Prediction of NMR parameters in the solidstate

 Luke Wood
 5 months ago
 Views:
Transcription
1 1J PO Prediction of NMR parameters in the solidstate Jonathan Yates Materials Modelling Laboratory, Oxford Materials 2J PSi 1
2 Nuclear Magnetic Resonance Applied Field Zero Field B Population differences! NMR signal is proportional to population difference For 1H in a 9.4 T field at 298 K 1 For H in 9.4T at 298K ω= γ B magnetogyric ratio fundamental nuclear constant! "E = 2.65 # J nupper/nlower = exp ( "E / kt) nupper/nlower = Sensitivity is an issue! Need Large γ and/or B Populations differences in NMR are very small sensitivity is alway
3 Common Isotopes Isotope Spin ϒ 10 7 T 1 rad s 1 Freq 9.4T Abundance % 1 H 1/ C 1/ Si 1/ P 1/
4 Common Isotopes Isotope Spin ϒ Freq 10 7 T 1 rad s T Abundance % 1 H 1/ C 1/ Si 1/ P 1/ O 5/ Ti 7/
5 Superconducting magnets SolidState NMR Spectrometers 600 MHz 14.1 T ~ 800,000 Image courtesy Sharon Ashbrook (St Andrews) 400 MHz 9.4 T ~ 300,000
6 Magnetic Shielding Flurbiprofen nonsteriodal antiinflamatory δ iso = (ω ω ref) 10 6 ω ref chemical shift (ppm) δ iso = σ ref σ iso Each distinct C atom experiences a different magnetic field and resonates at a unique frequency. Measure the change wrt a standard (for 13 C this is liquid tetramethylsilane) magnetic shielding (from calc)
7 Induced Current To compute the chemical shifts we just need to calculate the current induced by the external magnetic field BiotSavart B in (r) = 1 c d 3 r j(r ) r r r r 3. Obtain current within perturbation theory (linear response) O = O (0) + O (1) + O(B 2 ) Bin = σ B0 note: σ is a rank 2 tensor
8 Planewaves and Pseudopotentials To simulate periodic systems planewaves are a convenient choice: however describing the tightly bound core states, and oscillatory part of the valence states close to the nucleus are prohibitively expensive. We must approximate... Frozen Core Approximation Core electrons taken from free atom fixed during calculation Pseudopotential Approximation Valence electrons experience weak effective potential in the core region Note: Typically these two approximations are used together. But this does not have to be the case. Some codes can employ ʻselfconsistentʼ pseudopotentials which allow the core states to ʻrelaxʼ to their specific environment.
9 Atomic States Si
10 Approximations Overcoming the previous approximations Frozen Core Approximation Contribution of core electrons to shielding is not chemically sensitive 1s states in Carbon contribute ~200ppm in diamond, benzene, proteins ie core states contribute to shielding  but not shift. Pseudopotential Approximation Use PAW method to fixup valence wavefunction in the core region
11 pseudo = T, Projector Augmented Waves = T allelectron T = 1 + R,n[ φ R,n φ R,n ] p R,n T φ R,n φ R,n  + pseudo = allelectron GIPAW GaugeIncluding Projector Augmented Waves Modification of PAW by Pickard and Mauri for systems in an external magnetic field  plays a role similar to GIAO in quantum chemistry techniques
12 GIPAW vs Gaussian test on small molecules n.b. v. big Gaussian basis sets JRY, C. Pickard, F. Mauri PRB 76, (2007) Convergence of shielding with #planewaves GIPAW A theory for solidstate NMR with GIPAW using uncorrected valence GIPAW  USP (ppm) GIPAW  USP (ppm) (a) All Electron Shielding (ppm) (b) All Electron Shielding (ppm) H C F Si P H C F Si P
13 Firstprinciples NMR Crystal Structure Xray, Neutron diffraction Cambridge Structural Database C C H Calculate forces refine structure 311.0ppm Calculate chemical shifts 316.9ppm
14 Examples Steven Brown (Warwick) Maltose sugar used in brewing 13 C axis 1 H axis MASJHMQC
15 Examples Maltose sugar used in brewing 13 C x xx x x x 1 H axis xx x x x MASJHMQC x x  first principles
16 Examples 13 C axis 1 H axis Molecule to solid variation due to intermolecular interactions (weak hydrogen bonds) x  first principles J. Am. Chem. Soc (2005)
17 NMR Interactions Chemical Shift orbital currents Quadrupolar coupling (EFG) nuclei I>1/2 interact with local electric field gradients Function of charge density spinspin coupling (eg Jcoupling) splitting of resonance due to nucleusnucleus interaction hard to observe in solids...
18 EFG Eigenvalues V αβ (r) = d 3 r Electric Field Gradients Function of the charge density  ie groundstate property. Also computed by allelectron codes such as Wien2k, Crystal charge density n(r) r r 3 V xx, V yy, V zz V zz > V yy > V xx [ δ αβ 3 (r α r α )(r β r β ) r r 2 ] Quadrupolar Coupling Asymmetry C Q = eqv zz h η Q = V xx V yy V zz Note: The quadrupolar moment, Q, is a nuclear property. Most recent values given in Year2008 Standard Values of Nuclear Quadrupole Moments : P. Pyykkö, Mol. Phys. 106, (2008) But note Q appears as a simple scaling factor 17 O MAS Glutamic Acid. HCl
19 Jcoupling Electronmediated interaction of nuclear spins Nucleus A causes a magnetic field at nucleus B (and vice versa) A B No Jcoupling with Jcoupling J In solids J is rarely revealed in splitting of peaks in 1D spectra (anisotropic interactions broaden peaks) parallel antiparallel Increasing use of techniques, eg those using spinecho modulation, to measure J in solids.
