Hamiltonian modes quantum representation

Passing to the Boson operators by aid of Table II, and after neglecting the zero-point-energy of the fast mode, we obtain a quantum representation we shall name I, in which the effective Hamiltonians of the slow mode corresponding respectively to the ground and first excited states of the fast mode are... 

A more general description of the effects of vibronic coupling can be made using the model Hamiltonian developed by Koppel, Domcke and Cederbaum [65], The basic idea is the same as that used in Section III.C, that is to assume a quasidiabatic representation, and to develop a Hamiltonian in this picture. It is a useful model, providing a simple yet accurate analytical expression for the coupled PES manifold, and identifying the modes essential for the non-adiabatic effects. As a result it can be used for comparing how well different dynamics methods perform for non-adiabatic systems. It has, for example, been used to perform benchmark full-dimensional (24-mode) quantum dynamics calculations... 

Now, pass to quantum representation ///. Within it, the effective Hamiltonians corresponding to the ground-state fast mode is unchanged, whereas that corresponding to the first excited state is modified. Owing to Table VI, the following equations hold ... 

Now, it may be of interest to look at the connection between the autocorrelation functions appearing in the standard and the adiabatic approaches. Clearly, it is the representation I of the adiabatic approach which is the most narrowing to that of the standard one [see Eqs. (43) and (17)] because both are involving the diagonalization of the matricial representation of Hamiltonians, within the product base built up from the bases of the quantum harmonic oscillators corresponding to the separate slow and fast modes. However, among the... 

Here a and are the usual oscillator creation and annihilation operators with bosonic commutation relations (73), and 0i,..., 1 ,..., 0Af) denotes a harmonic-oscillator eigenstate with a single quantum excitation in the mode n. According to Eq. (80a), the bosonic representation of the Hamiltonian (79) is given by... 

Effective Hamiltonian of the two H-bond bridge quantum harmonic oscillator in representation II when the two moieties fast modes are in their eigenstates... 

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