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Hyperfine structure

In atomic physics, hyperfine structure is defined by small shifts in otherwise degenerate energy levels and the resulting splittings in those energy levels of atoms, molecules, and ions, due to electromagnetic multipole interaction between the nucleus and electron clouds.

In atoms, hyperfine structure arises from the energy of the nuclear magnetic dipole moment interacting with the magnetic field generated by the electrons and the energy of the nuclear electric quadrupole moment in the electric field gradient due to the distribution of charge within the atom. Molecular hyperfine structure is generally dominated by these two effects, but also includes the energy associated with the interaction between the magnetic moments associated with different magnetic nuclei in a molecule, as well as between the nuclear magnetic moments and the magnetic field generated by the rotation of the molecule.

Hyperfine structure contrasts with fine structure, which results from the interaction between the magnetic moments associated with electron spin and the electrons' orbital angular momentum. Hyperfine structure, with energy shifts typically orders of magnitudes smaller than those of a fine-structure shift, results from the interactions of the nucleus (or nuclei, in molecules) with internally generated electric and magnetic fields.

Schematic illustration of fine and hyperfine structure in a neutral hydrogen atom

History

The first theory of atomic hyperfine structure was given in 1930 by Enrico Fermi [1] for an atom containing a single valence electron with an arbitrary angular momentum. The Zeeman splitting of this structure was discussed by S. A. Goudsmit and R. F. Bacher later that year. In 1935, H. Schüler and Theodor Schmidt proposed the existence of a nuclear quadrupole moment in order to explain anomalies in the hyperfine structure.[citation needed]

Theory

The theory of hyperfine structure comes directly from electromagnetism, consisting of the interaction of the nuclear multipole moments (excluding the electric monopole) with internally generated fields. The theory is derived first for the atomic case, but can be applied to each nucleus in a molecule. Following this there is a discussion of the additional effects unique to the molecular case.

Atomic hyperfine structure

Magnetic dipole

The dominant term in the hyperfine Hamiltonian is typically the magnetic dipole term. Atomic nuclei with a non-zero nuclear spin   have a magnetic dipole moment, given by:

 

where   is the g-factor and   is the nuclear magneton.

There is an energy associated with a magnetic dipole moment in the presence of a magnetic field. For a nuclear magnetic dipole moment, μI, placed in a magnetic field, B, the relevant term in the Hamiltonian is given by:[2]

 

In the absence of an externally applied field, the magnetic field experienced by the nucleus is that associated with the orbital () and spin (s) angular momentum of the electrons:

 

Electron orbital angular momentum results from the motion of the electron about some fixed external point that we shall take to be the location of the nucleus. The magnetic field at the nucleus due to the motion of a single electron, with charge –e at a position r relative to the nucleus, is given by:

 

where −r gives the position of the nucleus relative to the electron. Written in terms of the Bohr magneton, this gives:

 

Recognizing that mev is the electron momentum, p, and that r×p/ħ is the orbital angular momentum in units of ħ, , we can write:

 

For a many-electron atom this expression is generally written in terms of the total orbital angular momentum,  , by summing over the electrons and using the projection operator,  , where  . For states with a well defined projection of the orbital angular momentum, Lz, we can write  , giving:

 

The electron spin angular momentum is a fundamentally different property that is intrinsic to the particle and therefore does not depend on the motion of the electron. Nonetheless it is angular momentum and any angular momentum associated with a charged particle results in a magnetic dipole moment, which is the source of a magnetic field. An electron with spin angular momentum, s, has a magnetic moment, μs, given by:

 

where gs is the electron spin g-factor and the negative sign is because the electron is negatively charged (consider that negatively and positively charged particles with identical mass, travelling on equivalent paths, would have the same angular momentum, but would result in currents in the opposite direction).

The magnetic field of a point dipole moment, μs, is given by:[3][4]

 

The complete magnetic dipole contribution to the hyperfine Hamiltonian is thus given by:

 

The first term gives the energy of the nuclear dipole in the field due to the electronic orbital angular momentum. The second term gives the energy of the "finite distance" interaction of the nuclear dipole with the field due to the electron spin magnetic moments. The final term, often known as the Fermi contact term relates to the direct interaction of the nuclear dipole with the spin dipoles and is only non-zero for states with a finite electron spin density at the position of the nucleus (those with unpaired electrons in s-subshells). It has been argued that one may get a different expression when taking into account the detailed nuclear magnetic moment distribution.[5]

For states with   this can be expressed in the form

 

where:

 [2]

If hyperfine structure is small compared with the fine structure (sometimes called IJ-coupling by analogy with LS-coupling), I and J are good quantum numbers and matrix elements of   can be approximated as diagonal in I and J. In this case (generally true for light elements), we can project N onto J (where J = L + S is the total electronic angular momentum) and we have:[6]

 

This is commonly written as

 

with   being the hyperfine-structure constant which is determined by experiment. Since I·J = 12{F·FI·IJ·J} (where F = I + J is the total angular momentum), this gives an energy of:

 

In this case the hyperfine interaction satisfies the Landé interval rule.

