Hamiltonian polyatomic molecule

Miller W H, Handy N C and Adams J E 1980 Reaction path Hamiltonian for polyatomic molecules J. Chem. Phys. 72 99... 

In diatomic VER, the frequency Q is often much greater than so VER requires a high-order multiphonon process (see example C3.5.6.1). Because polyatomic molecules have several vibrations ranging from higher to lower frequencies, only lower-order phonon processes are ordinarily needed [34]- The usual practice is to expand the interaction Hamiltonian > in equation (03.5.2) in powers of nonnal coordinates [34, 631,... 

Just as for an atom, the hamiltonian H for a diatomic or polyatomic molecule is the sum of the kinetic energy T, or its quantum mechanical equivalent, and the potential energy V, as in Equation (1.20). In a molecule the kinetic energy T consists of contributions and from the motions of the electrons and nuclei, respectively. The potential energy comprises two terms, and F , due to coulombic repulsions between the electrons and between the nuclei, respectively, and a third term Fg , due to attractive forces between the electrons and nuclei, giving... 

It is not possible to discuss highly excited states of molecules without reference to the recent progress in nonlinear dynamics.2 Indeed, the stimulation is mutual. Rovibrational spectra of polyatomic molecules provides both an ideal testing ground for the recent ideas on the manifestation of chaos in Hamiltonian systems and in turn provides many challenges for the theory. 

The construction of the symmetry-adapted operators and of the Hamiltonian operator of polyatomic molecules will be illustrated using the example of the benzene molecule. In order to do the construction, draw a figure corresponding to the geometric structure of the molecule (Figure 6.1). Number the degrees of freedom we wish to describe. 

The Born- Oppenheimer approximation. With spin-orbit and other relativistic interactions omitted, the Hamiltonian of a polyatomic molecule is... 

The vibration-rotation interaction term makes the Hamiltonian for nuclear motion of a polyatomic molecule difficult to deal with. Frequently, this term is small compared to the other terms. We shall make the initial approximation of omitting Tvib rot. The rotational kinetic energy TTOt involves the moments of inertia of the molecule, which in turn depend on the instantaneous nuclear configuration. However, the vibrational motions are much faster than the rotational motions, so that we can make the approximation of calculating the moments of inertia averaged over the vibrational motions. 

Theoretical calculation of a is not as straightforward as for, say, the dipole moment to find o one must include the applied electric field in the molecular Hamiltonian and calculate the resulting change in the molecular dipole moment. Theoretical values of the components of a have been calculated for several diatomic and small polyatomic molecules using a Hartree-Fock approach the calculated values are reasonably accurate. See Schaefer, pp. 243-250, for details.)... 

We now consider the nuclear motions of polyatomic molecules. We are using the Born-Oppenheimer approximation, writing the Hamiltonian HN for nuclear motion as the sum of the nuclear kinetic-energy TN and a potential-energy term V derived from solving the electronic Schrodinger equation. We then solve the nuclear Schrodinger equation... 

Adding the kinetic and potential energies (6.24) and (6.23) and replacing classical quantities by operators, we have as the (approximate) quantum-mechanical vibrational Hamiltonian for a polyatomic molecule... 

R. W. Field Prof. Rabitz, I like the idea of sending out a scout to map a local region of the potential-energy surface. But I get the impression that the inversion scheme you are proposing would make no use of what is known from frequency-domain spectroscopy or even from nonstandard dynamical models based on multiresonance effective Hamiltonian models. Your inversion scheme may be mathematically rigorous, unbiased, and carefully filtered against a too detailed model of the local potential, but I think it is naive to think that a play-and-leam scheme could assemble a sufficient quantity of information to usefully control the dynamics of even a small polyatomic molecule. 

There are many cases in which the molecular Hamiltonian and the interactions with the photon fields are not completely known. For many isolated polyatomic molecules or for molecules in condensed phases, for ex-... 

Only spatially degenerate states exhibit a first-order zero-field splitting. This condition restricts the phenomenon to atoms, diatomics, and highly symmetric polyatomic molecules. For a comparison with experiment, computed matrix elements of one or the other microscopic spin-orbit Hamiltonian have to be equated with those of a phenomenological operator. One has to be aware of the fact, however, that experimentally determined parameters are effective ones and may contain second-order contributions. Second-order SOC may be large, particularly in heavy element compounds. As discussed in the next section, it is not always distinguishable from first-order effects. 