20 Jcoupling Orbital Dipole induces orbital motion of electrons (due to electron charge) This creates a localised magnetic field similar mechanism to NMR shielding Orbital Current Spin Dipole induces spin density (relative displacement of and electrons) This creates induced field via: FermiContact (ʻsʼ like density at nucleus) Spindipolar (nonspherical distribution of spin) similar mechanism to EPRhyperfine & Knightshift Induced Spin density: C2H2 Total J = Orbital + Spin H ve C C H +ve ve
21 Jcoupling Guanosine selfassembles into ribbons molecular electronics (FET) a 2h JN7a,N1b a 2h JN7b,N1a = 6.2±0.4 Hz (expt) 6.5 Hz (calc) 2h JN7a,N1b = 7.4±0.4 Hz (expt) 7.7 Hz (calc) J. Am. Chem. Soc. 130, (2008) b b 2h JN7b,N1a
22 Practical Details *.param file task : magres magres_task : shielding efg nmr chemical shift/shielding electric field gradient both Must use onthefly pseudopotentials Highly sensitive to geometry (optimise H Xray positions) CONVERGE (basis cutoff & kpoints)
23 *.castep file =========================================================== Chemical Shielding Tensor Nucleus Shielding tensor Species Ion Iso(ppm) Aniso(ppm) Asym H H H O O O O =========================================================== Anisotropy σ aniso = σ zz 1/2(σ xx σ yy ) Asymmetry η = 3(σ yy σ xx )/2σ aniso
24 *.magres file ============ Atom: O 1 ============ O 1 Coordinates A TOTAL Shielding Tensor O 1 Eigenvalue sigma_xx (ppm) O 1 Eigenvector sigma_xx O 1 Eigenvalue sigma_yy (ppm) O 1 Eigenvector sigma_yy O 1 Eigenvalue sigma_zz (ppm) O 1 Eigenvector sigma_zz O 1 Isotropic: (ppm) O 1 Anisotropy: (ppm) O 1 Asymmetry: Note: shielding tensor has a symmetric and an antisymmetric component. Typical NMR experiments are only sensitive to the symmetric part. Therefore we only diagonalise the symmetric part of the shielding tensor
25 Practical Things Some practical things to keep in mind Structure NMR is very sensitive to structure! XRD atom positions are often not sufficient for accurate simulation of NMR parameters Dynamics Atoms move  spectra are recorded at finite T. How to account for that in (static) calculations? Accuracy How good are our present (approximate) density functionals?
26 Structure Anomeric Carbon Crystallises as: 80% αmaltose 20% βmaltose Compute spectra for both structures separately and superimpose
27 Structure Anomeric Carbon After relaxing neighbouring atom O1ʼ which had large force / thermal ellipsoid
28 Dynamics MLF peptide 13 C rms error Static relaxed structure abinitio MD classical MD 4.2ppm 3.3ppm 3.0ppm 2 pm 5 μm J. Am. Chem. Soc. 132, 3993 (2010) Abinitio MD Captures large (20ppm) fluctuations on fs timescale Classical MD Samples rotomeric states half of sites have errors <1ppm  limitations of PBE
29 Magnetic Resonance File Format Aim Provide a complete archival format for a first principles calculation of NMR parameters Visualisation Abinitio Abinit, CASTEP QE, Wien2k etc fileformat Spinsimulation Database
30 Jmol viewer Opensource Crystalviewer Multiplatform (Java) Can embed in website New developments display selected values on structure convert shielding to chemical shift switch isotopes visualization of tensors (D, J, σ, EFG) relative orientations (Euler angles) select spin system for export
31 Database Abinitio calculations provide NMR parameters for all atoms in the system Papers often report only selected results Store full information as abinitio nmr fileformat in a database Allows later retrieval and processing of data Establish structural trends
32 Consultation Draft specification and examples Feedback and Comments to by 19th October 2012
33 Getting more information NMR Books Good Introduction Nuclear Magnetic Resonance (Oxford Chemistry Primers) P. J. Hore More advanced Spin Dynamics: Basics of Nuclear Magnetic Resonance Malcolm H. Levitt Solid state NMR SolidState NMR: Basic Principles and Practice David Apperley, Robin Harris, Paul Hodgkinson Useful survey of applications Multinuclear SolidState Nuclear Magnetic Resonance of Inorganic Materials Kenneth J.D. MacKenzie, M.E. Smith Recent Review Articles Recent advances in solidstate NMR spectroscopy of spin I = 1/2 nuclei Anne Lesage, Phys. Chem. Chem. Phys., 2009, 11, 6876 Recent advances in solidstate NMR spectroscopy of quadrupolar nuclei Sharon E. Ashbrook, Phys. Chem. Chem. Phys., 2009, 11, 6892