Electric quadrupole

Atomic nuclei with spin   have an electric quadrupole moment.[7] In the general case this is represented by a rank-2 tensor,  , with components given by:[3]

 

where i and j are the tensor indices running from 1 to 3, xi and xj are the spatial variables x, y and z depending on the values of i and j respectively, δij is the Kronecker delta and ρ(r) is the charge density. Being a 3-dimensional rank-2 tensor, the quadrupole moment has 32 = 9 components. From the definition of the components it is clear that the quadrupole tensor is a symmetric matrix (Qij = Qji) that is also tracelessiQii = 0), giving only five components in the irreducible representation. Expressed using the notation of irreducible spherical tensors we have:[3]

 

The energy associated with an electric quadrupole moment in an electric field depends not on the field strength, but on the electric field gradient, confusingly labelled  , another rank-2 tensor given by the outer product of the del operator with the electric field vector:

 

with components given by:

 

Again it is clear this is a symmetric matrix and, because the source of the electric field at the nucleus is a charge distribution entirely outside the nucleus, this can be expressed as a 5-component spherical tensor,  , with:[8]

 

where:

 

The quadrupolar term in the Hamiltonian is thus given by:

 

A typical atomic nucleus closely approximates cylindrical symmetry and therefore all off-diagonal elements are close to zero. For this reason the nuclear electric quadrupole moment is often represented by Qzz.[7]

Molecular hyperfine structure

The molecular hyperfine Hamiltonian includes those terms already derived for the atomic case with a magnetic dipole term for each nucleus with   and an electric quadrupole term for each nucleus with  . The magnetic dipole terms were first derived for diatomic molecules by Frosch and Foley,[9] and the resulting hyperfine parameters are often called the Frosch and Foley parameters.

In addition to the effects described above, there are a number of effects specific to the molecular case.[10]

Direct nuclear spin–spin

Each nucleus with   has a non-zero magnetic moment that is both the source of a magnetic field and has an associated energy due to the presence of the combined field of all of the other nuclear magnetic moments. A summation over each magnetic moment dotted with the field due to each other magnetic moment gives the direct nuclear spin–spin term in the hyperfine Hamiltonian,  .[11]

 

where α and α' are indices representing the nucleus contributing to the energy and the nucleus that is the source of the field respectively. Substituting in the expressions for the dipole moment in terms of the nuclear angular momentum and the magnetic field of a dipole, both given above, we have

 

Nuclear spin–rotation

The nuclear magnetic moments in a molecule exist in a magnetic field due to the angular momentum, T (R is the internuclear displacement vector), associated with the bulk rotation of the molecule,[11] thus

 

Small molecule hyperfine structure

A typical simple example of the hyperfine structure due to the interactions discussed above is in the rotational transitions of hydrogen cyanide (1H12C14N) in its ground vibrational state. Here, the electric quadrupole interaction is due to the 14N-nucleus, the hyperfine nuclear spin-spin splitting is from the magnetic coupling between nitrogen, 14N (IN = 1), and hydrogen, 1H (IH = 12), and a hydrogen spin-rotation interaction due to the 1H-nucleus. These contributing interactions to the hyperfine structure in the molecule are listed here in descending order of influence. Sub-doppler techniques have been used to discern the hyperfine structure in HCN rotational transitions.[12]

The dipole selection rules for HCN hyperfine structure transitions are  ,  , where J is the rotational quantum number and F is the total rotational quantum number inclusive of nuclear spin ( ), respectively. The lowest transition ( ) splits into a hyperfine triplet. Using the selection rules, the hyperfine pattern of   transition and higher dipole transitions is in the form of a hyperfine sextet. However, one of these components ( ) carries only 0.6% of the rotational transition intensity in the case of  . This contribution drops for increasing J. So, from   upwards the hyperfine pattern consists of three very closely spaced stronger hyperfine components ( ,  ) together with two widely spaced components; one on the low frequency side and one on the high frequency side relative to the central hyperfine triplet. Each of these outliers carry ~  (J is the upper rotational quantum number of the allowed dipole transition) the intensity of the entire transition. For consecutively higher-J transitions, there are small but significant changes in the relative intensities and positions of each individual hyperfine component.[13]

Measurements

Hyperfine interactions can be measured, among other ways, in atomic and molecular spectra and in electron paramagnetic resonance spectra of free radicals and transition-metal ions.

Applications

Astrophysics

 
The hyperfine transition as depicted on the Pioneer plaque

As the hyperfine splitting is very small, the transition frequencies are usually not located in the optical, but are in the range of radio- or microwave (also called sub-millimeter) frequencies.

Hyperfine structure gives the 21 cm line observed in H I regions in interstellar medium.

Carl Sagan and Frank Drake considered the hyperfine transition of hydrogen to be a sufficiently universal phenomenon so as to be used as a base unit of time and length on the Pioneer plaque and later Voyager Golden Record.

