Hamiltonian spin interaction

In species with two or more unpaired electrons, a fine structure term must be added to the spin Hamiltonian to represent electron spin-spin interactions. We confine our attention here to radicals with one unpaired electron (S = 1 /2) but will address the S > 1/2 problem in Chapter 6. 

With this spin Hamiltonian and the appropriate wave function it is relatively easy to determine (Appendix B) that the spin interactions give rise to four energy levels which are a function of the external magnetic field ... 

Now we consider thermodynamic properties of the system described by the Hamiltonian (2.4.5) it is a generalized Hamiltonian of the isotropic Ashkin-Teller model100,101 expressed in terms of interactions between pairs of spins lattice site nm of a square lattice. Hamiltonian (2.4.5) differs from the known one in that it includes not only the contribution from the four-spin interaction (the term with the coefficient J3), but also the anisotropic contribution (the term with the coefficient J2) which accounts for cross interactions of spins a m and s m between neighboring lattice sites. This term is so structured that it vanishes if there are no fluctuation interactions between cr- and s-subsystems. As a result, with sufficiently small coefficients J2, we arrive at a typical phase diagram of the isotropic Ashkin-Teller model,101 102 limited by the plausible values of coefficients in Eq. (2.4.6). At J, > J3, the phase transition line... 

Molecules in ordinary liquids average out all anisotropic spin interactions due to isotropic Brownian motions, and their NMR spectra are governed by the Hamiltonian in units of Hz due to the Zeeman interaction, the isotropic chemical shift (a) and the isotropic indirect spin-spin coupling (7)... 

Wangsness and Bloch16>17 were the first to give a quantum mechanical treatment of spin relaxation using the density matrix formalism. The system considered is a spin interacting with an external magnetic field (which we suppose here to be constant) and with a heat bath. The corresponding Hamiltonian is... 

Although the same nuclear spin interactions are present in solid-state as in solution-state NMR, the manifestations of these effects are different because, in the solid, the anisotropic contribution to the spin interactions contributes large time-independent terms to the Hamiltonian that are absent in the liquid phase. Therefore, the experimental methods employed in solids differ from the ones in the liquid state. The spin Hamiltonian for organic or biological solids can be described in the usual rotating frame as the sum of the following interactions ... 

Two distinct sources contribute to the spin Hamiltonian of the form of (6), spin-orbit coupling and spin-spin interaction. The latter, magnetic dipole-dipole interaction between the unpaired electrons, is dominant in organic molecules that do not contain heavy elements. 

Spin-forbidden nonadiabaticity, 32 25 transitions, 32 25-26 Spin Hamiltonian, 38 194 four-iron clusters, 38 459-460 matrix, 38 453 parameters, 38 447, 449 Spin interactions, heterobinuclear units, 43 186... 

In this review we shall first establish the theoretical foundations of the semi-classical theory that eventually lead to the formulation of the Breit-Pauli Hamiltonian. The latter is an approximation suited to make the connection to phenomenological model Hamiltonians like the Heisenberg Hamiltonian for the description of electronic spin-spin interactions. The complete derivations have been given in detail in Ref. (21), but turn out to be very involved and are thus scattered over many pages in Ref. (21). For this reason, we aim here at a summary that is as brief and concise as possible so that all relevant connections between different levels of approximation are evident. This allows us to connect present-day quantum chemical methods to phenomenological Hamiltonians and hence to establish and review the current status of these first-principles methods applied to transition-metal clusters. 

A special focus will be on phenomenological Hamiltonians involving electronic spin interactions. For this it is necessary to define atomic surrogate spin operators—so-called local spin operators—that may be directly related to the effective spins in... 

Up to this point, we have presented the fully relativistic Hamiltonian. Of course, we could set out to calculate energies of molecules employing this Hamiltonian. However, the various spin-spin interactions are easier described in terms of a perturbation picture rather than as excited states of the full-fledged Hamiltonian. Especially for the fully relativistic Dirac-Coulomb-Breit Hamiltonian, the latter calculations would be computationally very demanding. 

The nuclear spins give rise to additional terms in the Breit-Pauli Hamiltonian due to the interaction of the electrons with the magnetic moment of the nuclei and the electrostatic interaction with the electric quadrupole interaction of the nuclei. The magnetic interaction term of the spins with the nuclei is of the same type as the spin-spin interaction and following Abragam and Pryce (61) can be written as... 

Though the true electron spin operators were employed here as well as in the Breit-Pauli Hamiltonian, the phenomenological Spin Hamiltonian, in which the spin coupling is an exchange effect, is in sharp contrast to the Breit-Pauli Hamiltonian, that is including the (magnetic) spin-spin interactions. Since the exchange effect is an effect introduced by the Pauli principle imposed on the wave function, we may write the electron-electron interaction as an expectation value,... 

In molecules, the interaction of surrogate spins localized at the atomic centers is calculated describing a picture of spin-spin interaction of atoms. This picture became prominent for the description of the magnetic behavior of transition-metal clusters, where the coupling type (parallel or antiparallel) of surrogate spins localized at the metal centers is of interest. Once such a description is available it is possible to analyze any wave function with respect to the coupling type between the metal centers. Then, local spin operators can be employed in the Heisenberg Spin Hamiltonian. An overview over wave-function analyses for open-shell molecules with respect to local spins can be found in Ref. (118). 

Hence, for a given total spin eigenvalue S there exist 2S + 1 states that all yield the same energy but may split when magnetic fields described as spin interactions are important in the Hamiltonian. The individual spin states are referred to as the S = 0 singlet state with 2S + 1 = 1, as doublet S — j with 2S + 1 = 2, as triplet S = 1 with 2S + 1 = 3, and so on. 

With the inclusion of spin-spin interaction, the NMR Hamiltonian (8.27) for a molecule with two magnetic nuclei in chemically different environments becomes... 

The decomposition eq. (2-6) of the spin-free space FSP induces a decomposition on the Pauli-allowed portion of the Hilbert space of the Hamiltonian H of eq. (2-1). The Hamiltonian H which includes spin interactions may operate on any ket of the space Fsp V", where V is the electronic spin space. Here the symbol indicates a tensor product, so that Fsp Va consists of all spatial-spin kets which are composed of linear combinations of a simple product of a spatial ket of FSP and a spin ket of Va. The Pauli-allowed portion of the total A-electron Hilbert space of is... 

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