34 Getting more information GIPAW Theory A more in depth introduction to the theory ( JRY for a copy) Computations of Magnetic Resonance Parameters for Crystalline Systems: Principles Jonathan R. Yates, Chris J. Pickard Encyclopedia of Magnetic Resonance (2008) doi: / emrstm1009 Exhaustive (and exhausting!) review of applications and theory ( JRY for a copy) FirstPrinciple Calculation of NMR Parameters Using the GIPAW (Gauge Including Projector Augmented Wave) Method: a Chemist's Point of View Bonhomme, Gervais, Babonneau, Coelho, Pourpoint, Azais, Ashbrook, Griffin, Yates, Mauri, Pickard, Chemical Reviews (in press 2012) Original Theory Papers: Allelectron magnetic response with pseudopotentials: NMR chemical shifts, Chris J. Pickard, and Francesco Mauri. Phys. Rev. B, 63, (2001) Calculation of NMR Chemical Shifts for extended systems using Ultrasoft Pseudopotentials Jonathan R. Yates, Chris J. Pickard, and Francesco Mauri. Physical Review B 76, (2007) A First Principles Theory of Nuclear Magnetic Resonance JCoupling in solidstate systems Sian A. Joyce, Jonathan R. Yates, Chris J. Pickard, Francesco Mauri J. Chem. Phys. 127, (2007)
Chem8028(1314)  Spin Dynamics: Spin Interactions
Chem8028(1314)  Spin Dynamics: Spin Interactions Malcolm Levitt see also IK m106 1 Nuclear spin interactions (diamagnetic materials) 2 Chemical Shift 3 Direct dipoledipole coupling 4 Jcoupling 5 Nuclear
More informationSpin Interactions. Giuseppe Pileio 24/10/2006
Spin Interactions Giuseppe Pileio 24/10/2006 Magnetic moment µ = " I ˆ µ = " h I(I +1) " = g# h Spin interactions overview Zeeman Interaction Zeeman interaction Interaction with the static magnetic field
More informationProbing Hydrogen Bonding by SolidState NMR. Steven P. Brown
Probing ydrogen Bonding by SolidState M Steven P. Brown SolutionState M: Isotropic Interactions Fast isotropic tumbling of the molecules averages to zero all anisotropic broadening Chemical Shift Differentiation
More informationNuclear Quadrupole Resonance Spectroscopy. Some examples of nuclear quadrupole moments
Nuclear Quadrupole Resonance Spectroscopy Review nuclear quadrupole moments, Q A negative value for Q denotes a distribution of charge that is "footballshaped", i.e. a sphere elongated at the poles; a
More informationQuímica Orgânica I. Nuclear Magnetic Resonance Spectroscopy (I) Ciências Farmacêuticas Bioquímica Química AFB QO I 2007/08 1 AFB QO I 2007/08 2
Química Orgânica I Ciências Farmacêuticas Bioquímica Química AFB QO I 2007/08 1 Nuclear Magnetic Resonance Spectroscopy (I) AFB QO I 2007/08 2 1 Adaptado de: Organic Chemistry, 6th Edition; L. G. Wade,
More informationChapter 8 Magnetic Resonance
Chapter 8 Magnetic Resonance 9.1 Electron paramagnetic resonance 9.2 Ferromagnetic resonance 9.3 Nuclear magnetic resonance 9.4 Other resonance methods TCD March 2007 1 A resonance experiment involves
More informationDistinguishing weak hydrogen bonding with NMR
Distinguishing weak hydrogen bonding with NMR Mikhail Kibalchenko, TCM Group, Cambridge University Results published: M. Kibalchenko, D. Lee, L. Shao, M. C. Payne, J. J. Titman, J. R. Yates, (2010). Distinguishing
More informationNMR parameters in alkali, alkaline earth and rare earth fluorides from first principle calculations
CREATED USING THE RSC ARTICLE TEMPLATE (VER. 3.1)  SEE WWW.RSC.ORG/ELECTRONICFILES FOR DETAILS Paper www.rsc.org/pccp Physical Chemistry Chemical Physics 5 NMR parameters in alkali, alkaline earth and
More informationNMR Dynamics and Relaxation
NMR Dynamics and Relaxation Günter Hempel MLU Halle, Institut für Physik, FG FestkörperNMR 1 Introduction: Relaxation Two basic magnetic relaxation processes: Longitudinal relaxation: T 1 Relaxation Return
More informationHyperfine interactions
Hyperfine interactions Karlheinz Schwarz Institute of Materials Chemistry TU Wien Some slides were provided by Stefaan Cottenier (Gent) nuclear point charges interacting with electron charge distribution
More informationNMR: Formalism & Techniques
NMR: Formalism & Techniques Vesna Mitrović, Brown University Boulder Summer School, 2008 Why NMR?  Local microscopic & bulk probe  Can be performed on relatively small samples (~1 mg +) & no contacts
More informationν + = e2 qq φ = 36.9,andθ = Pankratov [4] obtained ν 0 = ν + ν = e2 qq φ = 34.1, and θ = Boogaarts et al. [5]
14 N NQR Study of Diphenylamine Janez Seliger a,b and Veselko Žagar a a Jozef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia b University of Ljubljana, Faculty of Mathematics and Physics, Department
More informationBiophysical Chemistry: NMR Spectroscopy
Nuclear Magnetism Vrije Universiteit Brussel 21st October 2011 Outline 1 Overview and Context 2 3 Outline 1 Overview and Context 2 3 Context Proteins (and other biological macromolecules) Functional characterisation
