Subject: SUMMARY OF NMR SHIFTS, MP2 cf. HF

From: "E. Lewars" <[email-masked]>
Date: Tue, 27 Jul 1999 23:00:14 -0400 (EDT)

1999 July 26

   REPLIES TO QUESTION ABOUT MP2- cf. HF-LEVEL NMR CHEMICAL SHIFTS

THE QUESTION:

> Hello,  I read somewhere that NMR chemical shifts calc at the MP2 level are
> somewhat better than at the HF level. Has anyone a reference to this?
> Thanks.

 Thanks very much to all who responded. As you see, I got a lot of information.

For people who wish to look at just a few of the refs, I might suggest:
J. Gauss. JCP 99 3629 (1993)
Cheesman et al JCP 104 5497 (1996)
(I haven't yet got hold of the J. Gauss paper in Ber. Bunsenges. Phys. Chem.)
The Chem Rev 1999 review is physical-theoretical rather than a presentation
and analysis of calculated chemical shifts.

I did a few calcs on B3LYP/6-31G* geometries, using the G94 default
algorithm and the HF/6-31G* and HF/6-311+G(2d,p) wavefunctions. There was
not that much difference between the two basis sets, although the latter took
a lot longer. I was astonished at how accurate the chemical shifts were.

-------------
THE ANSWERS:

1999 July               MP2 cf. HF NMR SHIFTS

#1
Matthias Hofmann

> Hello,  I read somewhere that NMR chemical shifts calc at the MP2 level are
> somewhat better than at the HF level. Has anyone a reference to this?
> Thanks.

One early example is: 
Decisive Electron Correlation Effects on Computed 11B und 13C NMR Chemical 
Shifts. Application of the GIAO-MP2 Method to Boranes and Carbaboranes. 
M. Bue\237hl, J. Gauss, M. Hofmann, P. v. R. Schleyer, J. Am. Chem. Soc., 1993, 
115, 12385-12390.   

For other nuclei you might search for early papers by J. Gauss, who first
implemented the GIAO-MP2 methods (and higher correlated methods) in ACES2. 

Regards, 
Matthias
   --------------------------------------------------------------------
    Dr. Matthias Hofmann         | phone:  706 542-7748
    Ctr. for Comp. Quantum Chem. | fax:    706 542-0406
    University of Georgia        | e-mail: [email-masked]
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============-----------------------------------------------------------

#2
Michael D. Bartber                                                                                                                       Jul 21 '99 at 10:42 pm

Hello:

You might check the references of J. Gauss; he, along with John
Stanton have published a number of papers (I include references below) on
the computation of checmical shifts with MBPT.   Also R.J. Bartlett and
coworkers have investigated shifts and coupling constants at the
CC level.    A lot of this is nicely summarized in a recent Chem. Rev.
article by Helgaker et al.,  1999, v. 99, 293-352.

Other possibly useful references follow.

Best regards,
-Mike Bartberger
UCLA

+-----------------------------------------------------------------+
| Michael D. Bartberger, Ph.D.                                    |
| NIH Postdoctoral Fellow                      TEL:  310.206.0553 |
| Department of Chemistry and Biochemistry     FAX:  310.206.1843 |
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    Kollwitz, M; Haser, M; Gauss, J.
      Non-Abelian point group symmetry in direct second-order many-body
    perturbation theory calculations of NMR chemical shifts.
      JOURNAL OF CHEMICAL PHYSICS, 1998 MAY 22, V108 N20:8295-8301.

    Gauss, J; Stanton, JF.
      Electron correlation effects on the calculated C-13 NMR spectra of vinyl
    cations.
      THEOCHEM-JOURNAL OF MOLECULAR STRUCTURE, 1997 JUN 30, V398:73-80.

    STANTON JF; GAUSS J; SIEHL HU.
      CCSD(T) CALCULATION OF NMR CHEMICAL SHIFTS - CONSISTENCY OF CALCULATED
    AND MEASURED C-13 CHEMICAL SHIFTS IN THE
    1-CYCLOPROPYLCYCLOPROPYLIDENEMETHYL CATION.
      CHEMICAL PHYSICS LETTERS, 1996 NOV 15, V262 N3-4:183-186.

    KOLLWITZ M; GAUSS J.
      A DIRECT IMPLEMENTATION OF THE GIAO-MBPT(2) METHOD FOR CALCULATING NMR
    CHEMICAL SHIFTS - APPLICATION TO THE NAPHTHALENIUM AND ANTHRACENIUM IONS.
      CHEMICAL PHYSICS LETTERS, 1996 OCT 4, V260 N5-6:639-646.

    GAUSS J.
      ACCURATE CALCULATION OF NMR CHEMICAL SHIFTS.
      BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS,
    1995 AUG, V99 N8:1001-1008.

