Hamiltonian spectroscopic

Physically, why does a temi like the Darling-Dennison couplmg arise We have said that the spectroscopic Hamiltonian is an abstract representation of the more concrete, physical Hamiltonian fomied by letting the nuclei in the molecule move with specified initial conditions of displacement and momentum on the PES, with a given total kinetic plus potential energy. This is the sense in which the spectroscopic Hamiltonian is an effective Hamiltonian, in the nomenclature used above. The concrete Hamiltonian that it mimics is expressed in temis of particle momenta and displacements, in the representation given by the nomial coordinates. Then, in general, it may contain temis proportional to all the powers of the products of the... 

A classical Hamiltonian is obtained from the spectroscopic fitting Hamiltonian by a method that has come to be known as the Heisenberg correspondence [46], because it is closely related to the teclmiques used by Heisenberg in fabricating the fomi of quantum mechanics known as matrix mechanics. 

We have alluded to the comrection between the molecular PES and the spectroscopic Hamiltonian. These are two very different representations of the molecular Hamiltonian, yet both are supposed to describe the same molecular dynamics. Furthemrore, the PES often is obtained via ab initio quairtum mechanical calculations while the spectroscopic Hamiltonian is most often obtained by an empirical fit to an experimental spectrum. Is there a direct link between these two seemingly very different ways of apprehending the molecular Hamiltonian and dynamics And if so, how consistent are these two distinct ways of viewing the molecule ... 

There has been a great deal of work [62, 63] investigating how one can use perturbation theory to obtain an effective Hamiltonian like tlie spectroscopic Hamiltonian, starting from a given PES. It is found that one can readily obtain an effective Hamiltonian in temis of nomial mode quantum numbers and coupling. 

We have seen that resonance couplings destroy quantum numbers as constants of the spectroscopic Hamiltonian. Widi both the Darling-Deimison stretch coupling and the Femii stretch-bend coupling in H2O, the individual quantum numbers and were destroyed, leaving the total polyad number n + +... 

There are numerous methods for solving the time dependent Scln-ddinger equation (A3.13.43). and some of them were reviewed by Kosloff [118] (see also [119. 120]). Wlienever projections of the evolving wave fiinction on the spectroscopic states are usellil for the detailed analysis of the quanPun dynamics (and this is certainly the case for tlie detailed analysis of IVR), it is convenient to express the Hamiltonian based on spectroscopic states I... 

The most commonly used semiempirical for describing PES s is the diatomics-in-molecules (DIM) method. This method uses a Hamiltonian with parameters for describing atomic and diatomic fragments within a molecule. The functional form, which is covered in detail by Tully, allows it to be parameterized from either ah initio calculations or spectroscopic results. The parameters must be fitted carefully in order for the method to give a reasonable description of the entire PES. Most cases where DIM yielded completely unreasonable results can be attributed to a poor fitting of parameters. Other semiempirical methods for describing the PES, which are discussed in the reviews below, are LEPS, hyperbolic map functions, the method of Agmon and Levine, and the mole-cules-in-molecules (MIM) method. 

Non-rigidity has important consequences for the rotation and vibration spectra. Extensive experimental investigations exist in this domain they are based on the elaboration of model hamiltonians to describe the external motions. Recently, non-rigid molecule effects on the rovi-bronic levels of PF5 have been examined , so leading to the prediction of the spectroscopic consequences of Berry processes. 

The effective spectroscopic classical Hamiltonian for Fermi resonance between a nondegenerate mode vi and a doubly degenerate mode V2 takes the form [30, 31]... 

The standard effective spectroscopic Fermi resonant Hamiltonian allows more complicated types of behavior. The full three-dimensional aspects of the monodromy remain to be worked out, but it was shown, with the help of the Xiao—KeUman [28, 29] catastrophe map, that four main dynamical regimes apply, and that successive polyads of a given molecule may pass from one regime to another. 

The individual terms in (5.2) and (5.3) represent the nuclear-nuclear repulsion, the electronic kinetic energy, the electron-nuclear attraction, and the electron-electron repulsion, respectively. Thus, the BO Hamiltonian is of treacherous simplicity it merely contains the pairwise electrostatic interactions between the charged particles together with the kinetic energy of the electrons. Yet, the BO Hamiltonian provides a highly accurate description of molecules. Unless very heavy elements are involved, the exact solutions of the BO Hamiltonian allows for the prediction of molecular phenomena with spectroscopic accuracy that is... 

The reason for pursuing the reverse program is simply to condense the observed properties into some manageable format consistent with quantum theory. In favourable cases, the model Hamiltonian and wave functions can be used to reliably predict related properties which were not observed. For spectroscopic experiments, the properties that are available are the energies of many different wave functions. One is not so interested in the wave functions themselves, but in the eigenvalue spectrum of the fitted model Hamiltonian. On the other hand, diffraction experiments offer information about the density of a particular property in some coordinate space for one single wave function. In this case, the interest is not so much in the model Hamiltonian, but in the fitted wave function itself. 

From the above discussion, we can see that the purpose of this paper is to present a microscopic model that can analyze the absorption spectra, describe internal conversion, photoinduced ET, and energy transfer in the ps and sub-ps range, and construct the fs time-resolved profiles or spectra, as well as other fs time-resolved experiments. We shall show that in the sub-ps range, the system is best described by the Hamiltonian with various electronic interactions, because when the timescale is ultrashort, all the rate constants lose their meaning. Needless to say, the microscopic approach presented in this paper can be used for other ultrafast phenomena of complicated systems. In particular, we will show how one can prepare a vibronic model based on the adiabatic approximation and show how the spectroscopic properties are mapped onto the resulting model Hamiltonian. We will also show how the resulting model Hamiltonian can be used, with time-resolved spectroscopic data, to obtain internal... 

Hamiltonian equations, 610—615 minimal models, 615-618 multi-state effects, 624 pragmatic models, 618—621 spectroscopic properties, 598-610 linear molecules ... 

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