Nuclear Magneti c Shielding s

and Molecular Structur e

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Series C: Mathematical and Physical Sciences - Vol. 386

Nuclear Magneti c Shielding s and Molecula r Structur e

edited by

J. A. Tossel l Department of Chemistry an d Biochemistry , University of Maryland, College Park , Maryland, U.S.A.

w Springer Science+Business Media, B.V.

Proceedings of the NATO Advanced Research Workshop on The Calculation of NMR Shielding Constants and Their Use in the Determination of the Geometric and Electronic Structures of Molecule s and Solids College Park , Maryland, U.S.A. July 20-24, 199 2

ISBN 978-94-010-4722-7DOI 10.1007/978-94-011-1652- 7

Printed on acid-free paper

All Rights Reserve d © 199 3 Springer Science+Business Medi a Dordrech t Originally publishe d b y Kluwer Academic Publisher s i n 1993 No par t o f th e materia l protecte d b y thi s copyrigh t notic e ma y b e reproduce d o r utilized i n an y for m o r b y an y means , electroni c o r mechanical , includin g photo -copying, recordin g o r by any informatio n storag e an d retrieva l system , without writte n permission from the copyright owner .

ISBN 978-94-011-1652-7 (eBook)

TABLE OF CONTENTS

INTRODUCTION

LIST OF PARTICIPANTS

INVTIED LECIURES

iv

vii

An Overview of Nuclear Shielding Calculations 1 G.A. Webb*

Experimental and Theoretical Studies of the Chemical Shift Tensors of Pnictides 27 and Fluorophosphates

T. C. Farrar* and J. D. Trudeau

Solid State NMR Chemical Shifts of Chalcogeoides and Phosphides 49 H. Eckert*, K. Moran, D. Franke and C. Hudalla

Intra- and Intennolecular Electrical Effects on Nuclear Magnetic Resonance, Nuclear 75 Quadrupole Resonance and Infra-Red Spectroscopic Parameters from Ab Initio Calculation and Experiment From CO to Proteins

J. D. Augspurger, C. E. Dykstra*, E. OIdfield* and J. G. Pearson

The Nuclear Shielding Surface: The Shielding as a Function of Molecular Geometry 95 and Intennolecular Separation

C.J. Jameson* and A. C. de Dios

Ab-lnitio Calculation and Analysis of Nuclear Magnetic Shielding Tensors: 117 the LORG and SOLO Approaches

A. E. Hansen* and T. D. Bouman

The IGLO Method. Recent Developments 141 W. Kutzelnigg*, Ch. v. Wiillen, U. Fleischer, R. Franke and T. v.

Mourik

Electronic Current Density Induced by Magnetic Fields and Magnetic Moments 163 in Molecules

P. Lazzeretti*, M. Malagoli and R. Zanasi

Shielding Tensor Data and Structure: The Bond-Related Chemical Shift Concept 191 A.-R. Grimmer*

Investigation of Structural Phase Transitions in Oxide Materials Using 203 High-Resolution NMR Spectroscopy

B. L. Phillips, R. J. Kirkpatrick*, Y. Xiao and J. G. Thompson

A Model Study of Chemical Shielding in a Partially Hydrated Dipeptide 221 D. B. Chesnut* and C. G. Phung

Efficient Implementation of the GIAO Method for Magnetic Properties: 243 Theory and Application

P. Pulay*, J. F. Hinton* and K. Wolinski

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Electronic Mechanisms of Metal Chemical Shifts from Ab Initio Theory 263 H. Nakatsuji*

Applications of NMR Shielding Constant Calculations 279 in Mineralogy and Geochemistry

J.A. Tossell*

Applications of Dipolar NMR Spectroscopy in Characterizing Nitrogen and 297 Phosphorus Shielding Tensors

R. E. Wasylishen*, R. D. Curtis, K. Eichele, M. D. Lumsden, G. H. Penner, W. P. Power and G. Wu

Comparisons of Shielding Anisotropies for Different Nuclei and Other Insights 315 into Shielding from an Experimentalist's Viewpoint

K.W. Zilm* and J. C. Duchamp

An Origin-independent Theory for Calculation of NMR Shielding Constants 335 J. Geertsen*

Correlated and Gauge Invariant Calculations of Nuclear Shielding Constants 351 S. P. A. Sauer and J. Oddershede*