In submillimeter astronomy, heterodyne receivers are widely used in detecting electromagnetic signals from celestial objects such as star-forming core or young stellar objects. The separations among neighboring components in a hyperfine spectrum of an observed rotational transition are usually small enough to fit within the receiver's IF band. Since the optical depth varies with frequency, strength ratios among the hyperfine components differ from that of their intrinsic (or optically thin) intensities (these are so-called hyperfine anomalies, often observed in the rotational transitions of HCN[13]). Thus, a more accurate determination of the optical depth is possible. From this we can derive the object's physical parameters.[14]

Nuclear spectroscopy

In nuclear spectroscopy methods, the nucleus is used to probe the local structure in materials. The methods mainly base on hyperfine interactions with the surrounding atoms and ions. Important methods are nuclear magnetic resonance, Mössbauer spectroscopy, and perturbed angular correlation.

Nuclear technology

The atomic vapor laser isotope separation (AVLIS) process uses the hyperfine splitting between optical transitions in uranium-235 and uranium-238 to selectively photo-ionize only the uranium-235 atoms and then separate the ionized particles from the non-ionized ones. Precisely tuned dye lasers are used as the sources of the necessary exact wavelength radiation.

Use in defining the SI second and meter

The hyperfine structure transition can be used to make a microwave notch filter with very high stability, repeatability and Q factor, which can thus be used as a basis for very precise atomic clocks. The term transition frequency denotes the frequency of radiation corresponding to the transition between the two hyperfine levels of the atom, and is equal to f = ΔE/h, where ΔE is difference in energy between the levels and h is the Planck constant. Typically, the transition frequency of a particular isotope of caesium or rubidium atoms is used as a basis for these clocks.

Due to the accuracy of hyperfine structure transition-based atomic clocks, they are now used as the basis for the definition of the second. One second is now defined to be exactly 9192631770 cycles of the hyperfine structure transition frequency of caesium-133 atoms.

On October 21, 1983, the 17th CGPM defined the meter as the length of the path travelled by light in a vacuum during a time interval of 1/299,792,458 of a second.[15][16]

Precision tests of quantum electrodynamics

The hyperfine splitting in hydrogen and in muonium have been used to measure the value of the fine-structure constant α. Comparison with measurements of α in other physical systems provides a stringent test of QED.

Qubit in ion-trap quantum computing

The hyperfine states of a trapped ion are commonly used for storing qubits in ion-trap quantum computing. They have the advantage of having very long lifetimes, experimentally exceeding ~10 minutes (compared to ~1 s for metastable electronic levels).

The frequency associated with the states' energy separation is in the microwave region, making it possible to drive hyperfine transitions using microwave radiation. However, at present no emitter is available that can be focused to address a particular ion from a sequence. Instead, a pair of laser pulses can be used to drive the transition, by having their frequency difference (detuning) equal to the required transition's frequency. This is essentially a stimulated Raman transition. In addition, near-field gradients have been exploited to individually address two ions separated by approximately 4.3 micrometers directly with microwave radiation.[17]

See also

References

  1. ^ E. Fermi (1930), “Uber die magnetischen Momente der Atomkerne”. Z. Physik 60, 320-333.
  2. ^ a b Woodgate, Gordon K. (1999). Elementary Atomic Structure. Oxford University Press. ISBN 978-0-19-851156-4.
  3. ^ a b c Jackson, John D. (1998). Classical Electrodynamics. Wiley. ISBN 978-0-471-30932-1.
  4. ^ Garg, Anupam (2012). Classical Electromagnetism in a Nutshell. Princeton University Press. ISBN 978-0-691-13018-7. See Sec. 26.
  5. ^ C. E. Soliverez (1980) J. Phys. C: Solid State Phys. 13 L1017. [1] doi:10.1088/0022-3719/13/34/002
  6. ^ Woodgate, Gordon K. (1983). Elementary Atomic Structure. ISBN 978-0-19-851156-4. Retrieved 2009-03-03.
  7. ^ a b Enge, Harald A. (1966). Introduction to Nuclear Physics. Addison Wesley. ISBN 978-0-201-01870-7.
  8. ^ Y. Millot (2008-02-19). "Electric field gradient tensor around quadrupolar nuclei". Retrieved 2008-07-23.
  9. ^ Frosch and Foley; Foley, H. (1952). "Magnetic hyperfine structure in diatomics". Physical Review. 88 (6): 1337–1349. Bibcode:1952PhRv...88.1337F. doi:10.1103/PhysRev.88.1337.
  10. ^ Brown, John; Alan Carrington (2003). Rotational Spectroscopy of Diatomic Molecules. Cambridge University Press. ISBN 978-0-521-53078-1.
  11. ^ a b Brown, John; Alan Carrington (2003). Rotational Spectroscopy of Diatomic Molecules. ISBN 978-0-521-53078-1. Retrieved 2009-03-03.
  12. ^ Ahrens, V.; Lewen, F.; Takano, S.; Winnewisser, G.; et al. (2002). "Sub-Doppler Saturation Spectroscopy of HCN up to 1 THz and Detection of   Emission from TMC-1". Z. Naturforsch. 57a (8): 669–681. Bibcode:2002ZNatA..57..669A. doi:10.1515/zna-2002-0806. S2CID 35586070.
  13. ^ a b Mullins, A. M.; Loughnane, R. M.; Redman, M. P.; et al. (2016). "Radiative Transfer of HCN: Interpreting observations of hyperfine anomalies". Monthly Notices of the Royal Astronomical Society. 459 (3): 2882–2993. arXiv:1604.03059. Bibcode:2016MNRAS.459.2882M. doi:10.1093/mnras/stw835. S2CID 119192931.
  14. ^ Tatematsu, K.; Umemoto, T.; Kandori, R.; et al. (2004). "N2H+ Observations of Molecular Cloud Cores in Taurus". Astrophysical Journal. 606 (1): 333–340. arXiv:astro-ph/0401584. Bibcode:2004ApJ...606..333T. doi:10.1086/382862. S2CID 118956636.
  15. ^ Taylor, B.N. and Thompson, A. (Eds.). (2008a). The International System of Units (SI) 2016-06-03 at the Wayback Machine. Appendix 1, p. 70. This is the United States version of the English text of the eighth edition (2006) of the International Bureau of Weights and Measures publication Le Système International d' Unités (SI) (Special Publication 330). Gaithersburg, MD: National Institute of Standards and Technology. Retrieved 18 August 2008.
  16. ^ Taylor, B.N. and Thompson, A. (2008b). Guide for the Use of the International System of Units (Special Publication 811). Gaithersburg, MD: National Institute of Standards and Technology. Retrieved 23 August 2008.
  17. ^ Warring, U.; Ospelkaus, C.; Colombe, Y.; Joerdens, R.; Leibfried, D.; Wineland, D.J. (2013). "Individual-Ion Addressing with Microwave Field Gradients". Physical Review Letters. 110 (17): 173002 1–5. arXiv:1210.6407. Bibcode:2013PhRvL.110q3002W. doi:10.1103/PhysRevLett.110.173002. PMID 23679718. S2CID 27008582.