The vibration-rotation hamiltonian of a polyatomic molecule is more complicated than that of a diatomic molecule, both because of the increased number of co-ordinates, and because of the presence of Coriolis terms which are absent from the diatomic hamiltonian. These differences lead to many more terms in the formulae for a and x values obtained from the contact transformation, and they also lead to various kinds of vibrational and rotational resonance situations in which two or more vibrational levels are separated by so small an energy that interaction terms in the hamiltonian between these levels cannot easily be handled by perturbation theory. It is then necessary to obtain an effective hamiltonian over these two or more vibrational levels, and to use special techniques to relate the coefficients in this hamiltonian to the observed spectrum. 

Contact Transformation for the Effective Hamiltonian.—The vibration-rotation hamiltonian of a polyatomic molecule, expressed in terms of normal co-ordinates, has been discussed in particular by Wilson, Decius, and Cross,24 and by Watson.27- 28 It is given by the following expression for a non-linearf polyatomic molecule, to be compared with equation (17) for a diatomic molecule ... 

It took several decades for the effective Hamiltonian to evolve to its modem form. It will come as no surprise to learn that Van Vleck played an important part in this development for example, he was the first to describe the form of the operator for a polyatomic molecule with quantised orbital angular momentum [2], The present formulation owes much to the derivation of the effective spin Hamiltonian by Pryce [3] and Griffith [4], Miller published a pivotal paper in 1969 [5] in which he built on these ideas to show how a general effective Hamiltonian for a diatomic molecule can be constructed. He has applied his approach in a number of specific situations, for example, to the description of N2 in its A 3 + state [6], described in chapter 8. In this book, we follow the treatment of Brown, Colbourn, Watson and Wayne [7], except that we incorporate spherical tensor methods where advantageous. It is a strange fact that the standard form of the effective Hamiltonian for a polyatomic molecule [2] was established many years before that for a diatomic molecule [7]. 

The nuclear spin-rotation interaction becomes very simple for a diatomic molecule. The principal components of the tensor a for a polyatomic molecule were described in equation (8.163) this expression reveals that for a diatomic system the axial component (c/)zz is zero and, of course, the two perpendicular components are equal. The nuclear spin rotation interaction for a diatomic molecule is therefore described by a single parameter c/. The appropriate term in the effective Hamiltonian, first presented in equation (8.7), is... 

An alternative approach widely used in polyatomic molecule studies is based on the Golden Rule and a perturbative treatment of the anharmonic coupling (57,62). This approach is not much used for diatomic molecules. In the liquid O2 example cited above, the Hamiltonian must be expanded to 30th order or so to calculate the multiphonon emission rate. But for vibrations of polyatomic molecules, which can always find relatively low-order VER pathways for each VER step, perturbation theory is very useful. In the perturbation approach, the molecule s entire ladder of vibrational excitations is the system and the phonons are the bath. Only lower-order processes are ordinarily needed (57) because polyatomic molecules have many vibrations ranging from higher to lower frequencies and only a small number of phonons, usually one or two, are excited in each VER step. The usual practice is to expand the interaction Hamiltonian (qn, Q) in Equation (2) in powers of normal coordinates (57,62) ... 

M. Mladenovic, Rovibrational Hamiltonians for general polyatomic molecules in spherical polar parameterization I. Orthogonal representations. J. Chem. Phys. 112, 1070-1081 (2000). 

The model Hamiltonian of Section II captures some of the essential features of the electronic and vibrational structure of polyatomic molecules, like benzene and 5ym-triazine, that have both nondegenerate and degenerate, Jahn-Teller active, electronic levels. In this section interference experiments are described which will be sensitive to the geometric phase development accompanying adiabatic nuclear motion on either of the electronic potential energy surfaces in the Jahn-Teller pair. 

For a polyatomic molecule, nuclei are considered motionless, because the motion of electrons is on a much faster timescale than the motion of nuclei (the Born-Oppenheimer approximation). The corresponding Hamiltonian is ... 

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