NMR of Oriented Molecules, Fields of Research


Molecular Structure Determination

  • Basic Theory
  • Possible Accuracy
  • Accuracy Limiting Factors
  • Molecular Vibrations
  • Molecular Deformations
  • Molecular Orientation
  • Molecular Conformation
  • Solvents Effects
  • Isotope Effects
  • Nonrigid Molecules
  • Enantiomeric Analysis
  • Weak Molecular Interactions
  • Spectral Simplification
  • Alkyl Chain Dynamics
  • Combination with Other Data
  • Basic Theory

    NMR of Oriented Molecules, Fields of Research, Molecular Structure Determination, Basic Theory

  • The Order Tensor
  • Direct Coupling
  • Hamiltonian
  • The Zeeman Interaction
  • The Indirect Spin-Spin Interaction
  • Quadrupolar Interaction
  • Relaxation Rates
  • Molecular Symmetry
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  • Accuracy Limiting Factors

    NMR of Oriented Molecules, Fields of Research, Molecular Structure Determination, Accuracy Limiting Factors

  • Anisotropy of Indirect Coupling
  • Molecular Vibration
  • Molecular Deformation
  • Intramolecular Motion
  • Multiple Sites
  • Solvent Effects
  • Signal-to-Noise Ratio
  • Nonidentity of Magnetical and Mechanical Structure
  • Translational motion
  • Biaxiality of Liquid Crystal
  • Distribution Function
  • Time Averaging Substitution by Orientation Averaging
  • ?
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  • Nonrigid Molecules

    NMR of Oriented Molecules, Fields of Research, Molecular Structure Determination, Nonrigid Molecules

  • Single Rotors
  • Double Rotors
  • Fast Transition Between Conformers
  • Ring Inversion, Puckering, etc,
  • ?
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  • Valence Isomerization
  • NMR of Oriented Molecules, Fields of Research, Molecular Structure Determination, Possible Accuracy of Structure Determination

    Possible Accuracy of Structure Determination

    Most observed direct couplings are in the range of 102-103Hz. It is usually possible to obtain linewidths of the order of 1 Hz, so that 0.1 Hz can definitely be determined (sometimes even 0.01 Hz). So that the relatively accuracy of couplings is usually 0.0001.
    Since the internuclear distances are inversely proportional to cube of direct couplings, the relatively accuracy of the distances is alsu further increased to 0.00003.
    Consequently, distances should, in principle, be measurable with an accuracy of at least 0.01 pm. Unfortunately, this accuracy is not meaningful, because several approximation are made in the necessary corrections to the measured direct couplings. These are neglect of pseudodipolar coupling contributions to the measured couplings, limited accuracy in the vibration corrections, and assumptions made in the deformation corrections (see Factors Limiting the Accuracy of Structure Determination)
    Taking these facts into account, it is possible to state that an accuracy of distance determination by NMR of oriented molecules exceeding 0.1 pm in bond lengths and 0.1° in bond angles is definitely unrealistic.
    However 1 pm may measured reliably.

    Return to "NMR of Oriented Molecules"

    Last Update: April 22th, 1997
    By: Alexan Shahatuni (msrc@moon.yerphi.am)