External links

  • The Feynman Lectures on Physics Vol. III Ch. 12: The Hyperfine Splitting in Hydrogen
  •   Nuclear Magnetic and Electric Moments lookup—Nuclear Structure and Decay Data at the IAEA

hyperfine, structure, atomic, physics, hyperfine, structure, defined, small, shifts, otherwise, degenerate, energy, levels, resulting, splittings, those, energy, levels, atoms, molecules, ions, electromagnetic, multipole, interaction, between, nucleus, electro. In atomic physics hyperfine structure is defined by small shifts in otherwise degenerate energy levels and the resulting splittings in those energy levels of atoms molecules and ions due to electromagnetic multipole interaction between the nucleus and electron clouds In atoms hyperfine structure arises from the energy of the nuclear magnetic dipole moment interacting with the magnetic field generated by the electrons and the energy of the nuclear electric quadrupole moment in the electric field gradient due to the distribution of charge within the atom Molecular hyperfine structure is generally dominated by these two effects but also includes the energy associated with the interaction between the magnetic moments associated with different magnetic nuclei in a molecule as well as between the nuclear magnetic moments and the magnetic field generated by the rotation of the molecule Hyperfine structure contrasts with fine structure which results from the interaction between the magnetic moments associated with electron spin and the electrons orbital angular momentum Hyperfine structure with energy shifts typically orders of magnitudes smaller than those of a fine structure shift results from the interactions of the nucleus or nuclei in molecules with internally generated electric and magnetic fields Schematic illustration of fine and hyperfine structure in a neutral hydrogen atom Contents 1 History 2 Theory 2 1 Atomic hyperfine structure 2 1 1 Magnetic dipole 2 1 2 Electric quadrupole 2 2 Molecular hyperfine structure 2 2 1 Direct nuclear spin spin 2 2 2 Nuclear spin rotation 2 2 3 Small molecule hyperfine structure 3 Measurements 4 Applications 4 1 Astrophysics 4 2 Nuclear spectroscopy 4 3 Nuclear technology 4 4 Use in defining the SI second and meter 4 5 Precision tests of quantum electrodynamics 4 6 Qubit in ion trap quantum computing 5 See also 6 References 7 External linksHistory EditThe first theory of atomic hyperfine structure was given in 1930 by Enrico Fermi 1 for an atom containing a single valence electron with an arbitrary angular momentum The Zeeman splitting of this structure was discussed by S A Goudsmit and R F Bacher later that year In 1935 H Schuler and Theodor Schmidt proposed the existence of a nuclear quadrupole moment in order to explain anomalies in the hyperfine structure citation needed Theory EditThe theory of hyperfine structure comes directly from electromagnetism consisting of the interaction of the nuclear multipole moments excluding the electric monopole with internally generated fields The theory is derived first for the atomic case but can be applied to each nucleus in a molecule Following this there is a discussion of the additional effects unique to the molecular case Atomic hyperfine structure Edit Magnetic dipole Edit Main article Dipole The dominant term in the hyperfine Hamiltonian is typically the magnetic dipole term Atomic nuclei with a non zero nuclear spin I displaystyle mathbf I have a magnetic dipole moment given by m I g I m N I displaystyle boldsymbol mu text I g text I mu text N mathbf I where g I displaystyle g text I is the g factor and m N displaystyle mu text N is the nuclear magneton There is an energy associated with a magnetic dipole moment in the presence of a magnetic field For a nuclear magnetic dipole moment mI placed in a magnetic field B the relevant term in the Hamiltonian is given by 2 H D m I B displaystyle hat H text D boldsymbol mu text I cdot mathbf B In the absence of an externally applied field the magnetic field experienced by the nucleus is that associated with the orbital ℓ and spin s angular momentum of the electrons B B el B el ℓ B el s displaystyle mathbf B equiv mathbf B text el mathbf B text el ell mathbf B text el s Electron orbital angular momentum results from the motion of the electron about some fixed external point that we shall take to be the location of the nucleus The magnetic field at the nucleus due to the motion of a single electron with charge e at a position r relative to the nucleus is given by B el ℓ m 0 4 p e v r r 3 displaystyle mathbf B text el ell frac mu 0 4 pi frac e mathbf v times mathbf r r 3 where r gives the position of the nucleus relative to the electron Written in terms of the Bohr magneton this gives B el ℓ 2 m B m 0 4 p 1 r 3 r m e v ℏ displaystyle mathbf B text el ell 2 mu text B frac mu 0 4 pi frac 1 r 3 frac mathbf r times m text e mathbf v hbar