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Hyperbranched polymers will probably nd use in larger-scale or commodity applications where lower cost is a necessity and dendrimers in specialty applications where higher cost is justi ed..

Comparing (3.22) with the Taylor expansion of 'Ij;(r, t + tlt) around 'Ij;(r, t), we find that the time component of the four-momentum in configuration space must be given by .h 8 (3.23) Po ---+ z--.

3-166



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where r and Lw are the polymerization rate and weight-average degree of polymerization in the PLP-SEC experiment and d is the relative contribution of disproportionation to termination, de ned as the ratio ktd = ktd ktc [Beuermann and Buback, 2002]. 3-8d Typical Values of Reaction Parameters

So if we use (3.19) as it is, we obtain the following quantum-mechanical wave equation: h2 8 2 _ _ _ 'Ij; + h 2 \1 2 '1j; = m 2 c 2 . (3.24) c2 8t 2 This is the Klein-Gordon equation. I I Unfortunately, it is second order in the time,12 which leads to a probability density that is not positive definite. There are very





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Table 3-10 shows the values of the various concentrations, rates, and rate constants involved in the photopolymerization of methacrylamide as well as the range of values that are generally encountered in radical chain polymerizations. For the methacrylamide case, the experi1=2 mentally determined quantities were Ri , Rp s , [M], [I], kp =kt , ts , and kp =kt . All of the other

90ne of the problems in [497], for instance, is that the point of departure is the energy-momentum relation for a particle of vanishing rest mass, but the conclusion is that the rest mass must be nonvanishing. Also, the wave equations obtained in [497] are not those that are now known as Proca equations. lOWe notice that unlike Section 2.1, there is no delta function here, because we are no longer assuming that t/J(r, t) = (rlt/J), with Ir) being the eigenstates of the particle's position operator. Here r is a parameter like t. II It apparently was discovered by Schr&linger. 12Nevertheless, there are ways to avoid these problems, and the Klein-Gordon equation is still used to describe particles of spin zero.

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TABLE 3-10 Reaction Parameters in Radical Chain Polymerization Quantity Ri kd [I] M s Rp s [M] kp Rt kt ts kp =kt 1=2 kp kt

{Vat(k)an+V*a~a(k)}.

Units mol L 1 s 1 s 1 mol L 1 mol L 1 mol L 1 s 1 mol L 1 L mol 1 s 1 mol L 1 s 1 L mol 1 s 1 s 1 none L1=2 mol 1=2 s 1=2

(9.1)

General Range of Values 10 8 10 10 10 4 10 6 10 2 10 4 10 7 10 9 10 4 10 6 10 10 1 104 102 10 8 10 10 108 106 10 10 1 10 4 10 6 1 10 2

Note:To delete an index entry, select the XE field (including the braces that surround it) and press .

In the quantum optics literature this simple Hamiltonian is called the Gardiner-Collett Hamiltonian owing to its appearance in the two famous papers [109,225], where their input-output approach to damped quantum systems was developed. 3 From (9.1), one can deduce (see Problem 9.1) the Lindblad master equation for high-Q cavity damping (6.68) introduced in 6. This is fine as a first approximation that holds well for high-Q cavities, where as we have seen in Section 6.2, the photon round trip-time in the cavity is much shorter than the average time it takes to escape to the outside (lifetime). But as soon as the cavity Q decreases a little, this approximation starts to break down [37, 43, 228, 390, 391, 408, 603]. An exact solution can be obtained by expanding the fields in terms of the normal modes of the entire closed system formed by the cavity and the outside, as we did in Section 2.5.2. This is called the modes-of-the-universe approach. Unfortunately, these modes can only be calculated for the simplest of structures. Moreover, as they are modes of the entire system, a photon in one of these modes of the continuum is completely delocalized. What one would like is an exact treatment where cavity modes were singled out explicitly. Then a deeper conceptual question also arises: What is a mode of an open cavity This is the main theme of this chapter.

Methacrylamide Photopolymerizationa 8:75 10 9 3:97 10 2 2:30 10 8 3:65 10 6 0.20 7:96 102 8:73 10 9 8:25 106 2.62 9:64 10 5 2:77 10 1

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