More informationCenter for Sustainable Environmental Technologies, Iowa State University
NMR Characterization of Biochars By Catherine Brewer Center for Sustainable Environmental Technologies, Iowa State University Introduction Nuclear magnetic resonance spectroscopy (NMR) uses a very strong
More informationIntroduction to Electron Paramagnetic Resonance Spectroscopy
Introduction to Electron Paramagnetic Resonance Spectroscopy Art van der Est, Department of Chemistry, Brock University St. Catharines, Ontario, Canada 1 EPR Spectroscopy EPR is magnetic resonance on unpaired
More informationPrinciples of Molecular Spectroscopy: Electromagnetic Radiation and Molecular structure. Nuclear Magnetic Resonance (NMR)
Principles of Molecular Spectroscopy: Electromagnetic Radiation and Molecular structure Nuclear Magnetic Resonance (NMR) !E = h" Electromagnetic radiation is absorbed when the energy of photon corresponds
More informationNuclear magnetic resonance in condensed matter
University of Ljubljana Faculty of mathematics and physics Physics department SEMINAR Nuclear magnetic resonance in condensed matter Author: Miha Bratkovič Mentor: prof. dr. Janez Dolinšek Ljubljana, October
More informationNatural abundance solidstate 95 Mo MAS NMR of MoS 2 reveals precise 95 Mo anisotropic parameters from its central and satellite transitions
Electronic Supplementary Information for: Natural abundance solidstate 95 Mo MAS NMR of MoS 2 reveals precise 95 Mo anisotropic parameters from its central and satellite transitions Hans J. Jakobsen,*
More informationCONTENTS. 2 CLASSICAL DESCRIPTION 2.1 The resonance phenomenon 2.2 The vector picture for pulse EPR experiments 2.3 Relaxation and the Bloch equations
CONTENTS Preface Acknowledgements Symbols Abbreviations 1 INTRODUCTION 1.1 Scope of pulse EPR 1.2 A short history of pulse EPR 1.3 Examples of Applications 2 CLASSICAL DESCRIPTION 2.1 The resonance phenomenon
More informationNMR Study of Aluminium Coordination in Clays
WDS'13 Proceedings of Contributed Papers, Part III, 104 109, 2013. ISBN 9788073782528 MATFYZPRESS NMR Study of Aluminium Coordination in Clays K. Uličná, H. Štěpánková, V. Římal Charles University
More informationNMR Spectroscopy. Guangjin Hou
NMR Spectroscopy Guangjin Hou 22042009 NMR History 1 H NMR spectra of water H NMR spectra of water (First NMR Spectra on Water, 1946) 1 H NMR spectra ethanol (First bservation of the Chemical Shift,
More informationNuclear Magnetic Resonance
Nuclear Magnetic Resonance PRINCIPLES OF NMR SPECTROSCOPY Contents Principles of nuclear magnetic resonance The nmr spectrometer Basic principles in nmr application NMR tools used to obtain information
More informationNuclear Magnetic Resonance (NMR)
Nuclear Magnetic Resonance (NMR) E E increases with increasing magnetic field strength Boltzmann distribution at thermal equilibrium: N (m=1/2) /N (m=+1/2) = e ( E/kT) with E = γ(h/2π)b o NMR Physical
More informationNMR, the vector model and the relaxation
NMR, the vector model and the relaxation Reading/Books: One and two dimensional NMR spectroscopy, VCH, Friebolin Spin Dynamics, Basics of NMR, Wiley, Levitt Molecular Quantum Mechanics, Oxford Univ. Press,
More informationProtein dynamics from NMR Relaxation data
Protein dynamics from NMR Relaxation data Clubb 3/15/17 (S f2 ) ( e ) Nitrogen15 relaxation ZZexchange R 1 = 1/T 1 Longitudinal relaxation (decay back to zaxis) R 2 = 1/T 2 Spinspin relaxation (dephasing
More informationNuclear Magnetic Resonance
Nuclear Magnetic Resonance Lectures for CCB 538 James Aramini, PhD. CABM 014A jma@cabm.rutgers.edu J.A.! 04/21/14! April 21!!!!April 23!! April 28! Outline 1. Introduction / Spectroscopy Overview! 2. NMR
More informationESR spectroscopy of catalytic systems  a primer
ESR spectroscopy of catalytic systems  a primer Thomas Risse FritzHaberInstitute of MaxPlanck Society Department of Chemical Physics Faradayweg 46 14195 Berlin T. Risse, 11/6/2007, 1 ESR spectroscopy
More informationUses of Nuclear Magnetic Resonance (NMR) in Metal Hydrides and Deuterides. Mark S. Conradi
Uses of Nuclear Magnetic Resonance (NMR) in Metal Hydrides and Deuterides Mark S. Conradi Washington University Department of Physics St. Louis, MO 631304899 USA msc@physics.wustl.edu 1 Uses of Nuclear
More informationMagnetic Resonance Spectroscopy EPR and NMR
Magnetic Resonance Spectroscopy EPR and NMR A brief review of the relevant bits of quantum mechanics 1. Electrons have spin,  rotation of the charge about its axis generates a magnetic field at each electron.
