Coupled continuum states

Figure 1. Schematic illustration of two-pathway control in the (a) frequency and (b) time domains. In case (a) the ground state is excited to a coupled continuum by either one photon of frequency CO3 or three photons of frequency C >i. Control is achieved by introducing a phase lag between the two fields. In case (b) a two-pulse sequence has sufficient bandwidth to excite a superposition of two intermediate states. Control is achieved by introducing a delay, At, between the pulses, resulting in a phase difference of to At.

Considering again the case of a structureless continuum, we have that 8j3 arises from excitation of a superposition of continuum states, hence from coupling within PHmP [69]. The simplest model of this class of problems, depicted schematically in Fig. 5b, is that of dissociation of a diatomic molecule subject to two coupled electronic dissociative potential energy curves. Here the channel phase can be expressed as... 

Two-dimensional constant matrix, transition state trajectory, white noise, 203-207 Two-pathway excitation, coherence spectroscopy atomic systems, 170-171 channel phases, 148-149 energy domain, 178-182 extended systems and dissipative environments, 177-185 future research issues, 185-186 isolated resonance, coupled continuum, 168-169... 

The most important implication of not being a good quantum number is that blue and red states are coupled by their slight overlap at the core. In the region below the classical ionization limit blue and red states of adjacent n do not cross as they do in H, but exhibit avoided crossings as a result of their being coupled. Above the classical ionization limit blue states, which would be perfectly stable in H, are coupled to degenerate red states, which are unbound, and ionization occurs rapidly compared to radiative decay. It is really an autoionization process in which the blue state is coupled to the red continuum state at the ionic core. 

The autoionization rate T of a Ba 6pn( state converging to the Ba+ 6p state is given by the product of the squared coupling matrix element and the density of final continuum states. Explicitly,2... 

In the presence of coupling between the two excited manifolds, represented by the operator W, the bound states n) generated, for example, either by absorption of a photon (as illustrated in Figure 7.5), by electron impact, or in an atom-molecule collision will decay because they undergo transitions to the continuum states. W is assumed to be time-independent and for the discussion in this section its origin and particular form is not pertinent. It may represent nonadiabatic coupling between two electronic or two vibrational states, for example. We explicitly assume that W couples only the bound and the continuum states and that there is no coupling between the bound or between the continuum states,... 

If the coupling is zero, the bound states will live forever. However, immediately after we have switched on the coupling they start to decay as a consequence of transitions to the continuum states until they are completely depopulated. Our goal is to derive explicit expressions for the depletion of the bound states l iz) and the filling of the continuum states 2(E,0)). The method we use is time-dependent perturbation theory in the same spirit as outlined in Section 2.1, with one important extension. In Section 2.1 we explicitly assumed that the perturbation is sufficiently weak and also sufficiently short to ensure that the population of the initial state remains practically unity for all times (first-order perturbation theory). In this section we want to describe the decay process until the initial state is completely depleted and therefore we must necessarily go beyond the first-order treatment. The subsequent derivation closely follows the detailed presentation of Cohen-Tannoudji, Diu, and Laloe (1977 ch.XIII). 

In order to simplify the general picture we assume that the photodissociation separates into two consecutive steps as illustrated in Figure 7.5. The light pulse promotes the molecule from the initial nuclear state J o) in the ground electronic state to the vibrational-rotational states I J ii) with energies Ei in the (binding) excited electronic state. In the second step, the i/) couple to the manifold of continuum states and eventually they dissociate. Only the binding state is assumed to be dipole-allowed h-i iQ 7 0] whereas the dissociative state is dark p = 0]. 

The coupling to the continuum states (i.e., dissociation) broadens the discrete absorption lines and therefore the discrete spectrum turns into a continuous spectrum. 

Equation (7.22) is at the heart of spectroscopy. The positions of the absorption lines reflect the energy levels of the excited complex and the widths provide information about the lifetime and therefore about the coupling to the continuum states. The latter requires, however, that the measured widths are the true homogeneous line widths, i.e., unadulterated by poor resolution and/or thermal broadening, for example. Each resonance has a characteristic width. In Chapters 9 and 10 we will discuss how the final fragment distributions reflect the initial state in the complex and details of the fragmentation mechanism. 

The decay of Nal can be described in an alternative way [K.B. Mpller, N.E. Henriksen, and A.H. Zewail, J. Chem. Phys. 113, 10477 (2000)]. In the bound region of the excited-state potential energy surface, one can define a discrete set of quasi-stationary states that are (weakly) coupled to the continuum states in the dissociation channel Na + I. These quasi-stationary states are also called resonance states and they have a finite lifetime due to the coupling to the continuum. Each quasi-stationary state has a time-dependent amplitude with a time evolution that can be expressed in terms of an effective (complex, non-Hermitian) Hamiltonian. 

The value of coherent control experiments lies not only in their ability to alter the outcome of a reaction but also in the fundamental information that they provide about molecular properties. In the example of phase-sensitive control, the channel phase reveals information about couplings between continuum states that is not readily obtained by other methods. Examination of Eq. (15) reveals two possible sources of the channel phase—namely, the phase of the three-photon dipole operator and that of the continuum function, ESk). The former is complex if there exists a metastable state at an energy of (D or 2 >i, which contributes a phase to only one of the paths, as illustrated in Fig. 3b. In this case the channel phase equals the Breit-Wigner phase of the intermediate resonance (modulo n),... 

The Breit-Pauli spin-orbit operator has one major drawback. It implicitly contains terms coupling electronic states (with positive energy) and posi-tronic states (in the negative energy continuum) and is thus unbounded from below. It can be employed safely only in first-order perturbation theory. 

Flere X(Q) represents the electronic matrix element of any operator coupling the potentials under consideration. The Wentzel-Rice approximation restricts the coupling of a bound initial vibrational state %v. to a single continuum state with energy E = E,. Schematically, the interaction between a bound... 

Resonantly enhanced two-photon dissociation of Na2 from a bound state of the. ground electronic state occurs [202] by initial excitation to an excited intermediate bound state Em,Jm, Mm). The latter is a superposition of states of the A1 1+ and b3Il electronic curves, a consequence of spin-orbit coupling. The continuum states reached in the two-photon excitation can have either a singlet or a triplet character, but, despite the multitude of electronic states involved in the computation reported J below, the predominant contributions to the products Na(3s) + Na(3p) and Na(3s) + Na(4s) are found to come from the 1 flg and 3 + electronic states, respectively. The resonant character of the two-photon excitation allows tire selection of a Single initial state from a thermal ensemble here results for vt = Ji — 0, where vt,./, denote the vibrational and rotational quantum numbers of the initial state, are stJjseussed. 

Explicit expressions for the dipole matrix elements (6.2.18) were computed, e.g., by Bliimel and Smilansky (1987) and Susskind and Jensen (1988). At this point we make the crucial approximation. We neglect all coupling between the continuum states by dropping the integral over k in (6.2.17). By substituting... 

The formal coupled integral equations (6.73) and their explicitly-anti-symmetric form (7.35) require a discrete notation for the target continuum. In (7.123) discrete notation is used only for discrete states and the continuum states in the expansion of may be treated by integration. 

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