Carbon-13 Chemical Shielding Tensors in Sugars: Sucrose and Methyl-a-D- 367 glucopyranoside

D. M.Grant*, J. C. Facelli, D. W. Alderman and M. H. Sherwood

IGLO Calculations of 29Si NMR Chemical Shift Anisotropies in Silicate Models 385 R. Wolff*, C. Vogel and R. Radeglia

Effects of Isotopic Substitution and Temperature on Nuclear Magnetic Shielding 401 W.T. Raynes*

The Role of NMR Shifts in Structural Studies of Glasses, Ceramics and Minerals 421 R. Dupree*, S. C. Kohn, C. M. B. Henderson and A. M. T. Bell

The Influence of Structure and Geometrv on the 31p, 29Si, 13C and IH Chemical Shifts 435

U. Sternberg-

Nitrogen shielding tensors 449 J. Mason*

1 H and 13C Solid-State NMR Studies of Catalytic Reactions on Molecular Sieves 473 M. W. Anderson and J. Klinowski-

Theoretical Study of Chemical Shielding in Silatrane and its Derivatives 495 J. H. Iwamiya and G. E. Maciel-

Ab Initio IGLO Studies of the Confonnational Dependence of the "tEffect 523 in the 13C NMR Spectra of Cyclic Hydrocarbons

M. Barfield*

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Gas Phase Measurement and Ab Initio Calculations 539 of 77 Se and 113Cd Chemical Shifts

P. D. Ellis·, J. D. Odom, A. S. Lipton, Q. Chen and J. M. Gulick

Overview and Directions for the Future 557 C. J. Jameson·

ABSTRACTS OF POSTER PRESENTA nONS 561-577

The Structure of BgHg-2 in Solution. Is BgH9- also Involved? M. Buhl, A. M. Mebel, O. P. Charfin and P. v. R. SchlSchleyer

A General Shape for Intra- and Intennolecular Shielding Functions A. C. de Dios and C. J. Jameson

Experimental Characterization of 31 P Chemical Shift Tensors in Phosphine Derivatives K. Eichele and R. E. Wasylishen

IGLO Calculations of Phosphorus NMR Chemical Shifts U. Fleischer and W. Kutzelnigg

13C Orbital Shift Calculation in Graphite Intercalation Compounds C. Fretigny, M. Saint Jean and M. F. Quinton

Evaluation of Chemical Shifts in Solid State NMR by Electronegativity Equalization Principle

C. Gerardin, M. Henry and F. Taulelle 129xe Shielding as a Probe of Zeolite Structure and Dynamics

A. K. Jameson, C. J. Jameson and A.C. de Dios NMR Shielding and Atoms in Molecules

T.A. Keith Experimental and Calculated Nitrogen Shielding Tensors in the Nitroso Group

M. D. Lumsden, G. Wu, R. D. Curtis and R. E. Wasylishen Calculations of NMR Shielding Constants using a Combination of Pseudo-potential

and IGLO Methods V. G. Malkin, U. Fleischer and W. Kutzelnigg

Quantum-chemical Calculations of Chemical Shifts of Adsorbed Molecules V. G. Malkin, U. Fleischei', J. Sauer and W. Kutzelnigg

A New Analysis of Proton Chemical Shifts in Proteins K. Osapay and D. A. Case

Electron Surroundings of Cs+ in the Graphite Intercalation Compound CS=1(THF)",,1.5C24. as Observed by 133Cs NMR

M.-F. Quinton, F. Beguin and A. P. Legrand On the Calculations of Deuterium Long Range Isotope Effects on Carbon-13 Chemical

Shifts D. Vikic-Topic, M. Hodoscek, A. Graovac, E. D. Becker, G. Lodder

and H. Zuilhof GIAO Calculations of the NMR Chemical Shift for Large Molecules

K. Wolinski, J. F. Hinton and P. Pulay Is There a Viable Alternative to the Coulomb Gauge for GIAO Calculations of Magnetic

