Hamiltonian Subject

Consider a molecule in its ground state tj/g, an exact eigenstate of the molecular Hamiltonian, subjected to the very short external perturbation M S (Z) (such as caused by a very short radiation pulse, in which case M is proportional to the dipole moment operator). From Eq. (2.74) truncated at the level of first-order perturbation theory... 

Dennison coupling produces a pattern in the spectrum that is very distinctly different from the pattern of a pure nonnal modes Hamiltonian , without coupling, such as (Al.2,7 ). Then, when we look at the classical Hamiltonian corresponding to the Darling-Deimison quantum fitting Hamiltonian, we will subject it to the mathematical tool of bifiircation analysis [M]- From this, we will infer a dramatic birth in bifiircations of new natural motions of the molecule, i.e. local modes. This will be directly coimected with the distinctive quantum spectral pattern of the polyads. Some aspects of the pattern can be accounted for by the classical bifiircation analysis while others give evidence of intrinsically non-classical effects in the quantum dynamics. 

Finally, we consider the complete molecular Hamiltonian which contains not only temis depending on the electron spin, but also temis depending on the nuclear spin / (see chapter 7 of [1]). This Hamiltonian conmiutes with the components of Pgiven in (equation Al.4,1). The diagonalization of the matrix representation of the complete molecular Hamiltonian proceeds as described in section Al.4,1.1. The theory of rotational synnnetry is an extensive subject and we have only scratched the surface here. A relatively new book, which is concemed with molecules, is by Zare [6] (see [7] for the solutions to all the problems in [6] and a list of the errors). This book describes, for example, the method for obtaining the fimctioiis ... 

This establishes our assertion that the former roots are overwhelmingly more numerous than those of the latter kind. Before embarking on a formal proof, let us illustrate the theorem with respect to a representative, though specific example. We consider the time development of a doublet subject to a Schrodinger equation whose Hamiltonian in a doublet representation is [13,29]... 

Rather than solve a Schrodinger equation with the Nuclear Hamiltonian (above), a common approximation is to assume that atoms are heavy enough so that classical mechanics is a good enough approximation. Motion of the particles on the potential surface, according to the laws of classical mechanics, is then the subject of classical trajectory analysis or molecular dynamics. These come about by replacing Equation (7) on page 164 with its classical equivalent ... 

We then allow Ri and R2 to vary, subject to orthonormality, just as in the closed-shell case. Just as in the closed-shell case, Roothaan (1960) showed how to write a Hamiltonian matrix whose eigenvectors give the columns U] and U2 above. 

In the present implementation, the unperturbed functions are not subject to any orthogonality constraint nor are required to diagonalize any model hamiltonian. This freedom yields a faster convergence of the variational expansion with the basis size and allows to obtain the phaseshift of the basis states without the analysis of their asymptotic behaviour. 

The stream lines of a vector field v(x) are those trajectories where the vector v(x) is tangential to the path. In analogy to trajectories of atoms subject to the influence of a Hamiltonian, the stream lines obey an equation of motion of first order given by... 

Systems with more than one unpaired electron are not only subject to the electronic Zeeman interaction but also to the magnetic-field independent interelectronic zero-field interaction, and the spin Hamiltonian then becomes... 

Let us calculate the frequencies of transitions between Zeeman eigenstates s) and r), assuming that the nuclei are only subjected to an isotropic chemical shift and the first- and second-order quadrupolar interaction. As seen in Sect. 2.1, the Hamiltonian that governs the spin system in the frame of the Zeeman interaction (the rotating frame) is... 

Suppose that the atom (or nucleus) initially in an eigenstate 1 is subjected to a small time-dependent potential V (t) on top of the unperturbed Hamiltonian Ho2 It is then possible to treat the coefficients an in Eq. (A3.12) as functions of time, with ai 2(r) 1 being the probability that it is still in state 1 after a time x and a2 2(t) < C 1 the probability that it has undergone a transition to another eigenstate 2 . Substituting in Schrodinger s equation (A3.8),... 

By subjecting the amplitudes b b to the commutation relationships (34) the classical Hamiltonian... 

As for classical systems, measurement of the properties of macroscopic quantum systems is subject to experimental error that exceeds the quantum-mechanical uncertainty. For two measurable quantities F and G the inequality is defined as AFAG >> (5F6G.The state vector of a completely closed system described by a time-independent Hamiltonian H, with eigenvalues En and eigenfunctions is represented by... 

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