More informationNMR Spectroscopy of Polymers
UNESCO/IUPAC Course 2005/2006 Jiri Brus NMR Spectroscopy of Polymers Brus J 1. part At the very beginning the phenomenon of nuclear spin resonance was studied predominantly by physicists and the application
More informationK ex. Conformational equilibrium. equilibrium K B
Effects of Chemical Exchange on NMR Spectra Chemical exchange refers to any yprocess in which a nucleus exchanges between two or more environments in which its NMR parameters (e.g. chemical shift, scalar
More information2.1. NMR Spectroscopy, Anisotropic Nuclear Spin Interaction.
Chapter II. Molecular segments orientation study using 29 Si NMR methods. 2.1. NMR Spectroscopy, Anisotropic Nuclear Spin Interaction. The term Nuclear Magnetic Resonance (NMR) unifies a big variety of
More informationJournal of the Korean Magnetic Resonance Society 2003, 7, Kwangju, , KOREA Received September 29, 2003
Journal of the Korean Magnetic Resonance Society 2003, 7, 8088 11 B Nuclear Magnetic Resonance Study of Calciumhexaborides B. J. Mean 1, K. H. Lee 1, K. H. Kang 1, Moohee Lee 1*, J.S. Lee 2, and B. K.
More informationSpinspin coupling I Ravinder Reddy
Spinspin coupling I Ravinder Reddy Spininteractions External interactions Magnetic field Bo, RF field B1 Internal Interactions Molecular motions Exchange Chemical shifts Jcoupling Spin Diffusion Dipolar
More informationNuclear Magnetic Resonance HNMR Part 1 Introduction to NMR, Instrumentation, Sample Prep, Chemical Shift. Dr. Sapna Gupta
Nuclear Magnetic Resonance HNMR Part 1 Introduction to NMR, Instrumentation, Sample Prep, Chemical Shift Dr. Sapna Gupta Introduction NMR is the most powerful tool available for organic structure determination.
More informationProblem Set 2 Due Thursday, October 1, & & & & # % (b) Construct a representation using five d orbitals that sit on the origin as a basis:
Problem Set 2 Due Thursday, October 1, 29 Problems from Cotton: Chapter 4: 4.6, 4.7; Chapter 6: 6.2, 6.4, 6.5 Additional problems: (1) Consider the D 3h point group and use a coordinate system wherein
More informationNMR Predictor. Introduction
NMR Predictor This manual gives a walkthrough on how to use the NMR Predictor: Introduction NMR Predictor QuickHelp NMR Predictor Overview Chemical features GUI features Usage Menu system File menu Edit
More information3.15 Nuclear Magnetic Resonance Spectroscopy, NMR
3.15 Nuclear Magnetic Resonance Spectroscopy, NMR What is Nuclear Magnetic Resonance  NMR Developed by chemists and physicists together it works by the interaction of magnetic properties of certain nuclei
More informationOrigin of Scalar Couplings BCMB/CHEM 8190
Origin of Scalar Couplings BCMB/CHEM 8190 Traditional View of Scalar Coupling Splitting of NMR signals due to throughbond interactions between nuclei is called scalar coupling (or J coupling or throughbond
More informationSuperoperators for NMR Quantum Information Processing. Osama Usman June 15, 2012
Superoperators for NMR Quantum Information Processing Osama Usman June 15, 2012 Outline 1 Prerequisites 2 Relaxation and spin Echo 3 Spherical Tensor Operators 4 Superoperators 5 My research work 6 References.
More informationNuclear Magnetic Resonance (NMR)
Nuclear Magnetic Resonance (NMR) Nuclear Magnetic Resonance (NMR) The Nuclear Magnetic Resonance Spectroscopy (NMR) is one of the most important spectroscopic methods to explore the structure and dynamic
More informationNuclear Magnetic Resonance Spectroscopy
Chapter 5 Nuclear Magnetic Resonance Spectroscopy http://www.yteach.co.uk/page.php/resources/view_all?id=nuclear_magnetic _resonance_nmr_spectroscopy_spin_spectrometer_spectrum_proton_t_pag e_5&from=search
More information16.1 Introduction to NMR. Spectroscopy
16.1 Introduction to NMR What is spectroscopy? Spectroscopy NUCLEAR MAGNETIC RESNANCE (NMR) spectroscopy may be the most powerful method of gaining structural information about organic compounds. NMR involves
More informationPrinciples of Nuclear Magnetic Resonance in One and Two Dimensions
Principles of Nuclear Magnetic Resonance in One and Two Dimensions Richard R. Ernst, Geoffrey Bodenhausen, and Alexander Wokaun Laboratorium für Physikalische Chemie Eidgenössische Technische Hochschule
More informationThe quadrupole moments of Zn and Cd isotopes an update
Hyperfine Interact DOI 10.1007/s1075101002116 The quadrupole moments of Zn and Cd isotopes an update H. Haas J. G. Correia Springer Science+Business Media B.V. 2010 Abstract The nuclear quadrupole moments
More informationcompound Cs 2 Cu 2 Mo 3 O 12
133 CsNMR study on aligned powder of competing spin chain compound A Yagi 1, K Matsui 1 T Goto 1, M Hase 2 and T Sasaki 3 1 2 Sophia University, Physics Division, Tokyo, 1028554, Japan National Institute
More informationFundamental MRI Principles Module 2 N. Nuclear Magnetic Resonance. Xray. MRI Hydrogen Protons. Page 1. Electrons
Fundamental MRI Principles Module 2 N S 1 Nuclear Magnetic Resonance There are three main subatomic particles: protons positively charged neutrons no significant charge electrons negatively charged Protons
More informationChapter 13 Structure t Determination: Nuclear Magnetic Resonance Spectroscopy
John E. McMurry www.cengage.com/chemistry/mcmurry Chapter 13 Structure t Determination: ti Nuclear Magnetic Resonance Spectroscopy Revisions by Dr. Daniel Holmes MSU Paul D. Adams University of Arkansas
More informationMolecular Magnetism. Magnetic Resonance Parameters. Trygve Helgaker
Molecular Magnetism Magnetic Resonance Parameters Trygve Helgaker Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Oslo, Norway Laboratoire de Chimie Théorique,
More informationGeneral NMR basics. Solid State NMR workshop 2011: An introduction to Solid State NMR spectroscopy. # nuclei
: An introduction to Solid State NMR spectroscopy Dr. Susanne Causemann (Solid State NMR specialist/ researcher) Interaction between nuclear spins and applied magnetic fields B 0 application of a static
More informationPhysical Background Of Nuclear Magnetic Resonance Spectroscopy
Physical Background Of Nuclear Magnetic Resonance Spectroscopy Michael McClellan Spring 2009 Department of Physics and Physical Oceanography University of North Carolina Wilmington What is Spectroscopy?