Recognizing that mev is the electron momentum p and that r p ħ is the orbital angular momentum in units of ħ ℓ we can write B el ℓ 2 m B m 0 4 p 1 r 3 ℓ displaystyle mathbf B text el ell 2 mu text B frac mu 0 4 pi frac 1 r 3 mathbf ell For a many electron atom this expression is generally written in terms of the total orbital angular momentum L displaystyle mathbf L by summing over the electrons and using the projection operator f i ℓ displaystyle varphi i ell where i ℓ i i f i ℓ L textstyle sum i mathbf ell i sum i varphi i ell mathbf L For states with a well defined projection of the orbital angular momentum Lz we can write f i ℓ ℓ z i L z displaystyle varphi i ell hat ell z i L z giving B el ℓ 2 m B m 0 4 p 1 L z i ℓ z i r i 3 L displaystyle mathbf B text el ell 2 mu text B frac mu 0 4 pi frac 1 L z sum i frac hat ell zi r i 3 mathbf L The electron spin angular momentum is a fundamentally different property that is intrinsic to the particle and therefore does not depend on the motion of the electron Nonetheless it is angular momentum and any angular momentum associated with a charged particle results in a magnetic dipole moment which is the source of a magnetic field An electron with spin angular momentum s has a magnetic moment ms given by m s g s m B s displaystyle boldsymbol mu text s g s mu text B mathbf s where gs is the electron spin g factor and the negative sign is because the electron is negatively charged consider that negatively and positively charged particles with identical mass travelling on equivalent paths would have the same angular momentum but would result in currents in the opposite direction The magnetic field of a point dipole moment ms is given by 3 4 B el s m 0 4 p r 3 3 m s r r m s 2 m 0 3 m s d 3 r displaystyle mathbf B text el s frac mu 0 4 pi r 3 left 3 left boldsymbol mu text s cdot hat mathbf r right hat mathbf r boldsymbol mu text s right dfrac 2 mu 0 3 boldsymbol mu text s delta 3 mathbf r The complete magnetic dipole contribution to the hyperfine Hamiltonian is thus given by H D 2 g I m N m B m 0 4 p 1 L z i l z i r i 3 I L g I m N g s m B m 0 4 p 1 S z i s z i r i 3 3 I r S r I S 2 3 g I m N g s m B m 0 1 S z i s z i d 3 r i I S displaystyle begin aligned hat H D amp 2g text I mu text N mu text B dfrac mu 0 4 pi dfrac 1 L z sum i dfrac hat l zi r i 3 mathbf I cdot mathbf L amp g text I mu text N g text s mu text B frac mu 0 4 pi frac 1 S z sum i frac hat s zi r i 3 left 3 left mathbf I cdot hat mathbf r right left mathbf S cdot hat mathbf r right mathbf I cdot mathbf S right amp frac 2 3 g text I mu text N g text s mu text B mu 0 frac 1 S z sum i hat s zi delta 3 left mathbf r i right mathbf I cdot mathbf S end aligned The first term gives the energy of the nuclear dipole in the field due to the electronic orbital angular momentum The second term gives the energy of the finite distance interaction of the nuclear dipole with the field due to the electron spin magnetic moments The final term often known as the Fermi contact term relates to the direct interaction of the nuclear dipole with the spin dipoles and is only non zero for states with a finite electron spin density at the position of the nucleus those with unpaired electrons in s subshells It has been argued that one may get a different expression when taking into account the detailed nuclear magnetic moment distribution 5 For states with ℓ 0 displaystyle ell neq 0 this can be expressed in the form H D 2 g I m B m N m 0 4 p I N r 3 displaystyle hat H D 2g I mu text B mu text N dfrac mu 0 4 pi dfrac mathbf I cdot mathbf N r 3 where N ℓ g s 2 s 3 s r r displaystyle mathbf N mathbf ell frac g s 2 left mathbf s 3 mathbf s cdot hat mathbf r hat mathbf r right 2 If hyperfine structure is small compared with the fine structure sometimes called IJ coupling by analogy with LS coupling I and J are good quantum numbers and matrix elements of H D displaystyle hat H text D can be approximated as diagonal in I and J In this case generally true for light elements we can project N onto J where J L S is the total electronic angular momentum and we have 6 H D 2 g I m B m N m 0 4 p N J J J I J r 3 displaystyle hat H text D 2g I mu text B mu text N dfrac mu 0 4 pi dfrac mathbf N cdot mathbf J mathbf J cdot mathbf J dfrac mathbf I cdot mathbf J r 3 This is commonly written as H D A I J displaystyle hat H text D hat A mathbf I cdot mathbf J with A textstyle left langle hat A right rangle being the hyperfine structure constant which is determined by experiment Since I J 1 2 F F I I J J where F I J is the total angular momentum this gives an energy of D E D 1 2 A F F 1 I I 1 J J 1 displaystyle Delta E text D frac 1 2 left langle hat A right rangle F F 1 I I 1 J J 1 In this case the hyperfine interaction satisfies the Lande interval rule Electric quadrupole Edit Main article Quadrupole Atomic nuclei with spin I 1 displaystyle I geq 1 have