Electrical monopole

Quadmpole interaction lifts the degeneracy of nuclear states with spin quantum numbers I > 1/2, and is manifested in the Mossbauer spectmm as quadmpole splitting A q (as will be further discussed in Sect. 4.3). According to (4.5), the classical electric monopole and quadmpole interaction energies Ei and q are additive, that is, = E + Eq. 

The electric monopole interaction between a nucleus (with mean square radius k) and its environment is a product of the nuclear charge distribution ZeR and the electronic charge density e il/ 0) at the nucleus, SE = const (4.11). However, nuclei of the same mass and charge but different nuclear states isomers) have different charge distributions ZeR eR ), because the nuclear volume and the mean square radius depend on the state of nuclear excitation R R ). Therefore, the energies of a Mossbauer nucleus in the ground state (g) and in the excited state (e) are shifted by different amounts (5 )e and (5 )g relative to those of a bare nucleus. It was recognized very early that this effect, which is schematically shown in Fig. 4.1, is responsible for the occurrence of the Mossbauer isomer shift [7]. 

Fig. 4.1 The electric monopole interaction between the nuclear charge and the electron density at the nucleus shifts the energy of the nuclear states and gives the Mossbauer isomer shift...

Fig. 4.6 Quadrupole splitting of the excited state of Fe with I = 3/2 and the resulting Mossbauer spectrum. Quadrupole interaction splits the spin quartet into two degenerate sublevels 7, OT/) with energy separation A q = 2 q. The ground state with I = 1/2 remains unsplit. The nuclear states are additionally shifted by electric monopole interaction giving rise to the isomer shift 8...

Fig. 4.9 Magnetic dipole splitting (nuclear Zeeman effect) in pe and resultant Mossbauer spectrum (schematic). The mean energy of the nuclear states is shifted by the electric monopole interaction which gives rise to the isomer shift 5. Afi. g = Sg/tN and A M,e = refer to the...

To calculate Mossbauer spectra, which consist of a finite number of discrete lines, the nuclear Hamiltonian, and thus also Hsu, has to be set up and solved independently for the nuclear ground and excited states. The electric monopole interaction, that is, the isomer shift, can be omitted here since it is additive and independent of Mj. It can subsequently be added as an increment 5 to the transition energies of each of the obtained Mossbauer lines. 

Asymmetry in the ligand environment, either geometric or in charge distribution (or both), affect the asymmetry parameter, tp An r = 0 value corresponds to complete axial symmetry, whereas r = 1 corresponds to pure rhombic symmetry. Electric monopole interactions between the nuclear charge distributions and the electrons at the nucleus cause a shift of the nuclear ground and excited states. These interactions are known as the isomer shift, 8. Both the Mossbauer source and the absorber (the sample of interest) experience an isomer shift, and it is customary to quote 8 relative to a standard, usually Fe metal or Na2[Fe(CN)5NO] 2H2O at... 

Mossbauer isomer shift and quadrupole splitting are commonly used to obtain information about the bonding environment around source nuclides. The isomer shift arises from the electric monopole interaction of the nucleus with the electrons and depends on the... 

Fig. 7.4 Top Nuclear energy levels of Fe as shifted by electrical monopole (left), or as split by electrical quadrupole (center) or by magnetic dipole interaction (right), schematized for hematite at room temperature (5 > 0 vs. a-Fe, EQ < 0, Bhf 0). Bottom Schematic Mossbauer spectra corresponding to the energy levels schematized on top (J. FriedI, unpubl.).

The electric monopole interaction is a function of the s electron densities at the nucleus. This results in a displacement of the spectrum and is expressed as the velocity of the source (mm s ) necessary to counteract the displacement. This isomer (or chemical) shift, 6, provides information about the coordination number, the valency and spin state of the iron in the compound. 

The first term in the square bracket in this equation is the electric monopole moment, which is equal to the nuclear charge, Ze. The second term in the square bracket is the electric dipole moment while the third term in the square bracket is the electric quadmpole moment. For a quantum mechanical system in a well-defined quantum state, the charge density p is an even function, and because the dipole moment involves the product of an even and an odd function, the corresponding integral is identically zero. Therefore, there should be no electric dipole moment or any other odd electric moment for nuclei. For spherical nuclei, the charge density p does not depend on 0, and thus the quadmpole moment Q is given by... 

Calculate the electric monopole, dipole, and quadmpole moments of the following arrangements of charge ... 

As a final point on the topic of selection rules, we noted that AZ = 0 is forbidden for the emission of a single photon. The electric monopole distribution (E0)... 

The nuclear ground and excited levels involved in the Mossbauer transition are shifted or split because of the electrostatic interactions between the nuclear charge and the surrounding electric charge (Fig. 2). The first interaction, sometimes called the electric monopole interaction, shifts only the nuclear levels and is related to the perturbation resulting from the electrons inside the nuclear volume. This shift is... 

Mossbauer spectroscopy senses the hyperfine interactions, which are present at the nucleus of the Mossbauer isotope. The electrical monopole interaction causes the isomer shift and the electric quadrupole interaction leads to the quadrupole splitting, which in the case of Fe causes a two-line Mossbauer pattern. The magnetic dipole interaction leads to a magnetically split six-line pattern (Figure 4). In the following text, these interactions and their deduction from Mossbauer spectra will be discussed. 

The electric monopole interaction is proportional to the s-electron density at the iron nnclens [Pg.2821]

Electric monopole (net charge). By definition, the total charge of the system is ... 

Figure 1. Hyperfine interactions for Fe nuclei, showing the nuclear energy level diagram for (a) an unperturbed nucleus (b) electric monopole interaction (isomer shift) (c) electric quadrupole interaction (quadrupole splitting) and (d) magnetic dipole interaction (hyperfine magnetic splitting). Each interaction is shown individually, accompanied by the resulting Mossbauer spectrum.

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