Equilibrium points, quantization

Just above the saddle energy, the quantization can be performed by the usual perturbation theory applied to scattering systems as described by Miller and Seideman [24], This equilibrium point quantization uses Dunham expansions of the form (2.8) with imaginary coefficients. This method is valid for relatively low-lying resonances above the saddle, up to the point where anhar-monicities become so important that the Dunham expansion is no longer applicable (see the discussion in Section II.B). 

The derivation of (4.13) shows that the equilibrium point quantization and the periodic-orbit quantization can be compared term by term. This comparison shows that the periodic-orbit quantization is able to take into account the anharmonicities in the direction of symmetric stretch. However, the anhar-monicities are neglected in the other directions transverse to the periodic orbit. Their full treatment requires the calculation of h corrections to the Gutzwiller trace formula, as shown elsewhere [14]. 

Differences between the lifetimes obtained from equilibrium point quantization and periodic-orbit quantization appear as the bifurcation is approached. The lifetimes are underestimated by equilibrium point quantization but overestimated by periodic-orbit quantization. The reason for the upward deviation in the case of periodic-orbit quantization is that the Lyapunov exponent vanishes as the bifurcation is approached. The quantum eigenfunctions, however, are not characterized by the local linearized dynamics but extend over larger distances that are of more unstable character. 

Figure 13. Scattering resonances of a two-degree-of-freedom collinear model of the dissociation of Hgl2 [10], The filled dots are obtained by wavepacket propagation, the crosses by equilibrium point quantization with (2.8), the dotted circles from periodic-orbit quantization with (4.16). The solid lines are the curves corresponding to the Lyapunov exponents, Im E = -(A/2)Xp(Re ), of the fundamental periodic orbits p = 0, 1,2. The dashed line is the spectral gap, Im = ftP(l/2 Ref). The long-short dashed line is the curve corresponding to the escape rate, Im E = (h/2)P( Re ).

As the LEPS surface comprises all vibrational degrees of freedom, it is possible to include the effect of bending in the analysis. To this end, we have carried out the equilibrium point quantization for this system at energies just... 

Figure 16. Scattering resonances of the full rotational-vibrational Hamiltonian describing the dissociation of CO2 on a LEPS surface obtained by equilibrium point quantization with (2.8). The resonances with 7 = 0,..., 10 are given by dots. Their close vicinity explains the formation of hyphens , i.e., unresolved sequences of dots. Note that rotation is very slightly destabilizing in the present model. The successive hyphens are the bending progressions with V2 = 0,. .. 5. The solid line is given by the Lyapunov exponent of the symmetric-stretch periodic orbit 0 expressed as an imaginary energy.

In a more recent work, Joens [158] has assigned the structures of the Hartley band using a Dunham expansion, that is equilibrium point quantization. The lifetime predicted by his analysis is extremely short, equal to 3.2 fs, while the symmetric stretching period is of 30 fs. Recall, however, that the interpretations in terms of equilibrium point expansions and in terms of periodic orbits are strictly complementary only for regular regimes. 

P. Gaspard To answer the question by Prof. Marcus, let me say that we have observed, in particular in Hgl2, that higher order perturbation theory around the saddle equilibrium point of the transition state may indeed be used to predict with a good accuracy the resonances just above the saddle. However, deviations appear for higher resonances and periodic-orbit quantization then turns out to be in better agreement than equilibrium point quantization. 

II. Semiclassical Quantization around Equilibrium Points and Periodic Orbits... 

The anharmonicities of the potential contribute by the terms involving the constants x, g, y,. .. as well as the energy shifts AEx = 0(h2),. .. and the frequency shifts Aw, = 0(h2),. These anharmonic constants can be calculated by the Van Vleck contact transformations [20] as well as by a semi-classical method based on an h expansion around the equilibrium point [14], which confirms that the Dunham expansion (2.8) is a series in powers of h. Systematic methods have been developed to carry out the Van Vleck contact transformations, as in the algebraic quantization technique by Ezra and Fried [21]. It should be noted that the constants x and g can also be obtained from the classical-mechanical Birkhoff normal forms [22], The energy shifts AEx,... 

Note Frequencies and energies in reciprocal centimeters and times in femtoseconds. "Collinear two-degree-of-freedom model by Zewail et al. [151] by quantization around the equilibrium point of linear geometry (bending ignored). 

The Point Charge Concept and the Related Divergence Quantized Charged Equilibrium B.4.1. Conditions on Spin and Magnetic Moment... 

A further important aspect of optical pumping with a polarized laser is the selective population or depletion of degenerate M sublevels 17, M) of a level with angular momentum J. These sublevels differ by the projection Mtl of J onto the quantization axis. Atoms or molecules with a nonuniform population density N(J, M) of these sublevels are oriented because their angular momentum J has a preferred spatial distribution while under thermal equilibrium conditions J points into all directions with equal probability, that is, the orientational distribution is uniform. The highest degree of orientation is reached if only one of the (27+ 1) possible M sublevels is selectively populated. 

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