Hamiltonian problem formulation

The solution of single-particle quantum problems, formulated with the help of a matrix Hamiltonian, is possible along the usual line of finding the wave-functions on a lattice, solving the Schrodinger equation (6). The other method, namely matrix Green functions, considered in this section, was found to be more convenient for transport calculations, especially when interactions are included. 

Theoretical chemistry has two problems that remain unsolved in terms of fundamental quantum theory the physics of chemical interaction and the theoretical basis of molecular structure. The two problems are related but commonly approached from different points of view. The molecular-structure problem has been analyzed particularly well and eloquent arguments have been advanced to show that the classical idea of molecular shape cannot be accommodated within the Hilbert-space formulation of quantum theory [161, 2, 162, 163]. As a corollary it follows that the idea of a chemical bond, with its intimate link to molecular structure, is likewise unidentified within the quantum context [164]. In essence, the problem concerns the classical features of a rigid three-dimensional arrangement of atomic nuclei in a molecule. There is no obvious way to reconcile such a classical shape with the probability densities expected to emerge from the solution of a molecular Hamiltonian problem. The complete molecular eigenstate is spherically symmetrical [165] and resists reduction to lower symmetry, even in the presence of a radiation field. 

The aj therefore define the geometrical shape of the minimum in the usual way. If the minimum figure is a plane then the potential well is diffeomorphic to SO(3) while if it is non-planar then it is diffeomorphic to 0(3) and so the well is actually a symmetric double well. In either case, Klein et al show that the eigenvalues and eigenfunctions of the full problem can be obtained as WKB-type expansions to all orders of the expansion parameter, the square root of the ratio of the electronic to a typical nuclear mass. Because of the way the Hamiltonian is formulated the invariance of the Hamiltonian under permutations of the electronic variables is readily considered and the electronic wavefunction can easily be chosen in per-mutationally allowed form, no matter what the nuclear geometry happens to be. However it is much less easy to consider permutational invariance when some of... 

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. 

The problem of nonadiabatic tunneling has been already formulated in section 3.5, and in this subsection we study how dissipation affects the conclusions drawn there. The two-state Hamiltonian for the system coupled to a bath is conveniently rewritten via the Pauli matrices... 

Almost all problems that require knowledge of free energies are naturally formulated or can be framed in terms of (1.15) or (1.16). Systems 0 and 1 may differ in several ways. For example, they may be characterized by different values of a macroscopic parameter, such as the temperature. Alternatively, they may be defined by two different Hamiltonians, 3%o and 3%, as is the case in studies of free energy changes upon point mutation of one or several amino acids in a protein. Finally, the definitions of 0 and 1 can be naturally extended to describe two different, well-defined macroscopic states of the same system. Then, Q0 is defined as ... 

It applies for both formulations above that the expansion in principle contains an infinite number of terms. The convergence to a few lowest order terms relies on the ability to orderly separate influences of the dominant rf irradiation terms (through a suitable interaction frame) from the less dominant internal terms of the Hamiltonian. In principle, this may be overcome using the spectral theorem (or the Caley-Hamilton theorem [57]) providing a closed (i.e., exact) solution to the Baker-Campbell-Hausdorf problem with all dependencies included in n terms where n designates the dimension of the Hilbert-space matrix representation (e.g., 2 for a single spin-1/2, 4 for a two-spin-1/2 system) [58, 59]. 

Consequently, from the density the Hamiltonian can be readily obtained, and then every property of the system can be determined by solving the Schrodinger equation to obtain the wave function. One has to emphasize, however, that this argument holds only for Coulomb systems. By contrast, the density functional theory formulated by Hohenberg and Kohn is valid for any external potential. Kato s theorem is valid not only for the ground state but also for the excited states. Consequently, if the density n, of the f-th excited state is known, the Hamiltonian H is also known in principle and its eigenvalue problem ... 

In the classical approach, it is relatively simple to calculate the solvation energies. However, in the quantum mechanical formulations, the electronic structure of the solute molecule depends on the reaction held and the reaction held in turn depends on the structure of the solute. It is a typical nonlinear problem and has to be solved iteratively. Several approaches have been proposed for solving this problem [8-11]. All of them are based on the modihcation of the Hamiltonian in the following equation ... 

The aforementioned applications of recursive methods in reaction dynamics do not involve diagonalization explicitly. In some quantum mechanical formulations of reactive scattering problems, however, diagonalization of sub-Hamiltonian matrices is needed. Recursive diagonalizers for Hermitian and real-symmetric matrices described earlier in this chapter have been used by several authors.73,81... 

In this section, we introduce the model Hamiltonian pertaining to the molecular systems under consideration. As is well known, a curve-crossing problem can be formulated in the adiabatic as well as in a diabatic electronic representation. Depending on the system under consideration and on the specific method used, both representations have been employed in mixed quantum-classical approaches. While the diabatic representation is advantageous to model potential-energy surfaces in the vicinity of an intersection and has been used in mean-field type approaches, other mixed quantum-classical approaches such as the surfacehopping method usually employ the adiabatic representation. 

We assume for simplicity that the two-electron atom is described by a Hamiltonian (29) in which //(I) and //(2) are the hydrogen-like Dirac Hamiltonians and h, 2) = 0. Apparently, after this simplification the problem is trivial since it becomes separable to two one-electron problems. Nevertheless we present this example because it sheds some light upon formulations of the minimax principle in a many-electron case. 

The main reason why existing MR CC methods as well as related MR MBPT cannot be considered as standard or routine methods is the fact that both theories suffer from the Intruder state problem or generally from the convergence problems. As is well known, both MR MBPT/CC theories are built on the concept of the effective Hamiltonian that acts in a relatively small model or reference space and provides us with energies of several states at the same time by diagonalization of the effective Hamiltonian. In order to warrant size-extensivity, both theories employ the complete model space formulations. Although conceptually simpler, the use of the complete model space makes the calculations rather... 

In the 2-level limit a perturbative approach has been used in two famous problems the Marcus model in chemistry and the small polaron model in physics. Both models describe hopping of an electron that drags the polarization cloud that it is formed because of its electrostatic coupling to the enviromnent. This enviromnent is the solvent in the Marcus model and the crystal vibrations (phonons) in the small polaron problem. The details of the coupling and of the polarization are different in these problems, but the Hamiltonian formulation is very similar. ... 

Let us consider the 5s, 5p, 5d orbitals of lead and Is orbital of oxygen as the outercore and the ai, a2, os, tti, tt2 orbitals of PbO (consisting mainly of 6s, 6p orbitals of Pb and 2s, 2p orbitals of O) as valence. Although in the Cl calculations we take into account only the correlation between valence electrons, the accuracy attained in the Cl calculation of Ay is much better than in the RCC-SD calculation. The main problem with the RCC calculation was that the Fock-space RCC-SD version used there was not optimal in accounting for nondynamic correlations (see [136] for details of RCC-SD and Cl calculations of the Pb atom). Nevertheless, the potential of the RCC approach for electronic structure calculations is very high, especially in the framework of the intermediate Hamiltonian formulation [102, 131]. 

The model is oversimplified in the sense that we have not attempted to specify what effects are incorporated in u. We will, however, consider the main effects from the vacuum fluctuations as well as other possible perturbations needed to produce the degeneracy above as well as, if necessary, considering the weak energy dependence in the Hamiltonian referred to in Eq. (11). To see how the CPT theorem affects our formulation we note that our zero order problem is an irreducible representation of... 

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