Operator total electronic angular momentum

Here, 2T (X) is the total (electronic) angular momentum operator, R is the intemuclear distance as before, p, is the reduced mass, and A is the component of X along the molecular axis. The ladder operators and °U, are explicitly given as follows ... 

The operator J for the total electronic angular momentum commutes with the atomic Hamiltonian, and we may characterize an atomic state by a quantum number /, which has the possible values [Eq. (11.39)]... 

For the electro-nuclear model, it is the charge the only homogeneous element between electron and nuclear states. The electronic part corresponds to fermion states, each one represented by a 2-spinor and a space part. Thus, it has always been natural to use the Coulomb Hamiltonian Hc(q,Q) as an entity to work with. The operator includes the electronic kinetic energy (Ke) and all electrostatic interaction operators (Vee + VeN + Vnn)- In fact this is a key operator for describing molecular physics events [1-3]. Let us consider the electronic space problem first exact solutions exist for this problem the wavefunctions are defined as /(q) do not mix up these functions with the previous electro-nuclear wavefunctions. At this level. He and S (total electronic spin operator) commute the spin operator appears in the kinematic operator V and H commute with the total angular momentum J=L+S in the I-ffame L is the total orbital angular momentum, the system is referred to a unique origin. 

The operator of total quasispin angular momentum of the shell can be obtained by the vectorial coupling of quasispin momenta of all the pairing states. For a shell of equivalent electrons, instead of (15.35) we have... 

Thus, the use of wave function in the form (23.67) and operators in the form (23.62)—(23.66) makes it possible to separate the dependence of multi-configuration matrix elements on the total number of electrons using the Wigner-Eckart theorem, and to regard this form of superposition-of-configuration approximation itself as a one-configuration approximation in the space of total quasispin angular momentum. 

Here, as elsewhere, the subscripts i and a stand for electrons and nuclei respectively. The factor (S Si)/S(S + 1) is used to project the contribution from each open shell electron i onto the total spin angular momentum S. We remind ourselves that the effective Hamiltonian is constructed to operate within an electronic state with a given multiplicity (2S +1). 

Well-known realizations of the generators of this Lie algebra are given by the three components of the orbital angular momentum vector L = r x p, the three components of the spin S = a realized in terms of the Pauli spin matrices (Schiff, 1968), or the total one-electron angular momentum J = L + S. The components of each of these vector operators satisfy the defining commutation relations Eq. (4) if we use atomic units. We should also note that the vector cross-product example mentioned earlier also satisfies Eq. (4) if we define E = iey, j = 1, 2, 3. 

It is a fundamental fact of quantum mechanics, that a spin-independent Hamiltonian will have pure spin eigenstates. For approximate wave functions that do not fulfill this criterion, e.g. those obtained with various unrestricted methods, the expectation value of the square of the total spin angular momentum operator, (5 ), has been used as a measure of the degree of spin contamination. is obviously a two-electron operator and the evaluation of its expectation value thus requires knowledge of the two-electron density matrix. 

Stone applied similar reasoning to the problem of a three-dimensional cluster. Here, the solutions of the corresponding free-particle problem for an electron-on-a-sphere are spherical harmonics. These functions should be familiar because they also describe the angular properties of atomic orbitals.Two quantum numbers, L and M, are associated with the spherical harmonics, Yim 0,total orbital angular momentum and its projection on the z-axis, respectively. It is more convenient to use the real linear combinations of Yim 9,(p)dinA (except when M = 0), and... 

Many molecular hamiltonians commute with the total spin angular momentum operator, a fact that leads to the consideration of transformation properties of electron field operators under rotations in spin space. Basis functions, natural for such studies, are... 

A model hamiltonian should have the structure of the full hamiltonian, but could in principle have terms consisting of higher order products of annihilation and creation operators. Here we limit considerations to such operators that contain a one-electron part and an electron-electron interaction part. The number of independent matrix elements can be considerably reduced by symmetry considerations and by requiring compatibility with other operator representatives. It is clear that the form of the spectral density requires that the hamiltonian commutes with the total orbital angular momentum and with various spin operators. These are given in the limited basis as... 

We have based the discussion on a scheme in which we first added the individual electronic orbital angular momenta to form a total-orbital-angular-momentum vector and did the same for the spins L = S,- L, and S = 2i S,. We then combined L and S to get J. This scheme is called Russell-Saunders couplit (or L-S coupling) and is appropriate where the spin-orbit interaction energy is small compared with the interelec-tronic repulsion energy. The operators L and S commute with + W,ep, but when is included in the Hamiltonian, L and no longer commute with H. (J does commute with + //rep + Q ) If the spin-orbit interaction is small, then L and S almost commute with (t, and L-S coupling is valid. 

In these expressions, the operators appearing on the left hand side are, respectively, the hamiltonian of the system, the square and the laboratory-fixed z-component of its total spacial angular momentum, and the electron exchange and... 

In a many-electron system, the total spin angular momentum operator is simply the vector sum of the spin vectors of each of the electrons... 

We can operate quite analogously with spin angular momentums. As i = 1/2 and N is the number of electrons, the total spin angular momentums S can accept the values... 

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