Properties? K. Wolinski, J. F. Hinton and P. Pulay

INDEX 579

INTRODUCTION

In recent years a number of first principles or ab initio quantum mechanical

methods have been developed which allow the accurate calculation of NMR shielding

constant tensors for large molecules and for molecular models of solids. In addition to

more efficient implementations of the conventional common-origin coupled Hartree-Fock perturbation theory and finite perturbation theory methods which were applied to small

molecules in the 1960's, new methods have been developed based upon localized

molecular orbitals and methods employing so-called gauge-including atomic orbitals

have been improved. It has also become feasible to go beyound the Hartree-Fock level,

including the effects of electron correlation using many body perturbation theory,

polarization propagator techniques or multi-configuration SCF approachs. Greater

understanding of the basis set dependence of the calculated shieldings has also improved

their accuracy and reliability and has allowed their extension both to larger molecules

and to many different types of magnetic nuclei, including transition metals and heavy

main-group elements. As a result of these improvements in methodology, coupled with

dramatic increases in the speed and storage capacity of routinely available computers, it

has now become possible for many groups, using many different methods, to accurately

calculate NMR shielding constant tensors for fairly complicated molecules.

The status of the various methods was reviewed at this workshop, and it was

agreed that the results obtained with the various localized orbital and gauge including

orbital methods were quite similar. The gauge-including atomic orbital method seems to

have slightly superior accuracy if very small basis sets are used, but all the localized and

gauge-including methods seem to converge to the same result using larger bases.

Common-origin methods with core electron corrections can also give reasonably good

absolute shieldings, but are perhaps best used for small molecules (for which very large

basis sets can be employed and core corrections are small) or, when applied to large

molecules, for analysis of shielding trends (rather than absolute shieldings) and in the

elucidation of the electronic mechanisms of the shielding and the relationship between

the shielding and other electronic properties. Studies of correlation effects using the

various methods show many cases in which such effects seem fairly small, but also some

(e.g. compounds with both multiple bonds and lone pairs and compounds poorly

described by a single determinant wavefunction) in which they seem quite large. There is

not yet sufficient experience with such correlation effects to make possible a simple, reliable estimation of their magnitudes in all cases.

ix

x

Substantial advances have also recently occurred in experimental NMR

spectroscopy, with improved methhods for detennining the orientations of NMR

shielding tensors in liquids and solids, with the use of many-dimensional NMR

techniques to uniquesly assign resonances to structural sites and with studies of changes

in the shielding tensor with changes of temperaute, phase or crystal structure. Some new

NMR techniques uniquely relevant to the determination of the relationship between the

shielding tensor and the geometric structure were reviewed in the workshop. Changes in

shielding constants with changes in local geometry were also reviewed for minerals,

glasses, semiconductors and for the compounds of many main group and transition

elements. In many cases, predominantly experimental talks also incorporated first

principles calculations to help in the assignment of shieldings to sites and in the

determination of shielding tensor orientations. These calculations provided rigorous tests

for the efficiency and accuracy of these methods when applied to large molecules.

In addition to the discussions of ftrst principles calculations, there were several

presentations stressing the utility of qualitative molecular orbital or semiempirical

analyses of shielding trends. Some connections were made between these approachs and

those based on frrst principles calculations, and the validity of some of the semiempirical

approachs was discussed. The importance of validating the assumptions of the

semiempirical approachs by appeal to fust principles calculation or other electronic

structural data was stressed, but it was concluded that such approachs still had great

value for systematizing shielding constant data, interpolating high precision values of

shielding constants from strucural data and identifying correlations for futher study by

frrst principles methods.

Overall, the conclusion of the workshop was that present and emerging methods,

along with expected computational advances, would make possible calculations at post­

Hartree-Fock accuracy on quite large molecules in the near future. It was not so clear

exactly how these capabilites could best be used to update and improve the present non­

specialist's understanding of NMR shielding constants or to deepen our overall

understanding of molecular electronic strcture. These remain important general topics for

future discussion.

The Organizing Committe for the workshop consisted of:T. D. Bouman (Southern

Illinois Univ. at Edwardsville, USA, deceased); P. Lazzeretti (Univ. of Modena, Italy); G.