an electric quadrupole moment 7 In the general case this is represented by a rank 2 tensor Q displaystyle underline underline Q with components given by 3 Q i j 1 e 3 x i x j r 2 d i j r r d 3 r displaystyle Q ij frac 1 e int left 3x i prime x j prime left r prime right 2 delta ij right rho left mathbf r prime right d 3 r prime where i and j are the tensor indices running from 1 to 3 xi and xj are the spatial variables x y and z depending on the values of i and j respectively dij is the Kronecker delta and r r is the charge density Being a 3 dimensional rank 2 tensor the quadrupole moment has 32 9 components From the definition of the components it is clear that the quadrupole tensor is a symmetric matrix Qij Qji that is also traceless SiQii 0 giving only five components in the irreducible representation Expressed using the notation of irreducible spherical tensors we have 3 T m 2 Q 4 p 5 r r r 2 Y m 2 8 f d 3 r displaystyle T m 2 Q sqrt frac 4 pi 5 int rho left mathbf r prime right left r prime right 2 Y m 2 left theta prime varphi prime right d 3 r prime The energy associated with an electric quadrupole moment in an electric field depends not on the field strength but on the electric field gradient confusingly labelled q textstyle underline underline q another rank 2 tensor given by the outer product of the del operator with the electric field vector q E displaystyle underline underline q nabla otimes mathbf E with components given by q i j 2 V x i x j displaystyle q ij frac partial 2 V partial x i partial x j Again it is clear this is a symmetric matrix and because the source of the electric field at the nucleus is a charge distribution entirely outside the nucleus this can be expressed as a 5 component spherical tensor T 2 q displaystyle T 2 q with 8 T 0 2 q 6 2 q z z T 1 2 q q x z i q y z T 2 2 q 1 2 q x x q y y i q x y displaystyle begin aligned T 0 2 q amp frac sqrt 6 2 q zz T 1 2 q amp q xz iq yz T 2 2 q amp frac 1 2 q xx q yy iq xy end aligned where T m 2 q 1 m T m 2 q displaystyle T m 2 q 1 m T m 2 q The quadrupolar term in the Hamiltonian is thus given by H Q e T 2 Q T 2 q e m 1 m T m 2 Q T m 2 q displaystyle hat H Q eT 2 Q cdot T 2 q e sum m 1 m T m 2 Q T m 2 q A typical atomic nucleus closely approximates cylindrical symmetry and therefore all off diagonal elements are close to zero For this reason the nuclear electric quadrupole moment is often represented by Qzz 7 Molecular hyperfine structure Edit The molecular hyperfine Hamiltonian includes those terms already derived for the atomic case with a magnetic dipole term for each nucleus with I gt 0 displaystyle I gt 0 and an electric quadrupole term for each nucleus with I 1 displaystyle I geq 1 The magnetic dipole terms were first derived for diatomic molecules by Frosch and Foley 9 and the resulting hyperfine parameters are often called the Frosch and Foley parameters In addition to the effects described above there are a number of effects specific to the molecular case 10 Direct nuclear spin spin Edit Each nucleus with I gt 0 displaystyle I gt 0 has a non zero magnetic moment that is both the source of a magnetic field and has an associated energy due to the presence of the combined field of all of the other nuclear magnetic moments A summation over each magnetic moment dotted with the field due to each other magnetic moment gives the direct nuclear spin spin term in the hyperfine Hamiltonian H I I displaystyle hat H II 11 H I I a a m a B a displaystyle hat H II sum alpha neq alpha prime boldsymbol mu alpha cdot mathbf B alpha prime where a and a are indices representing the nucleus contributing to the energy and the nucleus that is the source of the field respectively Substituting in the expressions for the dipole moment in terms of the nuclear angular momentum and the magnetic field of a dipole both given above we have H I I m 0 m N 2 4 p a a g a g a R a a 3 I a I a 3 I a R a a I a R a a displaystyle hat H II dfrac mu 0 mu text N 2 4 pi sum alpha neq alpha prime frac g alpha g alpha prime R alpha alpha prime 3 left mathbf I alpha cdot mathbf I alpha prime 3 left mathbf I alpha cdot hat mathbf R alpha alpha prime right left mathbf I alpha prime cdot hat mathbf R alpha alpha prime right right Nuclear spin rotation Edit The nuclear magnetic moments in a molecule exist in a magnetic field due to the angular momentum T R is the internuclear displacement vector associated with the bulk rotation of the molecule 11 thus H IR e m 0 m N ℏ 4 p a a 1 R a a 3 Z a g a M a I a Z a g a M a I a T displaystyle hat H text IR frac e mu 0 mu text N hbar 4 pi sum alpha neq alpha prime frac 1 R alpha alpha prime 3 left frac Z alpha g alpha prime M alpha mathbf I alpha prime frac Z alpha prime g alpha M alpha prime mathbf I alpha right cdot mathbf T Small molecule hyperfine structure Edit A typical simple example of the hyperfine structure due to the interactions