Table Of ContentACS SYMPOSIUM SERIES 732
Modeling NMR Chemical Shifts
Gaining Insights into Structure
and Environment
Julio C. Facelli, EDITOR
University of Utah
Angel C. de Dios, EDITOR
Georgetown University
American Chemical Society, Washington, DC
Library of Congress Cataloging-in-Publication Data
Modeling NMR chemical shifts : gaining insights into structure and environment / Julio C. Facelli,
Angel C. de Dios, editors.
p. cm.—(ACS symposium series ; 732)
Developed from the Second International Symposium on NMR Chemical Shifts held at the
216th National Meeting of the American Chemical Society, Boston, Mass., Aug. 23-26, 1998.
Includes bibliographical references and index.
ISBN 0-8412-3622-4
1. Nuclear magnetic resonance spectroscopy—Congresses. 2. Molecular Structure—
Congresses.
I. Facelli, Julio C. II. Dios, Angel C. de. III. American Chemical Society. Meeting (216th :
1998 : Boston, Mass.). IV. International Symposium on NMR Chemical Shifts (2nd : 1998 :
Boston, Mass.) V. Series.
QD96.N8M59 1999
543'.0877—dc21 99-24229
CIP
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Table of Contents
Preface
Julio C. Facelli and Angel C. De Dios ix-x
1 Recent Advances in Nuclear Magnetic Shielding Theory and Computational Methods
Cynthia J. Jameson 1-23
2 Modeling NMR Chemical Shifts in Polymers and Amorphous Matter
Isao Ando, Shigeki Kuroki, Hiromichi Kurosu, Masahito Uchida, and Takeshi Yamanobe
24-39
3 NMR and Quantum Chemistry of Proteins and Model Systems
Christina M. Szabo, Lori K. Sanders, William Arnold, Joshua S. Grimley, Nathalie Godbout,
Michael T. McMahon, Benjamin Moreno, and Eric Oldfield 40-62
4 NMR in Catalysis: Theoretical and Experimental Approaches
John B. Nicholas and James F. Haw 63-78
5 Effects of a Static Electric Field on Molecular Magnetic Properties Employing the
CTOCD Method: Shielding Polarizabilities of CO, HO, and CH Compounds
2 4
M. B. Ferraro, M. C. Caputo, and C. Ridruejo 79-92
6 Extremely Fast Calculation of 1 3C Chemical Shift Tensors Using the Bond Polarization
Theory
Ulrich Sternberg and Wolfram Prieß 93-100
7 Covering the Entire Periodic Table: Relativistic Density Functional Calculations of NMR
Chemical Shifts in Diamagnetic Actinide Compounds
Georg Schreckenbach, Stephen K. Wolff, and Tom Ziegler 101-114
8 The Effect of Electron Correlation on the 19F Chemical Shifts in Fluorobenzenes
Peter B. Karadakov, Graham A. Webb, and James A. England 115-125
9 17O NMR Chemical Shifts in Peptides
S. Kuroki, K. Yamauchi, Hiromichi Kurosu, S. Ando, Isao Ando, A. Shoji, and T. Ozaki
126-137
10 A Conformational Study of the L-Alanine Residue in Polypeptides by Ab Initio 13C NMR
Shielding Calculation
Hiromichi Kurosu, Kouji Fukuyama, Shigeki Kuroki, and Isao Ando 138-147
11 13C Chemical Shift-Conformation Relationship in the Chromophores of Rhodopsin and
Bacteriorhodopsin
Minoru Sakurai, Mitsuhito Wada, Hirohiko Houjou, Naoki Asakawa, and Yoshio Inoue
148-161
12 Modeling of the 1 5 N and 1 3 C Chemical Shift Tensors in Purine
Julio C. Facelli, Jian Zhi Hu, Mark S. Solum, Ronald J. Pugmire, and David M. Grant
162-176
13 Effects of Hydrogen Bonding on 1 H Chemical Shifts
Yufeng Wei and Ann E. McDermott 177-193
14 An Empirical Analysis of Proton Chemical Shifts in Nucleic Acids
Annick Dejaegere, Richard A. Bryce, and David A. Case 194-206
15 A New Proton NMR Shielding Model for Alkenes
Ned H. Martin, Noah W. Allen, III, Everett K. Minga, Sal T. Ingrassia, and Justin D. Brown
207-219
16 The NMR Chemical Shift: Local Geometry Effects
Angel C. de Dios, Jennifer L. Roach, and Ann E. Walling 220-239
17 Correlations between Transition-Metal NMR Chemical Shifts and Reactivities
M. Bühl 240-250
18 Calculated Chemical Shielding Tensors as an Aid to Elucidating the Method of
Attachment of Alkoxysilanes to Magnesium Chloride
E. A. Moore and N. J. Clayden 251-258
19 Aluminum Magnetic Shielding Tensors and Electric Field Gradients for Aluminum(I)
Hydride, Aluminum(I) Isocyanide, and the Aluminum(I) Halides: Ab Initio Calculations
Myrlene Gee and Roderick E. Wasylishen 259-276
20 Modeling 17O NMR Tensors — efg and Chemical Shifts — in Oxides and Polyoxometallates
Marc Henry 277-303
21 Local and Long-Range Effects on NMR Shieldings in Main-Group Metal Oxides and Nitrides
J. A. Tossell 304-319
22 Ab Initio Calculations of 31P NMR Chemical Shielding Anisotropy Tensors in
Phosphates: The Effect of Geometry on Shielding
Todd M. Alam 320-334
23 Application of Nuclear Shielding Surfaces to the Fundamental Understanding of
Adsorption and Diffusion in Microporous Solids
Cynthia J. Jameson, A. Keith Jameson, Angel C. de Dios, Rex E. Gerald, II, Hyung-Mi Lim,
and Pavel Kostikin 335-348
Author Index 350
Subject Index 351-373
Preface
In the past fifty years, the NMR Chemical Shielding have evolved from "correc
tions to the measurement of nuclear magnetic moments" as quoted from Ramsey's
1950 original papers (Phys. Rev. 77, 567 and 78, 699), to one of the most important
tools for structural elucidation in many branches of chemistry. There are no
simple relationships between molecular structure and chemical shifts. Their de
pendence on the molecular electronic and geometrical structure can be derived
via complex quantum mechanical equations.