More informationMagnetic Resonance Spectroscopy ( )
Magnetic Resonance Spectroscopy In our discussion of spectroscopy, we have shown that absorption of E.M. radiation occurs on resonance: When the frequency of applied E.M. field matches the energy splitting
More informationChristopher Pavlik Bioanalytical Chemistry March 2, 2011
Nuclear Magnetic Resonance of Proteins Christopher Pavlik Bioanalytical Chemistry March 2, 2011 Nuclear Magnetic Resonance NMR Application of a magnetic field causes absorption of EM energy that induces
More informationNuclear spin maser with a novel masing mechanism and its application to the search for an atomic EDM in 129 Xe
Nuclear spin maser with a novel masing mechanism and its application to the search for an atomic EDM in 129 Xe A. Yoshimi RIKEN K. Asahi, S. Emori, M. Tsukui, RIKEN, Tokyo Institute of Technology Nuclear
More informationFundamental MRI Principles Module Two
Fundamental MRI Principles Module Two 1 Nuclear Magnetic Resonance There are three main subatomic particles: protons neutrons electrons positively charged no significant charge negatively charged Protons
More informationThe electronic structure of materials 2  DFT
Quantum mechanics 2  Lecture 9 December 19, 2012 1 Density functional theory (DFT) 2 Literature Contents 1 Density functional theory (DFT) 2 Literature Historical background The beginnings: L. de Broglie
More informationElectrons in Crystals. Chris J. Pickard
Electrons in Crystals Chris J. Pickard Electrons in Crystals The electrons in a crystal experience a potential with the periodicity of the Bravais lattice: U(r + R) = U(r) The scale of the periodicity
More informationProblem Set 2 Due Tuesday, September 27, ; p : 0. (b) Construct a representation using five d orbitals that sit on the origin as a basis: 1
Problem Set 2 Due Tuesday, September 27, 211 Problems from Carter: Chapter 2: 2ad,g,h,j 2.6, 2.9; Chapter 3: 1ad,f,g 3.3, 3.6, 3.7 Additional problems: (1) Consider the D 4 point group and use a coordinate
More informationReading. What is EPR (ESR)? Spectroscopy: The Big Picture. Electron Paramagnetic Resonance: Hyperfine Interactions. Chem 634 T.
Electron Paramagnetic Resonance: yperfine Interactions hem 63 T. ughbanks Reading Drago s Physical Methods for hemists is still a good text for this section; it s available by download (zipped, password
More informationApplications of Nuclear Magnetic Resonance to Metal Hydrogen Materials
Applications of Nuclear Magnetic Resonance to Metal Hydrogen Materials Part I: Basic Principles & General Applications Robert C. Bowman, Jr. and SonJong Hwang California Institute of Technology Pasadena,
More informationDetermination of quadrupolar and chemical shielding tensors using solidstate twodimensional NMR spectroscopy
Determination of quadrupolar and chemical shielding tensors using solidstate twodimensional NMR spectroscopy J. S. Shore a) and S. H. Wang Materials Science Division, Lawrence Berkeley Laboratory and
More informationMagnetized Materials: Contributions Inside Lorentz Ellipsoids
Magnetized Materials: Contributions Inside Lorentz Ellipsoids S.Aravamudhan Department of Chemistry North Eastern Hill University PO NEHU Campus Mawkynroh Umshing Shillong (Meghalaya) 793022 Email: saravamudhan@nehu.ac.in
More informationIntroduction to Nuclear Magnetic Resonance Spectroscopy
Introduction to Nuclear Magnetic Resonance Spectroscopy Dr. Dean L. Olson, NMR Lab Director School of Chemical Sciences University of Illinois Called figures, equations, and tables are from Principles
More informationLecturenotes Chem 781 Part 3: Chemical Shift
Lecturenotes hem 781 Part 3: hemical Shift F. olger Försterling, September 25, 2012 1 General 1.1 istory and origin of chemical shift Early NMR spectra were all taken of solids. Due to very small T 2 in
More informationUNESCO  EOLSS SAMPLE CHAPTER
NMR SPECTROSCOPY Juan Carlos Paniagua and Miquel Pons University of Barcelona, Spain Keywords: chemical shift, correlation spectroscopy, diffusion coefficient, Fourier transform spectroscopy, imaging,
More informationIntermission: Let s review the essentials of the Helium Atom
PHYS3022 Applied Quantum Mechanics Problem Set 4 Due Date: 6 March 2018 (Tuesday) T+2 = 8 March 2018 All problem sets should be handed in not later than 5pm on the due date. Drop your assignments in the
More informationExperiment 7: Dynamic NMR spectroscopy (Dated: April 19, 2010)
