Hilbert space effective Hamiltonians

Produces the same Fock space effective Hamiltonian and, thus, Hilbert space h as variant a. 

First, as the molecule on which the chromophore sits rotates, this projection will change. Second, the magnitude of the transition dipole may depend on bath coordinates, which in analogy with gas-phase spectroscopy is called a non-Condon effect For water, as we will see, this latter dependence is very important [13, 14]. In principle there are off-diagonal terms in the Hamiltonian in this truncated two-state Hilbert space, which depend on the bath coordinates and which lead to vibrational energy relaxation [4]. In practice it is usually too difficult to treat both the spectral diffusion and vibrational relaxation problems at the same time, and so one usually adds the effects of this relaxation phenomenologically, and the lifetime 7j can either be calculated separately or determined from experiment. Within this approach the line shape can be written as [92 94]... 

The outline of the review is as follows in the next section (Sect. 2) we introduce the basic ideas of effective Hamiltonian theory based on the use of projection operators. The effective Hamiltonian (1-5) for the ligand field problem is constructed in several steps first by analogy with r-electron theory we use the group product function method of Lykos and Parr to define a set of n-electron wavefimctions which define a subspace of the full -particle Hilbert space in which we can give a detailed analysis of the Schrodinger equation for the full molecular Hamiltonian H (Sect. 3 and 4). This subspace consists of fully antisymmetrized product wavefimctions composed of a fixed ground state wavefunction, for the electrons in the molecule other than the electrons which are placed in states, constructed out of pure d-orbitals on the... 

The renormalized theory of the effective Hamiltonian implied by the restriction to some subspace S of the full Hilbert space also imposes a requirement for renonnalisation of expectation values of other operators (Freed ). Suppose that we have some operator B and we require its expectation value in a state 0 of the full Schrddinger Eq. (2-2) in complete analogy with the effective Hamiltonian theory described above we define an effective operator B by the requirement that its expectation value in a state A ) in the subspace should equal the exact expectation value (c.f. Eq. (2-4)),... 

The OOA, also known as Kugel-Khomskii approach, is based on the partitioning of a coupled electron-phonon system into an electron spin-orbital system and crystal lattice vibrations. Correspondingly, Hilbert space of vibronic wave functions is partitioned into two subspaces, spin-orbital electron states and crystal-lattice phonon states. A similar partitioning procedure has been applied in many areas of atomic, molecular, and nuclear physics with widespread success. It s most important advantage is the limited (finite) manifold of orbital and spin electron states in which the effective Hamiltonian operates. For the complex problem of cooperative JT effect, this partitioning simplifies its solution a lot. 

The quantum description of N coupled protons in Hilbert space is given by a spin Hamiltonian of dimension 2 equalling the number of direct product spin-i states. Two experimental tools have been used for the decoupling of spin interactions, RF irradiation and MAS. In the following, any discussion of sample spinning assumes MAS conditions. MAS effectively eliminates the CSA and DDfcetero interaction between protons and other spin-i nuclei. 

At this point we have expressed the Hamiltonian, the density operator and the evolution operator in Fourier space. We have introduced an effective Hamiltonian, defined in the Hilbert space of the same dimension 2 as the total time-dependent Hamiltonian itself, and we have shown how to transform operators between the two representations. The definition of the effective Hamiltonian enables us to predict the overall evolution of the spin system, despite the fact that we can not find time-points for synchronous detection, f, where Uint f) = exp —iWe//t In actual experiments the time dependent signals are monitored and after Fourier transformation they result in frequency sideband... 

In the sum above the values of n and k as well as n" and k" are not simultaneously zero. This second-order correction term must be added to the effective Hamiltonian in Eq. 88. To obtain this result it was not necessary to change defining Dp. Thus to obtain the effective Hamiltonian in the original spin Hilbert space, it is again sufficient to apply exp(+iS j ). Only when we are interested in higher-order terms is an additional van Vleck transformation with exp(+iS ) required. This is, however, outside the scope of our discussion here. 

Since in the Floquet representation the Hamiltonian K defined on the enlarged Hilbert space is time-independent, the analysis of the effect of perturbations (like, e.g., transition probabilities) can be done by stationary perturbation theory, instead of the usual time-dependent one. Here we will present a formulation of stationary perturbation theory based on the iteration of unitary transformations (called contact transformations or KAM transformations) constructed such that the form of the Hamiltonian gets simplified. It is referred to as the KAM technique. The results are not very different from the ones of Rayleigh-Schrodinger perturbation theory, but conceptually and in terms of speed of convergence they have some advantages. 

Some properties of the Fock space transformations W and effective Hamiltonians h and, thus, of the resulting h, appear to differ from those obtciined by Hilbert space transformations. For example, their canonical unitary W is not separable and yields an h and, thus, an h with disconnected diagrams on each degenerate subspace. However, the analogous U of Eq. (5.13) may be shown to be separable 71), and the resulting He on each complete subspace flo is fully linked , as proven by Brandow [8]. These differences are not explained. 

We define an operator as closed , if its action on any model function G P produces only internal excitations within the IMS. An operator is quasi-open , if there exists at least one model function which gets excited to the complementary model space R by its action. Obviously, both closed and quasi-open operators are all labeled by only active orbitals. An operator is open , if it involves at least one hole or particle excitation, leading to excitations to the g-space by acting on any P-space function. It was shown by Mukheijee [28] that a size-extensive formulation within the effective Hamiltonians is possible for an IMS, if the cluster operators are chosen as all possible quasi-open and open excitations, and demand that the effective Hamiltonian is a closed operator. Mukhopadhyay et al. [61] developed an analogous Hilbert-space approach using the same idea. We note that the definition of the quasi-open and closed operators depends only on the IMS chosen by us, and not on any individual model function. 

It will be important to continue the development of the effective Hilbert space formalism (58) for converting problems with explicitly time-dependent Hamiltonians to stationary problems in an extended Hilbert space. This feature will permit the use of propagation algorithms now used for problems with time-independent Hamiltonians to also be used for pulsed laser-molecule interactions. Peskin and Moiseyev (162) have recently developed and applied a version of the extended space formalism (they refer to it as the (t, / ) formalism). 

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