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where the subscript in each displacement operator denotes the mode it corresponds to (e.g., De. corresponds to the cavity mode), and the productory is over the continuum of external modes. The steady-state quantum state of our closed system is obtained by applying (8.106) to the initial quantum state. Assuming that we started with the quantum vacuum before switching on our ideal laser, both the cavity and outside are in a product of coherent states in the steady state. 19 In particular, the cavity mode is in the coherent state (8.107) where Ii> is a number state with i photons. The main effect of spontaneous emission is to make the phase of this coherent state perform a random walk which leads to a very slow phase diffusion. For times short enough compared with this diffusion time, a coherent state is a good approximation to the quantum state of laser light.



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Also, optimization of the physical properties of the product often required removal of the atactic fraction The initiator systems were inef cient with less than 1% of the Ti being active in polymerization The later generations of initiators, starting in the late 1970s, increased initiator ef ciency and activity without sacri cing stereoselectivity [Bohm, 2001; Busico and Cipullo, 2001; Cecchin et al, 2001; Chadwick, 2001; Chadwick et al, 2001; Chien et al, 1982; Hu and Chien, 1988] The effective surface area of the active component of the initiator system was increased by close to 2 orders of magnitude by using MgCl2 as a solid support in which TiCl4 is nely dispersed Stereoselectivity was kept high and actually increased by the addition of electron-donor additives.





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The first ASER was the ammonia-beam maser, whose idea came to Charles Townes in 1951 on a park bench [602] and was realized three years later by James P. Gordon, Herbert J. Zeiger, and Townes at Columbia University [242]. It consisted of a microwave cavity through which a beam of excited ammonia molecules was sent (Figure 8.4). At any given time there would be a large number of ammonia molecules in the cavity; otherwise, it would not mase. Incoherent processes such as cavity damping, thermal blackbody radiation, decay from the molecular energy levels of the masing transition, and the velocity spread of the molecular beam played a major role in the dynamics of the device. It took 31 years to reduce most of these incoherent processes to a negligible level and to build a much simpler device20: a maser that mases in the quantum regime of no, No 1. The first such micromaser was realized by Dieter Meschede, Herbert Walther, and GUnter MUller at the Max-Planck Institute for Quantum Optics in Garching, Germany [440]. As in the first maser, the gain medium was also a material beam that flowed across the cavity rather than something that remained inside it (Figure 8.5). But the

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A typical recipe for a present-day superactive or high-mileage initiator system involves ball milling of MgCl2 (or the alkoxide) and TiCl4 followed by the addition of Al(C2 H5 )3 with an electron donor (such as dialkyl phthalate and alkoxysilane) usually added in each step of preparation Activity is 50 200 kg polymer per gram of initiator system Typically, the initiator system is no more than 2 4% Ti, which makes the activity about 1500 6000 kg polymer per gram of Ti The high activity not only minimizes initiator and production costs but also avoids the costly task of initiator removal from the polymer product (except possibly for food- and medical-grade products) Isotactic indices for polypropene have been increased to 98% or higher with (mmmm) pentad fractions up to 98% and higher This not only improves the product s physical properties but also avoids the need to remove the atactic fraction..

19Notice that, in general, a dissipative system and its environment would become entangled rather than remain in a product state through time evolution. 2OFrom the point of view of theory.

Some early polymerizations reported as Ziegler Natta polymerizations were conventional free-radical, cationic, or anionic polymerizations proceeding with low stereoselectivity. Some Ziegler Natta initiators contain components that are capable of initiating conventional ionic polymerizations of certain monomers, such as anionic polymerization of methacrylates by alkyllithium and cationic polymerization of vinyl ethers by TiCl4 . Most Ziegler Natta components participate in a complex set of reactions involving alkylation and reduction of the transition-metal component by the group I III component as shown below for TiCl4 AlR3 :

Figure 8_4 Schematic diagram of the first maser. A beam of ammonia emerges from an oven and goes into the focuser, which separates out the molecules in the lower state. As the beam enters the microwave cavity, it consists basically of molecules in the upper state of the masing transition. (Reproduced from [242], 1955 The American Physical Society.)

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TiCl 4 + AlR3 TiCl 4 + AlR2Cl TiCl 3R + AlR3 TiCl 3R TiCl 3 + AlR3 R TiCl 3R + AlR2Cl TiCl 3R + AlRCl2 TiCl 2R2 + AlRCl2 TiCl 3 + R TiCl 2R + AlR2Cl

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