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Nature

Magnetic Susceptibilities and Dielectric Constants in the New Quantum Mechanics

John Hasbrouck Van Vleck

Published Aug 1, 1926• 35 citations
Publisher
DOI
10.1038/118226c0

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Enrico Fermi

Nature•Dec 18, 1926•10 citations

On Dielectric Constants and Magnetic Susceptibilities in the New Quantum Mechanics Part III—Application to Dia- and Paramagnetism

John Hasbrouck Van Vleck

1.General mathematical theory.---Modifications are given in the general derivation of the Langevin-Debye formula by means of quantum mechanics published in part I which are required by the moment now being magnetic rather than electric. The main additions are the appearance of a diamagnetic term, and allowance for the fact that the magnetic moment consists of two parts arising respectively from orbital electronic motions and from the electrons' internal spins. These parts cannot always be treated as rigidly coupled to form a "permanent" resultant moment. The Hamiltonian function used for the internal spin is that of a spherical top.2.Diamagnetism.---The writer's previous claim that Pauli's formula for the diamagnetic susceptibility can be applied to molecules as well as atoms is shown to be invalid because of the anomalous fact that the square of the angular momentum, unlike the average angular momentum, does not vanish even in $S$ states when there is more than one nucleus. Pauli's formula is instead an upper limit to the diamagnetism in non-monatomic molecules and is a good approximation when the Schr\"odinger wave function has nearly as much symmetry as in an atomic $S$ state.3.Paramagnetism of atoms.---Limiting values for the paramagnetic susceptibilities of atoms are $\ensuremath{\chi}=N\frac{[4s(s+1)+k(k+1)]{\ensuremath{\beta}}^{2}}{3kT}$ and $\ensuremath{\chi}=[\frac{N{g}^{2}j(j+1){\ensuremath{\beta}}^{2}}{3kT}]+N\ensuremath{\alpha}$ where $\ensuremath{\beta}$ is the Bohr magneton and $\ensuremath{\alpha}$ is a constant. These two formulas are rigorously applicable when the multiplet intervals are respectively very small or very large compared to $\mathrm{kT}$, and are valid regardless of whether the magnetic field is strong enough to change the quantization by producing a Paschen-Back effect. The formula for small multiplets yields susceptibilities slightly different from those given by Laporte and Sommerfeld's expression for this case, and is much simpler, as they overlooked the contribution of the portion of the magnetic moment which is perpendicular to the invariable axis.4.Paramagnetism of molecules.---The susceptibility is calculated on the basis of the Hund theory of molecular quantization. Formulas are given applicable to his couplings of type (a) and type (b) provided in the former the multiplet intervals are either very large or very small compared to $\mathrm{kT}$. The experimental susceptibilities for ${\mathrm{O}}_{2}$ and Cl${\mathrm{O}}_{2}$ are in accord with the assumption that the normal states are respectively $^{3}S$ and $^{2}S$ terms. In the particular case of $S$ terms the numerical results are the same in the atomic and molecular formulas, but, unlike previous theories, it is not necessary to suppose the orbits are as freely oriented in molecules as in atoms. Polyatomic molecules may have lower paramagnetic susceptibilities than diatomic ones because the dissymmetry causes large fluctuations in electronic angular momentum.5.Paramagnetism of nitic oxide.---Spectroscopists have recently found that the normal states of the NO molecule are $^{2}P$ terms separated by 120.9 ${\mathrm{cm}}^{\ensuremath{-}1}$. This permits an unambigous calculation of the susceptibility of NO which agrees with the experimental value within 1.5 per cent. Deviations from Curie's law are calculated which result from the doublet interval being comparable with $\mathrm{kT}$. These deviations should be detectable experimentally if the susceptibility of NO could be measured over a wide temperature range.

Physical Review•Apr 1, 1928•110 citations

A new expression for photoionization cross sections and its application in high density system

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A new expression for photoionization cross section has been proposed based on the Beer_Lambert's law and Maxwell equations for a material.And we also proposed a function varying with the number density of the system,which includes the local field effect and the higher_order dielectric correction to the famous formula for photoionization cross section of isolated atoms,proposed by Fano and Cooper in 1968The photoionization cross sections of solid xenon have been studied by using this alternative expression which couples the macroproperty and the quantum quantity of the photoionization system,and which makes it possible for one to study the influence of induced dipoles on the photoionization.The dielectric behaviors of the matter in condensed state under several physical conditions (given the complex dielectric constants or the model of electric susceptibility of the system) are considered using our new expression for photoionization cross sections.The results show that it is reasonable in physics to calculate the cross sections of atoms in a real system by using the accurate expression.Furthermore,the more correct the model of electric susceptibility for the real system,the more accurate the cross section obtained from our formula will be.

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Theory of Magnetism and Many-Body Quantum Mechanics

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Enhanced magnetoelectric effect near a field-driven zero-temperature quantum phase transition of the spin-1/2 Heisenberg-Ising ladder

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The magnetoelectric effect of a spin-1/2 Heisenberg-Ising ladder in the presence of external electric and magnetic fields is rigorously examined by taking into account the Katsura-Nagaosa-Balatsky mechanism. It is shown that an applied electric field may control the quantum phase transition between a Néel (stripy) ordered phase and a disordered paramagnetic phase. The staggered magnetization vanishes according to a power law with an Ising-type critical exponent 1/8, the electric polarization exhibits a weak singularity, and the dielectric susceptibility shows a logarithmic divergence at this particular quantum phase transition. The external electric field may alternatively invoke a discontinuous phase transition accompanied with abrupt jumps of the dielectric polarization and susceptibility on the assumption that the external magnetic field becomes nonzero.