E. Maciel (Cororado State Univ., USA); J. A. Tossell (Univ. of Maryland, USA); and G.

A. Webb (Univ. of Surrey, UK). Generous ftnancial support was provided by the NATO

Scientiftc Affairs Division. Additional support was provided by Biosym Technologies,

Chemagnetics, Cray Research, Inc., Hytec Electronics, Ltd. and by the Dept. of

Chemistry and Biochemistry of the University of Maryland at College Park.

xi

To give more of the flavor of the workshop the papers are presented in the order given,

with the names of the lecturers marked with an asterix. Informal discussions were also

held on the topics: (1) "How does the compound in the computer relate to that in the

NMR spectrometer?", (2) "Do other electronic properties correlate with NMR

shieldings?", and (3) "How do correlation and relativity affect NMR shieldings?". A

review of the methods used for shielding constant calculations and an evaluation of their

accuracy is given by G. A. Webb in the fIrst chapter, entitled "An Overview of Nuclear

Shielding Calculations" and a brief summary of the meeting lectures and discussions,

along with some suggestions for future research, is given by C. J. Jameson in the fInal

chapter, entitled "Overview and Directions for the Future". Also included are one-page

abstracts of most of the posters presented at the workshop.

J. A. Tossell College Park, MD, USA October, 1992

LIST OF PARTICIPANTS

Michael Barfield Dept. of Chemistry University of Arizona Tucson, AZ 85721

AdBax Laboratory of Chemical Physics NIDDK, National Institutes of health Bethesda, MD 20892

Michael Buhl Center for Computational Quantum Chemistry University of Georgia Athens, GA 30602

David Case Dept. of Molecular Biology The Scripps Research Institute 10666 Torrey Pines Rd. La Jolla, CA 92037

Donald Chesnut Dept. of Chemistry Duke University Durham, NC 27706

Angel deDios Dept. of Chemistry University of Illinois at Chicago P.O. Box 4348 Chicago, IL 60680

Joseph Delhalle Dept. of Chemistry Facultes Univeresitaires Notre-Dame de la Paix Rue de Bruxelles, 61 B-5000 Namur Belgium

Ross Dickson Dept. of Chemistry Queens University Kingston, Ontario K7L 3N6 Canada

James Duchamp Dept. of Chemical Engineering Cornell University 120 Olin Hall Ithaca, NY

xiii

Ray Dupree Dept. of Physics University of Warwick Coventry CV 4 7 AL UK

Clifford E. Dykstra Dept. of Chemistry Indiana university-Purdue University at Indianapolis 1125 E. 38th St. Indianapolis, IN 46205

Hellmut Eckert Dept. of Chemistry University of California Santa Barbara, CA 93106

Klaus Eichele Dept. of Chemistry Dalhousie University Halifax, Nova Scotia B3H 4J3 Canada

Paul Ellis Dept. of Chemistry University of south Carolina Columbia, SC 29036

Julio Facelli Dept. of Chemistry University of Utah 1320HEB Salt Lake City, UT 84112

Thomas Farrar Dept. of Chemistry University of Wisconsin 1101 University Avenue Madison, WI 53706

Ulrich Fleischer Lehrstuhl fur Theoretische Chemie Ruhr-Universitat Bochum 4630 Bochum Germany

Eugene Fleishcmann Cray Research, Inc. 4041 Powder Mill Rd. Calverton, MD

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Jan Geertsen Dept. of Chemistry Odense University Campusvej 55 Odense N 5230 Denmark

Corine Gerardin Dept. of Geological and Geophysical Sciences Princeton University Guyot Hall Princeton, NJ 08566

David Grant Dept. of Chemistry University of Utah 1320HEB Salt Lake City, UT 84112

Arnd-Rudiger Grimmer Projektgruppe Festkorper-NMR KAI e.v. Berlin Rudower Chaussee 5 D-0-1199 Berlin Germany

AageHansen Dept. of Chemistry H.C. Orsted Institute University of Copenhagen Copenhagen DK-2100 CPH 0 Denmark

Marc Henry Dept.Chimie de la Matiere Condensee Universite P. et M. Curie 4 Place J ussieu 75252 Paris Cedex 05 France

Judith Herzfeld Dept. of Chemistry Brandeis University 415 South St. Waltham, MA 02254-9110

James Hinton Dept. of Chemistry University of Arkansas Fayetteville, AK 72701

Milan Hoodscek MGSL DCRT/NIH Bethesda, MD 20892

A. Keith Jameson Dept. of Chemistry Loyola University Chicago 6525 N. Sheridan St. Chicago, IL 60626

Cynthia Jameson Dept. of Chemistry University of lllinois at Chicago P.O. Box 4348 Chicago, IL 60680

