Coupling, weak

A covalent bond (or particular nomial mode) in the van der Waals molecule (e.g. the I2 bond in l2-He) can be selectively excited, and what is usually observed experimentally is that the unimolecular dissociation rate constant is orders of magnitude smaller than the RRKM prediction. This is thought to result from weak coupling between the excited high-frequency intramolecular mode and the low-frequency van der Waals intemiolecular modes [83]. This coupling may be highly mode specific. Exciting the two different HE stretch modes in the (HF)2 dimer with one quantum results in lifetimes which differ by a factor of 24 [84]. Other van der Waals molecules studied include (NO)2 [85], NO-HF [ ], and (C2i J )2 [87]. 

Canet D 1989 Construction, evolution and detection of magnetization modes designed for treating longitudinal relaxation of weakly coupled spin 1/2 systems with magnetic equivalence Prog. NMR Spectrosc. 21 237-91... 

The xy magnetizations can also be complicated. Eor n weakly coupled spins, there can be n 2" lines in the spectrum and a strongly coupled spin system can have up to (2n )/((n-l) (n+l) ) transitions. Because of small couplings, and because some lines are weak combination lines, it is rare to be able to observe all possible lines. It is important to maintain the distinction between mathematical and practical relationships for the density matrix elements. 

The mean field teclmique is one of the most robust and simple methods used to handle larger molecules in gas and liquid enviromnents [M, 134. 135 and 136]. The basic premise of all mean-field methods is that the fiill wavefiinction represents N very weakly coupled modes (2 ) and can be approximated as... 

In many instances tire adiabatic ET rate expression overestimates tire rate by a considerable amount. In some circumstances simply fonning tire tire activated state geometry in tire encounter complex does not lead to ET. This situation arises when tire donor and acceptor groups are very weakly coupled electronically, and tire reaction is said to be nonadiabatic. As tire geometry of tire system fluctuates, tire species do not move on tire lowest potential energy surface from reactants to products. That is, fluctuations into activated complex geometries can occur millions of times prior to a productive electron transfer event. 

In tills weakly coupled regime, ET in an encounter complex can be described approximately using a two-level system model [23]. As such, tlie time-dependent wave function is... 

Also, rotational state resolution of cross-sections can be obtained by employing a coherent state analysis [51] for the situation of weak coupling between rotational and vibrational degrees of freedom. A suitable rotational coherent state can be expressed as... 

Thus, we still relate to the same sub-space but it is now defined for P-states that are weakly coupled to <2"States. We shall prove the following lemma. If the interaction between any P- and Q-state measures like 0(e), the resultant P-diabatic potentials, the P-adiabatic-to-diabatic bansfomiation maOix elements and the P-curl t equation are all fulfilled up to 0(s ). 

We prove our statement in two steps First, we consider the special case of a Hilbert space of three states, the two lowest of which are coupled strongly to each other but the third state is only weakly coupled to them. Then, we extend it to the case of a Hilbert space of N states where M states are strongly coupled to each other, and L = N — M) states, are only loosely coupled to these M original states (but can be stiongly coupled among themselves). 

Next, we analyze the P-curl condition with the aim of examining to what extent it is affected when the weak coupling is ignored as described in Section IV.B.l [81]. For this purpose, we consider two components of the (unperturbed) X matrix, namely, the mafiices Xq and Xp, which are written in the following form [see Eq. (43)] ... 

The idea of having two distinct quasi-Fermi levels or chemical potentials within the same volume of material, first emphasized by Shockley (1), has deeper implications than the somewhat similar concept of two distinct effective temperatures in the same block of material. The latter can occur, for example, when nuclear spins are weakly coupled to atomic motion (see Magnetic spin resonance). Quasi-Fermi level separations are often labeled as Im p Fermi s name spelled backwards. 

Moreover, in this linear-response (weak-coupling) limit any reservoir may be thought of as an infinite number of oscillators qj with an appropriately chosen spectral density, each coupled linearly in qj to the particle coordinates. The coordinates qj may not have a direct physical sense they may be just unobservable variables whose role is to provide the correct response properties of the reservoir. In a chemical reaction the role of a particle is played by the reaction complex, which itself includes many degrees of freedom. Therefore the separation of reservoir and particle does not suffice to make the problem manageable, and a subsequent reduction of the internal degrees of freedom in the reaction complex is required. The possible ways to arrive at such a reduction are summarized in table 1. 

