Harman Patil (Editor)

Isotopic shift

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The isotopic shift (also called isotope shift) is the shift in various forms of spectroscopy that occurs when one nuclear isotope is replaced by another.

Contents

Atomic spectra

If atomic spectra also have hyperfine structure the shift refers to the center of gravity of the spectra. There are two effects which contribute to this shift:

  • The mass difference. This difference induces a change in the reduced electronic mass. This purely kinematical effect, studied theoretically by Hughes and Eckart is important for light elements.
  • The volume difference. This difference induces a change in the electric charge distribution of the nucleus. This effect is important in heavy elements and its first theory was formulated by Pauli and Peierls.

    • NMR spectroscopy

    In NMR spectroscopy, Isotopic effects on chemical shifts are typically small, far less than1 ppm the typical unit for measuring shifts. The 1
    H     NMR signals for 1
    H
    2     and 1
    H    2
    H     ("HD") are readily distinguished in terms of their chemical shifts. The asymmetry of the signal for the "protio" impurity in CD
    2    Cl
    2     arises from the differing chemical shifts of CDHCl
    2     and CH
    2    Cl
    2    .

    Vibrational spectra

    Isotopic shifts are best known and most widely used in vibration spectroscopy where the shifts are large, being proportional to the ratio of the square root of the isotopic masses. In the case of hydrogen, the "H-D shift" is (1/2)1/2 or 1/1.41. Thus, the (totally symmetric) C-H vibration for CH
    4     and CD
    4     occur at 2917 cm−1 and 2109 cm−1, respectively. This shift reflects the differing Reduced mass for the affected bonds.

    References

    Isotopic shift Wikipedia
    (Text) CC BY-SA