Hamiltonian equation bound motion

Here, Q is the projector on the bound subspace and P projects onto the open, continuum channels. The intramolecular coupling is written as V+ U so that, as before, U is any additional coupling brough about by external perturbations. The equation H = Hq + V+U, where Ho is the zero-order Hamiltonian of the Rydberg electron and so includes only the central part of the potential due to the core plus the motion (vibration, rotation) of the core, uncoupled to the electron. The perturbations V + U can act within the bound subspace, as the operator Q(V+l/)Q is not necessarily diagonal and is the cause of any intramolecular dynamics even in the absence of coupling to the continuum. The intramolecular terms can also couple the bound and dissociative states. 

Equation (1-13) or its body-fixed equivalent is of little use for Van der Waals complexes, as it discriminates one nuclear coordinate, e.g. y = 1. Specific mathematical forms of Hamiltonians describing the nuclear motions in Van der Waals dimers have been developed (7). This point will be discussed in more details in Section 12.4. Here we only want to stress that whatever the mathematical form of the Hamiltonian is used to solve the problem of nuclear motions, the results will be the same, if the Schrodinger equation is solved exactly. However, in weakly bound complexes there is a hierarchy of motions due to the strong intramolecular forces which determine the internal vibrations of the molecules, and to much weaker intermolecular forces which determine their relative translations and rotations. This hierarchy allows to make a separation between the intramolecular vibrations with high frequencies and the intermolecular modes with much lower frequencies. Such a separation of the fast intramolecular vibrations and slow rotation-vibration-tunneling motions can be performed if a suitable form of the Hamiltonian for the nuclear motions in Van der Waals molecules is used. 

The Born-Oppenheimer approximation allows us to decouple the electronic and nuclear motions of the free molecule of the Hamiltonian Hq. Solving the Schrodinger equation //o l = with respect to the electron coordinates r = r[, O, gives rise to the electronic states (r, R) = (r n(R)), n = 0,..., Ne, of respective energies En (R) as functions of the nuclear coordinates R, with the electronic scalar product defined as (n(R) n (R))r = j dr rj( r. R) T,-(r, R). We assume Ne bound electronic states. The Floquet Hamiltonian of the molecule perturbed by a field (of frequency co, of amplitude 8, and of linear polarization e), in the dipole coupling approximation, and in a coordinate system of origin at the center of mass of the molecule can be written as... 

Whatever way it is intended to go in specifying the electronic coordinates, they must be specifiable as translationally invariant so that the centre of mass motion can be separated from Schrodinger s equation for the system. It is only the translationally invariant part of the Hamiltonian that can have a bound state spectrum and thus be relevant to both the scattering and the bound molecule problem. 

We will discuss the case where the motion of heavy atoms is confined to two dimensions, while the motion of light atoms can be either two- or three-dimensional. It will be shown that the Hamiltonian 10.76 with Ues in 10.44 supports the first-order quantum gas-crystal transition at T = 0 [68], This phase transition resembles the one for the flux lattice melting in superconductors, where the flux lines are mapped onto a system of bosons interacting via a two-dimensional Yukawa potential [73]. In this case Monte Carlo studies [74,75] identified the first-order liquid-crystal transition at zero and finite temperatures. Aside from the difference in the interaction potentials, a distinguished feature of our system is related to its stability. The molecules can undergo collisional relaxation into deeply bound states, or form weakly bound trimers. Another subtle question is how dilute the system should be to enable the use of the binary approximation for the molecule-molecule interaction, leading to Equations 10.76 and 10.44. 

Hi in Equation 7.82 is the Hamiltonian for the bound component of the motion over the final surface... 

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