The equation of motion for the expectation < in the weak-coupling limit has a Langevin-like form... 

Our conclusions about the case of large /tls have a rather speculative character, and pursue merely an illustrative goal, since (2.41) and (2.42) are obtained in the weak-coupling limit. 

Coupling to these low-frequency modes (at n < 1) results in localization of the particle in one of the wells (symmetry breaking) at T = 0. This case, requiring special care, is of little importance for chemical systems. In the superohmic case at T = 0 the system reveals weakly damped coherent oscillations characterised by the damping coefficient tls (2-42) but with Aq replaced by A ft-If 1 < n < 2, then there is a cross-over from oscillations to exponential decay, in accordance with our weak-coupling predictions. In the subohmic case the system is completely localized in one of the wells at T = 0 and it exhibits exponential relaxation with the rate In k oc - hcoJksTY ". 

In this model there is a quantitative difference between RLT and electron transfer stemming from the aforementioned difference in phonon spectra. RLT is the weak-coupling case S < 1, while for electron transfer in polar media the strong-coupling limit is reached, when S > 1. In particular, in the above example of ST conversion in aromatic hydrocarbon molecules S = 0.5-1.0. 

Therefore, the tunneling splitting decreases with increasing n, in accord with experiment. The weak-coupling formula holds for C Ql/hmiCol <4 1. 

The early approaches to this model used perturbative expansion for weak coupling [Silbey and Harris 1983]. Generally speaking, perturbation theory allows one to consider a TLS coupled to an arbitrary bath via the term where / is an operator that acts on the bath variables. The equations of motion in the Heisenberg representation for the a operators, 8c/8t = ih [H, d], have the form... 

Solving now the Heisenberg equations of motion for the a operators perturbatively in the same way as in the weak-coupling case, one arrives (at = 0) at the celebrated non-interacting blip approximation [Dekker 1987b Aslangul et al. 1985]... 

Working in the same weak-coupling approximation, it takes little effort to produce the expression for the rate constant in the asymmetric case, by simply replacing J in (2.42)-(2.44) by the energy bias . 

The normal modes for solid Ceo can be clearly subdivided into two main categories intramolecular and intermolecular modes, because of the weak coupling between molecules. The former vibrations are often simply called molecular modes, since their frequencies and eigenvectors closely resemble those of an isolated molecule. The latter are also called lattice modes or phonons, and can be further subdivided into librational, acoustic and optic modes. The frequencies for the intermolecular modes are low, reflecting, the... 

Uncoupled solutions for current and electric field give simple and explicit descriptions of the response of piezoelectric solids to shock compression, but the neglect of the influence of the electric field on mechanical behavior (i.e., the electromechanical coupling effects) is a troublesome inconsistency. A first step toward an improved solution is a weak-coupling approximation in which it is recognized that the effects of coupling may be relatively small in certain materials and it is assumed that electromechanical effects can be treated as a perturbation on the uncoupled solution. 

Fig. 4.5. The degree of approximation for the increase of current in time for uncoupled and weakly coupled solutions for impact-loaded, x-cut quartz and z-cut lithium niobate is shown by comparison to the numerically predicted, fully coupled case. In the figure, the initial current is set to the value of 1.0 at the measured value (after Davison and Graham [79D01]).

The determination of piezoelectric constants from current pulses is based on interpretation of wave shapes in the weak-coupling approximation. It is of interest to use the wave shapes to evaluate the degree of approximation involved in the various models of piezoelectric response. Such an evaluation is shown in Fig. 4.5, in which normalized current-time wave forms calculated from various models are shown for x-cut quartz and z-cut lithium niobate. In both cases the differences between the fully coupled and weakly coupled solutions are observed to be about 1%, which is within the accuracy limits of the calculations. Hence, for both quartz and lithium niobate, weakly coupled solutions appear adequate for interpretation of observed current-time waveforms. On the other hand, the adequacy of the uncoupled solution is significantly different for the two materials. For x-cut quartz the maximum error of about 1%-1.5% for the nonlinear-uncoupled solution is suitable for all but the most precise interpretation. For z-cut lithium niobate the maximum error of about 8% for the nonlinear-uncoupled solution is greater than that considered acceptable for most cases. The linear-uncoupled solution is seriously in error in each case as it neglects both strain and coupling. 

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