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Quantum Mechanics of Magnetic Moments in External Fields

Paul L. Corio

Elsevier eBooks•Jan 1, 1967•0 citations
1.General mathematical theory.---Modifications are given in the general derivation of the Langevin-Debye formula by means of quantum mechanics published in part I which are required by the moment now being magnetic rather than electric. The main additions are the appearance of a diamagnetic term, and allowance for the fact that the magnetic moment consists of two parts arising respectively from orbital electronic motions and from the electrons' internal spins. These parts cannot always be treated as rigidly coupled to form a "permanent" resultant moment. The Hamiltonian function used for the internal spin is that of a spherical top.2.Diamagnetism.---The writer's previous claim that Pauli's formula for the diamagnetic susceptibility can be applied to molecules as well as atoms is shown to be invalid because of the anomalous fact that the square of the angular momentum, unlike the average angular momentum, does not vanish even in SSS states when there is more than one nucleus. Pauli's formula is instead an upper limit to the diamagnetism in non-monatomic molecules and is a good approximation when the Schr\"odinger wave function has nearly as much symmetry as in an atomic SSS state.3.Paramagnetism of atoms.---Limiting values for the paramagnetic susceptibilities of atoms are $\ensuremath{\chi}=N\frac{[4s(s+1)+k(k+1)]{\ensuremath{\beta}}^{2}}{3kT}$ and $\ensuremath{\chi}=[\frac{N{g}^{2}j(j+1){\ensuremath{\beta}}^{2}}{3kT}]+N\ensuremath{\alpha}$ where $\ensuremath{\beta}$ is the Bohr magneton and $\ensuremath{\alpha}$ is a constant. These two formulas are rigorously applicable when the multiplet intervals are respectively very small or very large compared to kT\mathrm{kT}kT, and are valid regardless of whether the magnetic field is strong enough to change the quantization by producing a Paschen-Back effect. The formula for small multiplets yields susceptibilities slightly different from those given by Laporte and Sommerfeld's expression for this case, and is much simpler, as they overlooked the contribution of the portion of the magnetic moment which is perpendicular to the invariable axis.4.Paramagnetism of molecules.---The susceptibility is calculated on the basis of the Hund theory of molecular quantization. Formulas are given applicable to his couplings of type (a) and type (b) provided in the former the multiplet intervals are either very large or very small compared to kT\mathrm{kT}kT. The experimental susceptibilities for O2{\mathrm{O}}_{2}O2​ and ClO2{\mathrm{O}}_{2}O2​ are in accord with the assumption that the normal states are respectively 3S^{3}S3S and 2S^{2}S2S terms. In the particular case of SSS terms the numerical results are the same in the atomic and molecular formulas, but, unlike previous theories, it is not necessary to suppose the orbits are as freely oriented in molecules as in atoms. Polyatomic molecules may have lower paramagnetic susceptibilities than diatomic ones because the dissymmetry causes large fluctuations in electronic angular momentum.5.Paramagnetism of nitic oxide.---Spectroscopists have recently found that the normal states of the NO molecule are 2P^{2}P2P terms separated by 120.9 ${\mathrm{cm}}^{\ensuremath{-}1}$. This permits an unambigous calculation of the susceptibility of NO which agrees with the experimental value within 1.5 per cent. Deviations from Curie's law are calculated which result from the doublet interval being comparable with kT\mathrm{kT}kT. These deviations should be detectable experimentally if the susceptibility of NO could be measured over a wide temperature range.
A new expression for photoionization cross section has been proposed based on the Beer_Lambert's law and Maxwell equations for a material.And we also proposed a function varying with the number density of the system,which includes the local field effect and the higher_order dielectric correction to the famous formula for photoionization cross section of isolated atoms,proposed by Fano and Cooper in 1968The photoionization cross sections of solid xenon have been studied by using this alternative expression which couples the macroproperty and the quantum quantity of the photoionization system,and which makes it possible for one to study the influence of induced dipoles on the photoionization.The dielectric behaviors of the matter in condensed state under several physical conditions (given the complex dielectric constants or the model of electric susceptibility of the system) are considered using our new expression for photoionization cross sections.The results show that it is reasonable in physics to calculate the cross sections of atoms in a real system by using the accurate expression.Furthermore,the more correct the model of electric susceptibility for the real system,the more accurate the cross section obtained from our formula will be.
The magnetoelectric effect of a spin-1/2 Heisenberg-Ising ladder in the presence of external electric and magnetic fields is rigorously examined by taking into account the Katsura-Nagaosa-Balatsky mechanism. It is shown that an applied electric field may control the quantum phase transition between a Néel (stripy) ordered phase and a disordered paramagnetic phase. The staggered magnetization vanishes according to a power law with an Ising-type critical exponent 1/8, the electric polarization exhibits a weak singularity, and the dielectric susceptibility shows a logarithmic divergence at this particular quantum phase transition. The external electric field may alternatively invoke a discontinuous phase transition accompanied with abrupt jumps of the dielectric polarization and susceptibility on the assumption that the external magnetic field becomes nonzero.