1980 written every year by C.Jameson: in Specialist Periodical Report on
Nuclear Magnetic Resonance, Vol.8,1980-... (edited by G.A.Webb, and 
published by the Royal Society of Chemistry, Cambridge)

Now more specific comments on your various questions.

1.1 
Methods with distributed gauge origins (IGLO, LORG, GIAO,...) are 
generally preferable (for a given basis set) over 
methods with a common gauge origin. For examples, see the various reviews.
GIAO seems to converge slightly faster with the size of the basis set
then IGLO (see Wolinski, Hinton, Pulay, JACS 1990, 112, 8251). This
would also make sense from a theoretical point of view.
   I don't know off hand about IGAIM, CSGT.

1.2 Correlation.
there are cases where correlation is necessary, e.g., M.Buehl et al.
J.Phys.Chem.
99, 4000 (1995), and M.Buehl et al. Chem.Phys.Lett. 241 (1995), 248.
These papers contain examples where MP2 fails completely to predict the 
shift while DFT and CCSD are able to achieve quantitative results.
   There are however many other cases where the HF level works just fine
(all the
respective literature up to -- say -- five years ago).

Basis sets.
See about any paper with calculated shifts. E.g., the one by Pulay et al.
mentioned above, or various papers by the Kutzelnigg group, or the various
reviews.

1.3 Solvation effects can be considerable, indeed. Look for experiments
that were
done in the gas phase (in addition to solution studies). A review of gas phase 
NMR was written by C. Jameson:
Chem.Rev.1991, 91, 1375.

> 2. Do you know the program or references which one can calculate not only
> chemical shift but also 
> the coupling constant 
> ( for example, 1H-1H and 13C-13C) and NOE in quantum chemistry other than
> G94? As to 1H-1H 
> coupling constant, 
> many programs such as PCMODEL was supported but its calculation  is not QC. 

Coupling constants are MUCH tougher to calculate than chemical shifts.
The reason is (in my opinion) that you are dealing with operators that 
evaluate the electron density in essentially just one point of space rather
than over an entire region of space.
     Annual reviews of calculations are contained in the same series of books
that was metioned before:
Specialist Periodical Report on Nuclear Magnetic Resonance

Calculations have been done recently, e.g., by Erikson/Malkin/Salahub et al. but
I don't have the references on hand right now.

I am looking forward to your summary!

Yours, Georg

==============================================================================
Georg Schreckenbach                      Tel: (Canada)-403-220 8204
Department of Chemistry                  FAX: (Canada)-403-289 9488
University of Calgary                    Email: [email-masked]
2500 University Drive N.W.,  Calgary,  Alberta,  Canada,  T2N 1N4
==============================================================================
---2---
From: "Steve Gwaltney" <[email-masked]>
Received:  by red11 (SMI-8.6/4.11)
        id KAA08969; Mon, 27 Nov 1995 10:51:20 -0500
Date: Mon, 27 Nov 1995 10:51:20 -0500

> 2. Do you know the program or references which one can calculate not only
> chemical shift but also 
> the coupling constant 
> ( for example, 1H-1H and 13C-13C) and NOE in quantum chemistry other than
> G94? As to 1H-1H 

ACES II can calculate chemical shifts using GIAO's and MBPT(2)
wavefunctions.  ACES II can also calculate CCSD coupling constants.
For information about ACES II contact [email-masked].  I believe
TURBOMOLE can also calculate chemical shifts, but you should check
with them to make sure.

Steve

Steven Gwaltney
[email-masked]
Quantum Theory Project
University of Florida
---3---
From: [email-masked] (Wagener Thomas)
Subject: CCL:NMR shift and coupling constant calculation
Date: Mon, 27 Nov 1995 14:12:47 +0100 (CET)
Dear Seiji Mori,

since I have finished my thesis on the ab-initio calculation a few month
ago, I hopefully can help you with some of your questions.
 
> 1. How is the reliablities of 
>    1.1  methods (GIAO, IGAIM, CSGT, IGLO)
>    1.2  theory (HF,DFT,MP2...CC) and basis-sets
>    1.3  How is the solvent effect of polarity on the NMR shift, coupling
> constant

I had only the opportunity to work with GIAO and IGLO so I can only make a 
statement on these methods.
Basically IGLO and GIAO are quite reliable for the calculation of "standard"
organic compounds though the accuracy of the methods is not as high as the
experimental accuracy. A rough estimate would be an accuracy of about 5ppm
for 13C chemical shifts - probably better. Taking into account that you are
comparing gas phase values at absolute zero with values taken from a sample
in solution at a temperature of, say, 200-300K that is probably as close as
you can get.
The computational effort for the IGLO method is somewhat higher than for the
GIAO calculation (at HF-level) though the information you get from IGLO is 
more extensive. Because IGLO works with localized molecular orbitals (LMOs) 
you get an anlysis of the contribution of the LMOs to the chemical shift 
while you only get the shielding constant out of the GIAO calculation.

IGLO is available at HF level and there is a DFT version using the IGLO
code to calculate chemical shifts. The GIAO method in MO theory is available
up to CC level though the computational effort is extremely high so the
calculation of the shielding constant at such a highly coorelated level is
only possible for small molecules. The GAUSSIAN94 manual states that the GIAO 
module of the program can cope with DFT but I have no experience with that.

> 2. Do you know the program or references which one can calculate not only
> chemical shift but also 
> the coupling constant 
> ( for example, 1H-1H and 13C-13C) and NOE in quantum chemistry other than
> G94? As to 1H-1H coupling constant, 

As far as I know (and I really may not be up to date) the only programs
capable of calculating coupling constants is DeMon with DFT-IGLO and ACESII
(at MP2 level). 

Some useful references are:
- IGLO: Kutzelnigg, W.; Fleischer, U.; Schindler, M.:"The IGLO-Method: Ab-
initio Calculation and Interpretation of NMR chemical Shifts and magnetic
Susceptibilities", NMR Basic Princ. Prog., Vol. 23, Springer-Verlag, Berlin
Heidelberg, 1990, 165
- DFT-IGLO: Malkin, M. G.; Malkina, O. L.; Casida, M. E.; Salahub, D. R.,
JACS, 116(1994), 5898
- HF-GIAO: Wolinski, K.; Hilton, J. F.; Pulay, P., JACS, 112(1990), 8251
- MP2-GIAO: Gauss, J., Chem. Phys. Lett., 191(1992), 614

Hope, this was of some help
                        Thomas Wagener

- "You are wrong! 2+2=5.8354! Please adjust your equipment accordingly."
                        The Computer (your friend)

*****************************************************************************
* Thomas Wagener                   *  Tel: ++49-(0)6421-285561              *
* FB Chemie                        *                                        *
* Phillips-Universitaet Marburg    *  Email: [email-masked] *
*                                  *                                        *
* 35032 Marburg                    *                                        *
* Germany                          *                                        *
*****************************************************************************

---end --

####################################################

  Seiji Mori
  Graduate student in Nakamura Laboratory
  Department of Chemistry
  The University of Tokyo
  Hongo 7-3-1, Bunkyou-ku, Tokyo 113, JAPAN.
  email:[email-masked]
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