discussed above is in the rotational transitions of hydrogen cyanide 1H12C14N in its ground vibrational state Here the electric quadrupole interaction is due to the 14N nucleus the hyperfine nuclear spin spin splitting is from the magnetic coupling between nitrogen 14N IN 1 and hydrogen 1H IH 1 2 and a hydrogen spin rotation interaction due to the 1H nucleus These contributing interactions to the hyperfine structure in the molecule are listed here in descending order of influence Sub doppler techniques have been used to discern the hyperfine structure in HCN rotational transitions 12 The dipole selection rules for HCN hyperfine structure transitions are D J 1 displaystyle Delta J 1 D F 0 1 displaystyle Delta F 0 pm 1 where J is the rotational quantum number and F is the total rotational quantum number inclusive of nuclear spin F J I N displaystyle F J I text N respectively The lowest transition J 1 0 displaystyle J 1 rightarrow 0 splits into a hyperfine triplet Using the selection rules the hyperfine pattern of J 2 1 displaystyle J 2 rightarrow 1 transition and higher dipole transitions is in the form of a hyperfine sextet However one of these components D F 1 displaystyle Delta F 1 carries only 0 6 of the rotational transition intensity in the case of J 2 1 displaystyle J 2 rightarrow 1 This contribution drops for increasing J So from J 2 1 displaystyle J 2 rightarrow 1 upwards the hyperfine pattern consists of three very closely spaced stronger hyperfine components D J 1 displaystyle Delta J 1 D F 1 displaystyle Delta F 1 together with two widely spaced components one on the low frequency side and one on the high frequency side relative to the central hyperfine triplet Each of these outliers carry 1 2 J 2 displaystyle tfrac 1 2 J 2 J is the upper rotational quantum number of the allowed dipole transition the intensity of the entire transition For consecutively higher J transitions there are small but significant changes in the relative intensities and positions of each individual hyperfine component 13 Measurements EditHyperfine interactions can be measured among other ways in atomic and molecular spectra and in electron paramagnetic resonance spectra of free radicals and transition metal ions Applications EditAstrophysics Edit The hyperfine transition as depicted on the Pioneer plaque As the hyperfine splitting is very small the transition frequencies are usually not located in the optical but are in the range of radio or microwave also called sub millimeter frequencies Hyperfine structure gives the 21 cm line observed in H I regions in interstellar medium Carl Sagan and Frank Drake considered the hyperfine transition of hydrogen to be a sufficiently universal phenomenon so as to be used as a base unit of time and length on the Pioneer plaque and later Voyager Golden Record In submillimeter astronomy heterodyne receivers are widely used in detecting electromagnetic signals from celestial objects such as star forming core or young stellar objects The separations among neighboring components in a hyperfine spectrum of an observed rotational transition are usually small enough to fit within the receiver s IF band Since the optical depth varies with frequency strength ratios among the hyperfine components differ from that of their intrinsic or optically thin intensities these are so called hyperfine anomalies often observed in the rotational transitions of HCN 13 Thus a more accurate determination of the optical depth is possible From this we can derive the object s physical parameters 14 Nuclear spectroscopy Edit In nuclear spectroscopy methods the nucleus is used to probe the local structure in materials The methods mainly base on hyperfine interactions with the surrounding atoms and ions Important methods are nuclear magnetic resonance Mossbauer spectroscopy and perturbed angular correlation Nuclear technology Edit The atomic vapor laser isotope separation AVLIS process uses the hyperfine splitting between optical transitions in uranium 235 and uranium 238 to selectively photo ionize only the uranium 235 atoms and then separate the ionized particles from the non ionized ones Precisely tuned dye lasers are used as the sources of the necessary exact wavelength radiation Use in defining the SI second and meter Edit The hyperfine structure transition can be used to make a microwave notch filter with very high stability repeatability and Q factor which can thus be used as a basis for very precise atomic clocks The term transition frequency denotes the frequency of radiation corresponding to the transition between the two hyperfine levels of the atom and is equal to f DE h where DE is difference in energy between the levels and h is the Planck constant Typically the transition frequency of a particular isotope of caesium or rubidium atoms is used as a basis for these clocks Due to the accuracy of hyperfine