Since the first Symposium on theoretical and physical aspects of the NMR
chemical shielding organized in 1992 by Professor Tossel, at a NATO workshop
entitled "Nuclear Magnetic Shielding and Molecular Structure", a number of
significant findings, new methodologies, and novel applications have been re
ported. In addition, the number of practitioners using NMR chemical shifts to
gain information on molecular structure and function has dramatically increased
given impetus to the idea of organizing a second meeting in 1998.
This volume was developed from the second international symposium on NMR
chemical shifts. This meeting was organized by the editors at the 216th National
Meeting of the American Chemical Society, Boston, Massachusetts, August 23-
26,1998, and was cosponsored by the ACS Divisions of Computers in Chemistry
and Physical Chemistry. The symposium included four extended lectures by
Jameson, Ando, Oldfield, and Nicholas, which are included in this volume as
Chapters 1-4, respectively. These lectures provide a convenient review of the
current state of the art in the calculation of the NMR chemical shielding (Jameson,
Chapter 1), and its application to different areas of chemistry: polymers (Ando),
biomolecules (Oldfield), and catalysis (Nicholas).
The rest of the papers included in the volume provide a "snap shot" of the
field at the time of the symposium. The papers by Ferraro, Sternberg, Schrecken-
bach, and Webb address new methodologies to calculate NMR chemical shifts.
The papers by Kuroki, Kurosu, Sakurai, and Facelli present novel calculations
of chemical shifts in molecular systems of biological interest. The contributions
by McDermott, Case, and Martin report important advances in the understanding
of Ή chemical shifts, and the contribution from de Dios emphasizes the impor
tance of the local geometry on the determination of the NMR chemical shifts.
The modeling of chemical shifts in inorganic compounds is discussed in detail in
the contributions from Buhl, Moore, Wasylishen, Henry, Tossell, Alam, and
Jameson (Chapter 23).
ix
Acknowledgments
We thank the contributing authors and the ACS editorial staff for their timely
contributions in making this volume a success. Financial support from the ACS
Computers in Chemistry Division in supporting the symposium is gratefully ap
preciated.
JULIO C. FACELLI
Center for High Performance Computing
University of Utah
405 INSCC
Salt Lake City, UT 84112
ANGEL C. DE DIOS
Department of Chemistry
Georgetown University
37th and Ο Streets, N.W.
Washington, DC 20057
χ
Chapter 1
Recent Advances in Nuclear Magnetic Shielding
Theory and Computational Methods
Cynthia J. Jameson
Department of Chemistry, University of Illinois at Chicago, Chicago, IL 60607
As the well-established methods employing multiple origins, GIAO,
IGLO, LORG, IGAIM, and common origin CHF methods are applied
to diverse molecular systems, using ever larger basis sets up to near
Hartree-Fock limit, the limitations of calculations at the SCF level in
accurately predicting the nuclear shielding becomes more evident. The
challenge of applying ab initio methods and density functional
methods to heavier nuclei or to nuclei having neighboring halogens
and other atoms with large spin orbit coupling constants demanded the
development of theoretical methods for improved description of
shielding in systems where electron correlation is important, and
systems where relativistic effects are important. At the same time, the
calculations on small molecules have become sufficiently accurate that
comparisons with experiment have to include accurate rovibrational
averaging. This overview of the recent successes, new challenges, and
new directions for the theory of nuclear magnetic shielding, provides
only a hint of the new and exciting results that are reported in this
Symposium.
The first conference devoted to the NMR chemical shift was held in Maryland, July
20-24, 1992, as a NATO Advanced Scientific Workshop on Nuclear Magnetic
Shielding and Molecular Structure (7). Experimentalists measuring fundamental
quantities such as the chemical shift tensor and its dependence on geometry and
intermolecular interactions and theoreticians involved in computations of the nuclear
magnetic shielding exchanged information on the state of the subject. At that time, the
following was already known:
1. The use of distributed origins (IGLO, LORG, GIAO) leads to dramatic
improvement in damping the errors arising from incomplete cancellation of long-
range contributions due to basis set inadequacies.
© 1999 American Chemical Society 1
Description:Content: Recent advances in nuclear magnetic shielding theory and computational methods / Cynthia J. Jameson -- Modeling NMR chemical shifts in polymers and amorphous matter / Isao Ando, Shigeki Kuroki, Hiromichi Kurosu, Masahito Uchida, and Takeshi Yamanobe -- NMR and quantum chemistry of proteins