    BUHL M; GAUSS J; STANTON JF.
      ACCURATE COMPUTATIONS OF SE-77 NMR CHEMICAL SHIFTS WITH THE GIAO-CCSD
    METHOD.
      CHEMICAL PHYSICS LETTERS, 1995 JUL 21, V241 N3:248-252.

    SIEHL HU; MULLER T; GAUSS J; BUZEK P; and others.
      CYCLOPROPYLCYCLOPROPYLIDENEMETHYL CATION - A UNIQUE STABILIZED VINYL
    CATION CHARACTERIZED BY NMR SPECTROSCOPY AND QUANTUM CHEMICAL AB INITIO
    CALCULATIONS.
      JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994 JUL 13, V116
    N14:6384-6387.

    BUHL M; GAUSS J; HOFMANN M; SCHLEYER PV.
      DECISIVE ELECTRON CORRELATION EFFECTS ON COMPUTED B-11 AND C-13 NMR
    CHEMICAL SHIFTS - APPLICATION OF THE GIAO-MP2 METHOD TO BORANES AND
    CARBABORANES.
      JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993 DEC 29, V115
    N26:12385-12390.

    SCHLEYER PV; GAUSS J; BUHL M; GREATREX R; and others.
      EVEN MORE RELIABLE NMR CHEMICAL SHIFT COMPUTATIONS BY THE GIAO-MP2
    METHOD.
      JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1993 DEC 7,
    N23:1766-1768.

    SIEBER S; SCHLEYER PV; GAUSS J.
      THE ACCURATE C(2V) PHENONIUM AND BENZENONIUM ION STRUCTURES CONFIRMED BY
    CORRELATED GIAO-MP2 NMR CHEMICAL SHIFT CALCULATIONS.
      JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993 JUL 28, V115
    N15:6987-6988.
      Pub type:  Note.

    GAUSS J; SCHNEIDER U; AHLRICHS R; DOHMEIER C; and others.
    AL-27 NMR SPECTROSCOPIC INVESTIGATION OF ALUMINUM(I) COMPOUNDS - ABINITIO
    CALCULATIONS AND EXPERIMENT.
      JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993 MAR 24, V115 N6:2402-2408.

    GAUSS J.
      CALCULATION OF NMR CHEMICAL SHIFTS AT 2ND-ORDER MANY-BODY PERTURBATION
    THEORY USING GAUGE-INCLUDING ATOMIC ORBITALS.
      CHEMICAL PHYSICS LETTERS, 1992 APR 17, V191 N6:614-620.

    PERERA SA; BARTLETT RJ.
      STRUCTURE AND NMR SPECTRA OF THE 2-NORBORNYL CARBOCATION - PREDICTION OF
    (1)J((CC)-C-13-C-13) FOR THE BRIDGED, PENTACOORDINATE CARBON ATOM.
      JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996 AUG 21, V118
    N33:7849-7850.

    PERERA SA; BARTLETT RJ; SCHLEYER PV.
      PREDICTED NMR COUPLING CONSTANTS AND SPECTRA FOR ETHYL CARBOCATION - A
    FINGERPRINT FOR NONCLASSICAL HYDROGEN-BRIDGED STRUCTURES.
      JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995 AUG 16, V117
    N32:8476-8477.
      Pub type:  Note.
===============

#3
                          MP2 NMR chemical shifts
 [email-masked]
                                                         Jul 22 '99 at 9:32 am

Hi
although they were more concerned with MCSCF, the group of Kutzelnigg has
investigated the effect of correlation on the chemical shifts. So you can look
at its bibliography.
As far as I remember, the effects were not amazing.
Of course when the ground state and the first excited ones are very near in
energy, correlation may play a role and paramagnetic contributions become more
difficult to compute.
Good luck
Guglielmo Monaco
Dip. di Chimica
Universit\340 di Napoli
ITALY
=============

#4
[email-masked]

Hi,

while I can't find the original references in the moment, I would suggest
to start with some reviews on ab initio NMR calculations:
J. Gauss, Ber. Bunsenges. Phys. Chem. 1995, 99, 1001
T. Helgaker et al., Chem.Rev.1999, 99, 293
Both should have something on your question or, at least, give you further
references. Besides, some limited SCF-MP2 comparison is also in B=FChl et al=
.
J. Phys. Chem. 1995, 99, 4000.

Best regards, Georg

P.S. Please summarize to the CCL.

--------------------
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Theoretical Chemistry T-12        FAX:     (USA)-505-665 3909
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===================

#5
Doug Fox                                                                                                                             Jul 22 '99 at 12:47 (noon)

  Errol,

   Check J. Gauss, JCP vol 99 3629 (1993).  We draw from this and compare
it with DFT methods in Cheesman et.al. JCP vol 104, 5497 (1996).

   Schleyer has also made comparisons in some of his Boron work but I don't
have a good reference.

  Douglas J. Fox
  Director of Technical Support
  [email-masked]
==========================