Experiment 7: Dynamic NMR spectroscopy (Dated: April 19, 2010) I. INTRODUCTION In general spectroscopic experiments are divided into two categories: optical spectroscopy and magnetic spectroscopy. In previous
More informationLecture #6 (The NOE)
Lecture #6 (The OE) 2/18/15 Clubb Determining Protein tructures by MR: Measure thousands of shorter interhydrogen atom distances. Use these to restrain the structure of protein computationally. Distance
More informationLecture #6 Chemical Exchange
Lecture #6 Chemical Exchange Topics Introduction Effects on longitudinal magnetization Effects on transverse magnetization Examples Handouts and Reading assignments Kowalewski, Chapter 13 Levitt, sections
More informationProbing the Origins of Intermolecular Vibrational and Relaxational Dynamics in Organic Solids with CP2K
Probing the Origins of Intermolecular Vibrational and Relaxational Dynamics in Organic Solids with CP2K Michael Ruggiero Department of Chemical Engineering and Biotechnology, University of Cambridge CP2K
More informationUse of spatial encoding in NMR photography
Journal of Magnetic Resonance 171 (2004) 359 363 www.elsevier.com/locate/jmr Use of spatial encoding in NMR photography Krishna Kishor Dey a,1, Rangeet Bhattacharyya a, Anil Kumar a,b, * a Department of
More informationCHAPTER 2. Atomic Structure And Bonding 21
CHAPTER 2 Atomic Structure And Bonding 21 Structure of Atoms ATOM Basic Unit of an Element Diameter : 10 10 m. Neutrally Charged Nucleus Diameter : 10 14 m Accounts for almost all mass Positive Charge
More informationDFT calculations of NMR indirect spin spin coupling constants
DFT calculations of NMR indirect spin spin coupling constants Dalton program system Program capabilities Density functional theory Kohn Sham theory LDA, GGA and hybrid theories Indirect NMR spin spin coupling
More informationStructure Determination: Nuclear Magnetic Resonance Spectroscopy
Structure Determination: Nuclear Magnetic Resonance Spectroscopy Why This Chapter? NMR is the most valuable spectroscopic technique used for structure determination More advanced NMR techniques are used
More informationWeak Halogen Bonding in Solid Haloanilinium Halides Probed Directly via Chlorine35, Bromine81, and Iodine127 NMR Spectroscopy
pubs.acs.org/crystal Weak Halogen Bonding in Solid Haloanilinium Halides Probed Directly via Chlorine35, Bromine81, and Iodine127 NMR Spectroscopy Published as part of the Crystal Growth & Design virtual
More informationTimescales of Protein Dynamics
Timescales of Protein Dynamics From HenzlerWildman and Kern, Nature 2007 Dynamics from NMR Show spies Amide Nitrogen Spies Report On Conformational Dynamics Amide Hydrogen Transverse Relaxation Ensemble
More informationSpectral Resolution. Spectral resolution is a measure of the ability to separate nearby features in wavelength space.
Spectral Resolution Spectral resolution is a measure of the ability to separate nearby features in wavelength space. R, minimum wavelength separation of two resolved features. Delta lambda often set to
More informationChemistry 843 "Advanced NMR Spectroscopy" Gerd Gemmecker, 1999
Dr. Gerd Gemmecker Room 5333a Phone 28619 email gemmecker@chem.wisc.edu Gerd.Gemmecker@ch.tum.de Chemistry 843 "Advanced NMR Spectroscopy" Gerd Gemmecker, 1999 This course will cover the theory required
More informationDensity Functional Theory
Density Functional Theory Iain Bethune EPCC ibethune@epcc.ed.ac.uk Overview Background Classical Atomistic Simulation Essential Quantum Mechanics DFT: Approximations and Theory DFT: Implementation using
More informationQuantum Chemistry. NC State University. Lecture 5. The electronic structure of molecules Absorption spectroscopy Fluorescence spectroscopy
Quantum Chemistry Lecture 5 The electronic structure of molecules Absorption spectroscopy Fluorescence spectroscopy NC State University 3.5 Selective absorption and emission by atmospheric gases (source:
More informationNMR Assay of Purity and Folding
NMR Assay of Purity and Folding Don t Need Resonance Assignments or Labeling 1D requires only 1050 µm protein concentration 2D Provides A More Detailed Assay 15 N 1 H HSQC 1 H COSY 13 C HSQC also! Analyze
More informationNMR Spectroscopy. Chapter 19
NMR Spectroscopy Chapter 19 Nuclear Magnetic Resonance spectroscopy is a powerful analytical technique used to characterize organic molecules by identifying carbonhydrogen frameworks within molecules.
