Hamiltonian linear

Dirac s theory therefore leads to a Hamiltonian linear in the space and time variables, but with coefficients that do not commute. It turns out that these coefficients can be represented as 4 x 4 matrices, related in turn to the well-known Pauli spin matrices. I have focused on electrons in the discussion it can be shown... 

G. Constraints on Off-Diagonal Elements from Other Positive-Definite Hamiltonians Linear Inequalities from the Spatial Representation Linking the Orbital and Spatial Representations... 

Let the ground state of the lanthanide ion be the BCramers doublet (effective spin S=5). Then the spin Hamiltonian, linear in lattice strains, is given in eq. (116). In accordance with eq. (233) we obtain the parastriction due to the strain modulation of the doublet shift and splitting as follows... 

In relation to the above, a brief account will be given here of the Jahn-Teller effect.When the electronic level of a molecule is degenerate at a structure of high symmetry, this structure is generally unstable and nuclear displacement may remove the degeneracy to stabilize the system. Distortion due to the effect will take place as the result of the terms of the vibrational Hamiltonian linear in the normal coordinates. 

The translational linear momentum is conserved for an isolated molecule in field free space and, as we see below, this is closely related to the fact that the molecular Hamiltonian connmites with all... 

Perturbation theory is also used to calculate free energy differences between distinct systems by computer simulation. This computational alchemy is accomplished by the use of a switching parameter X, ranging from zero to one, that transfonns tire Hamiltonian of one system to the other. The linear relation... 

Linear response theory is an example of a microscopic approach to the foundations of non-equilibrium thennodynamics. It requires knowledge of tire Hamiltonian for the underlying microscopic description. In principle, it produces explicit fomuilae for the relaxation parameters that make up the Onsager coefficients. In reality, these expressions are extremely difficult to evaluate and approximation methods are necessary. Nevertheless, they provide a deeper insight into the physics. 

The linear response of a system is detemiined by the lowest order effect of a perturbation on a dynamical system. Fomially, this effect can be computed either classically or quantum mechanically in essentially the same way. The connection is made by converting quantum mechanical conmuitators into classical Poisson brackets, or vice versa. Suppose tliat the system is described by Hamiltonian where denotes an... 

The usual context for linear response theory is that the system is prepared in the infinite past, —> -x, to be in equilibrium witii Hamiltonian H and then is turned on. This means that pit ) is given by the canonical density matrix... 

The diabatic LHSFs are not allowed to diverge anywhere on the half-sphere of fixed radius p. This boundary condition furnishes the quantum numhers n - and each of which is 2D since the reference Hamiltonian hj has two angular degrees of freedom. The superscripts n(, Q in Eq. (95), with n refering to the union of and indicate that the number of linearly independent solutions of Eqs. (94) is equal to the number of diabatic LHSFs used in the expansions of Eq. (95). 

Yarkoni [108] developed a computational method based on a perturbative approach [109,110], He showed that in the near vicinity of a conical intersection, the Hamiltonian operator may be written as the sum a nonperturbed Hamiltonian Hq and a linear perturbative temr. The expansion is made around a nuclear configuration Q, at which an intersection between two electronic wave functions takes place. The task is to find out under what conditions there can be a crossing at a neighboring nuclear configuration Qy. The diagonal Hamiltonian matrix elements at Qy may be written as... 

Until now we have implicitly assumed that our problem is formulated in a space-fixed coordinate system. However, electronic wave functions are naturally expressed in the system bound to the molecule otherwise they generally also depend on the rotational coordinate 4>. (This is not the case for E electronic states, for which the wave functions are invariant with respect to (j> ) The eigenfunctions of the electronic Hamiltonian, v / and v , computed in the framework of the BO approximation ( adiabatic electronic wave functions) for two electronic states into which a spatially degenerate state of linear molecule splits upon bending. 

Since the form of the electronic wave functions depends also on the coordinate p (in the usual, parametric way), the matrix elements (21) are functions of it too. Thus it looks at first sight as if a lot of cumbersome computations of derivatives of the electronic wave functions have to be carried out. In this case, however, nature was merciful the matrix elements in (21) enter the Hamiltonian matrix weighted with the rotational constant A, which tends to infinity when the molecule reaches linear geometry. This means that only the form of the wave functions, that is, of the matrix elements in (21), in the p 0 limit are really needed. In the above mentioned one-elecbon approximation... 

Thus, for a particular value of the good quantum number K, the only possible values for I are /f A. The matrix representation of the model Hamiltonian in the linear basis, obtained by integrating over the electronic coordinates and is thus... 

In Table I, 3D stands for three dimensional. The symbol symbol in connection with the bending potentials means that the bending potentials are considered in the lowest order approximation as already realized by Renner [7], the splitting of the adiabatic potentials has a p dependence at small distortions of linearity. With exact fomi of the spin-orbit part of the Hamiltonian we mean the microscopic (i.e., nonphenomenological) many-elecbon counterpart of, for example, The Breit-Pauli two-electron operator [22] (see also [23]). 

The appearance of the (normally small) linear term in Vis a consequence of the use of reference, instead of equilibrium configuration]. Because the stretching vibrational displacements are of small amplitude, the series in Eqs. (40) should converge quickly. The zeroth-order Hamiltonian is obtained by neglecting all but the leading terms in these expansions, pjjjf and Vo(p) + 1 /2X) rl2r and has the... 

The expressions for the rotational energy levels (i.e., also involving the end-over-end rotations, not considered in the previous works) of linear triatomic molecules in doublet and triplet II electronic states that take into account a spin orbit interaction and a vibronic coupling were derived in two milestone studies by Hougen [72,32]. In them, the isomorfic Hamiltonian was inboduced, which has later been widely used in treating linear molecules (see, e.g., [55]). 

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