Todd Keith Dept. of Chemistry McMaster University 1280 Main St. West Hamilton, Ontario L8S 4Ml Canada

R. James Kirkpatrick Dept. of Geology University of lllinois 1301 W. Green St. Urbana, IL 61801

Jacek Klinowski Dept. of Chemistry University of Cambridge Lensfield Rd. Cambridge CB2 lEW UK

Werner Kutzelnigg Dept. of Chemistry Ruhr-Universit Bochum 4630 Bochum-Querenburg Germany

Yiu-Fai Lam Dept. of Chemistry University of Mayrland College Park, MD 20742

Paolo Lazzeretti Dept. of Chemistry University of Modena Via Campi 183 41100 Modena Italy

Hongbiao Le Dept. of Chemistry University of lllinois 505 S. Mathews Ave. Urbana, IL 61801

Michael Lumsden Dept. of Chemistry Dalhousie University Halifax, Nova Scotia B3H 413 Canada

Gary Maciel Dept. of Chemistry Colorado State Univ. Ft. Collins, CO 80523

Vladimir Malkin Dept. of Chemistry U niversite de Montreal c.P. 6128, Succ. A Montreal, Quebec H3C 317 Canada

Joan Mason Dept. of Chemistry The Open University Milton Keynes MK7 6AA UK

Hiroshi Nakatsuji Dept. of Synthetic Chemistry Faculty of Engineering Kyoto University Kyoto 606 Japan

Jens Oddershede Dept. of Chemistry Odense University Campusvej 55 Odense DK-5230 Denmark

Eric Oldfield Dept. of Chemistry Univ of lllinois 505 S. Matthews Urbana, IL 61801

Victor Parziale Technical Sales Dept. Chemagnetics 2555 Midpoint Dr. Fort Collins, CO 80525

John Pearson Dept. of Chemistry University of lllinois 505 S. Matthews Urbana, IL 61801

William Power Dept. of Chemistry Yale University 225 Prospect S t. New Havem , CT 06511

Peter Pulay Dept. of Chemistry and Biochemistry University of Arkansas Fayetteville, AK 72701

Marie-Francoise Quinton ESPCI, Lab. de Physique Quantique 10 rue Vauquelin 75231 Paris Cedex 05 France

William Raynes Dept. of Chemistry Univ. of Sheffield Sheffield S37HF UK

Gotthard Saghi-Szabo Dept. of Chemisty and Biochemistry Univ.ofMayland College Park, MD 20742

Paul v.R. Schleyer Institut fur Organische Chemie Friedrich-Alexander-U niversitat Erlangen-Nurnberg Henkestr. 42 D-8520 Erlangen Gennany

Ulrich Sternberg Physikalisch-Astronomische Fakultat Friedrich-Schiller-Universitat Jena Max-Wien-Platz 1 0-6900 Jena Gennany

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Walter Stevens Center for Advanced Research in Biotechnology Maryland Biotechnology Institute 9600 Gudelsky Dr. Rockville, MD 20850

Francis Taulelle Dept.Chimie de la Matiere Condensee Universite P. et M. Curie 4 Place J ussieu 75252 Paris Cedex 05 France

Jack Tossell Dept. of Chemistry and Biochemistry Univ. of Maryland College Park, MD 20742

John Trudeau Dept. of Chemistry University of Wisconsin 1101 University Ave. Madison, WI 53706

Drazen Vikic-Topic LCP NIDDK/NIH Bethesda, MD 20892

Roderick Wasylsihen Dept. of Chemistry Dalhousie University Halifax, Nova Scotia B3H 4J3 Canada

Graham Webb Dept. of Chemistry University of Surrey Guildford, Surrey GU2 S4H UK

Dennis Winkler Dept. of Chemistry and Biochemistry Univ.ofMaryland College Park, MD 20742

Renate Wolff Analytisches Zentrum Rudower Chaussee 5 D-1199 Berlin Germany

Krysztof Wolinski Dept. of Chemistry University of Arkansas Fayetteville, AK 72701

Ping Yip Science Dept. Biosym Technologies 9685 Scranton Rd. San Diego, CA 92121

Riccardo Zanasi Dept. of Chemistry University of Modena Via Campi 183 41100 Modena Italy

KurtZilm Dept. of Chemistry Yale University 225 Prospect St. New Haven, CT 06511