More informationElectronic Properties of (NH 3 ) x NaK 2 C 60
Electronic Properties of (NH 3 ) x NaK 2 C 60 M. Riccò a, T. Shiroka a, A. Sartori a, F. Bolzoni b and M. Tomaselli c a Dipartimento di Fisica and Istituto Nazionale di Fisica della Materia, Università
More informationNuclear Magnetic Resonance Spectroscopy Chem 4010/5326: Organic Spectroscopic Analysis Andrew Harned
Nuclear Magnetic Resonance Spectroscopy Chem 4010/5326: Organic Spectroscopic Analysis 2015 Andrew Harned NMR Spectroscopy NMR Spectroscopy All nuclei have a nuclear spin quantum number (I) I = 0, 1/2,
More informationIntroduction solution NMR
2 NMR journey Introduction solution NMR Alexandre Bonvin Bijvoet Center for Biomolecular Research with thanks to Dr. Klaartje Houben EMBO Global Exchange course, IHEP, Beijing April 28  May 5, 20 3 Topics
More informationProtein Dynamics, Allostery and Function
Protein Dynamics, Allostery and Function Lecture 3. Protein Dynamics Xiaolin Cheng UT/ORNL Center for Molecular Biophysics SJTU Summer School 2017 1 Obtaining Dynamic Information Experimental Approaches
More informationMolecular Crystals And Molecules (Physical Chemistry Monograph Volume 29) By A.I. Kitaigorodsky READ ONLINE
Molecular Crystals And Molecules (Physical Chemistry Monograph Volume 29) By A.I. Kitaigorodsky READ ONLINE Physical Chemistry  Scribd  Text file (.txt) or read book online. Physical Chemistry, Undergraduate.
More informationInfluence of Calciuminduced Aggregation on the Sensitivity of. Aminobis(methylenephosphonate)Containing Potential MRI Contrast.
Supporting Information for Influence of Calciuminduced Aggregation on the Sensitivity of Aminobis(methylenephosphonate)Containing Potential MRI Contrast Agents Jörg Henig, Ilgar Mamedov, Petra Fouskova,
More informationNMR = Nuclear Magnetic Resonance
NMR = Nuclear Magnetic Resonance NMR spectroscopy is the most powerful technique available to organic chemists for determining molecular structures. Looks at nuclei with odd mass numbers or odd number
More informationElectric and magnetic multipoles
Electric and magnetic multipoles Trond Saue Trond Saue (LCPQ, Toulouse) Electric and magnetic multipoles Virginia Tech 2017 1 / 22 Multipole expansions In multipolar gauge the expectation value of the
More information/2Mα 2 α + V n (R)] χ (R) = E υ χ υ (R)
Spectroscopy: Engel Chapter 18 XIV 67 Vibrational Spectroscopy (Typically IR and Raman) BornOppenheimer approx. separate electronnuclear Assume electnuclear motion separate, full wave fct. ψ (r,r) =
More informationDFT EXERCISES. FELIPE CERVANTES SODI January 2006
DFT EXERCISES FELIPE CERVANTES SODI January 2006 http://www.csanyi.net/wiki/space/dftexercises Dr. Gábor Csányi 1 Hydrogen atom Place a single H atom in the middle of a largish unit cell (start with a
More informationChemistry 4715/8715 Physical Inorganic Chemistry Fall :20 pm 1:10 pm MWF 121 Smith. Kent Mann; 668B Kolthoff; ;
Chemistry 4715/8715 Physical Inorganic Chemistry Fall 2017 12:20 pm 1:10 pm MWF 121 Smith Instructor: Text: be made available). Kent Mann; 668B Kolthoff; 6253563; krmann@umn.edu R.S. Drago, Physical Methods
More informationNUCLEAR MAGNETIC RESONANCE
uclear Magnetic Resonance CAPTER UCLEAR MAGETIC REOACE Properties of nucleus to give MR signal: All the nucleus their isotopes present in periodic table are not MR active. For a nucleus to be MR active
More informationSpectroscopy. Empirical Formula: Chemical Formula: Index of Hydrogen Deficiency (IHD)
Spectroscopy Empirical Formula: Chemical Formula: Index of Hydrogen Deficiency (IHD) A)From a structure: B)From a molecular formula, C c H h N n O o X x, Formula for saturated hydrocarbons: Subtract the
More informationXe line shapes in dipeptide channels: AV and VA
Xe line shapes in dipeptide channels: AV and VA Cynthia J. Jameson and Devin N. Sears University of Illinois at Chicago with Ripmeester et al. 1 Motivation: Xenon has an affinity for hydrophobic cavities
More informationTuesday, January 13, NMR Spectroscopy
NMR Spectroscopy NMR Phenomenon Nuclear Magnetic Resonance µ A spinning charged particle generates a magnetic field. A nucleus with a spin angular momentum will generate a magnetic moment (μ). If these
More informationNMR Studies of Polyethylene: Towards the Organization of Semi Crystalline Polymers
NMR Studies of Polyethylene: Towards the Organization of Semi Crystalline Polymers Yefeng Yao, Robert Graf, Hans Wolfgang Spiess MaxPlanckInstitute for Polymer Research, Mainz, Germany Leibniz Institut
More informationMolecular Modeling lecture 2
Molecular Modeling 2018  lecture 2 Topics 1. Secondary structure 3. Sequence similarity and homology 2. Secondary structure prediction 4. Where do protein structures come from? Xray crystallography
More information