structure transition based atomic clocks they are now used as the basis for the definition of the second One second is now defined to be exactly 9192 631 770 cycles of the hyperfine structure transition frequency of caesium 133 atoms On October 21 1983 the 17th CGPM defined the meter as the length of the path travelled by light in a vacuum during a time interval of 1 299 792 458 of a second 15 16 Precision tests of quantum electrodynamics Edit The hyperfine splitting in hydrogen and in muonium have been used to measure the value of the fine structure constant a Comparison with measurements of a in other physical systems provides a stringent test of QED Qubit in ion trap quantum computing Edit The hyperfine states of a trapped ion are commonly used for storing qubits in ion trap quantum computing They have the advantage of having very long lifetimes experimentally exceeding 10 minutes compared to 1 s for metastable electronic levels The frequency associated with the states energy separation is in the microwave region making it possible to drive hyperfine transitions using microwave radiation However at present no emitter is available that can be focused to address a particular ion from a sequence Instead a pair of laser pulses can be used to drive the transition by having their frequency difference detuning equal to the required transition s frequency This is essentially a stimulated Raman transition In addition near field gradients have been exploited to individually address two ions separated by approximately 4 3 micrometers directly with microwave radiation 17 See also EditDynamic nuclear polarisation Electron paramagnetic resonanceReferences Edit E Fermi 1930 Uber die magnetischen Momente der Atomkerne Z Physik 60 320 333 a b Woodgate Gordon K 1999 Elementary Atomic Structure Oxford University Press ISBN 978 0 19 851156 4 a b c Jackson John D 1998 Classical Electrodynamics Wiley ISBN 978 0 471 30932 1 Garg Anupam 2012 Classical Electromagnetism in a Nutshell Princeton University Press ISBN 978 0 691 13018 7 See Sec 26 C E Soliverez 1980 J Phys C Solid State Phys 13 L1017 1 doi 10 1088 0022 3719 13 34 002 Woodgate Gordon K 1983 Elementary Atomic Structure ISBN 978 0 19 851156 4 Retrieved 2009 03 03 a b Enge Harald A 1966 Introduction to Nuclear Physics Addison Wesley ISBN 978 0 201 01870 7 Y Millot 2008 02 19 Electric field gradient tensor around quadrupolar nuclei Retrieved 2008 07 23 Frosch and Foley Foley H 1952 Magnetic hyperfine structure in diatomics Physical Review 88 6 1337 1349 Bibcode 1952PhRv 88 1337F doi 10 1103 PhysRev 88 1337 Brown John Alan Carrington 2003 Rotational Spectroscopy of Diatomic Molecules Cambridge University Press ISBN 978 0 521 53078 1 a b Brown John Alan Carrington 2003 Rotational Spectroscopy of Diatomic Molecules ISBN 978 0 521 53078 1 Retrieved 2009 03 03 Ahrens V Lewen F Takano S Winnewisser G et al 2002 Sub Doppler Saturation Spectroscopy of HCN up to 1 THz and Detection of J 3 2 4 3 displaystyle J ce 3 gt 2 4 gt 3 Emission from TMC 1 Z Naturforsch 57a 8 669 681 Bibcode 2002ZNatA 57 669A doi 10 1515 zna 2002 0806 S2CID 35586070 a b Mullins A M Loughnane R M Redman M P et al 2016 Radiative Transfer of HCN Interpreting observations of hyperfine anomalies Monthly Notices of the Royal Astronomical Society 459 3 2882 2993 arXiv 1604 03059 Bibcode 2016MNRAS 459 2882M doi 10 1093 mnras stw835 S2CID 119192931 Tatematsu K Umemoto T Kandori R et al 2004 N2H Observations of Molecular Cloud Cores in Taurus Astrophysical Journal 606 1 333 340 arXiv astro ph 0401584 Bibcode 2004ApJ 606 333T doi 10 1086 382862 S2CID 118956636 Taylor B N and Thompson A Eds 2008a The International System of Units SI Archived 2016 06 03 at the Wayback Machine Appendix 1 p 70 This is the United States version of the English text of the eighth edition 2006 of the International Bureau of Weights and Measures publication Le Systeme International d Unites SI Special Publication 330 Gaithersburg MD National Institute of Standards and Technology Retrieved 18 August 2008 Taylor B N and Thompson A 2008b Guide for the Use of the International System of Units Special Publication 811 Gaithersburg MD National Institute of Standards and Technology Retrieved 23 August 2008 Warring U Ospelkaus C Colombe Y Joerdens R Leibfried D Wineland D J 2013 Individual Ion Addressing with Microwave Field Gradients Physical Review Letters 110 17 173002 1 5 arXiv 1210 6407 Bibcode 2013PhRvL 110q3002W doi 10 1103 PhysRevLett 110 173002 PMID 23679718 S2CID 27008582 External links EditThe Feynman Lectures on Physics Vol III Ch 12 The Hyperfine Splitting in Hydrogen Nuclear Magnetic and Electric Moments lookup Nuclear Structure and Decay Data at the IAEA Retrieved from https en wikipedia org w index php title Hyperfine structure amp oldid 1141579824, wikipedia, wiki, book, books, library,

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