Bundles

Figure 10.36 Electro-Hydraulic Control Umbilical Bundle...

If the solid in question is available only as a finely divided powder, it may be compressed into a porous plug so that the capillary pressure required to pass a nonwetting liquid can be measured [117]. If the porous plug can be regarded as a bundle of capillaries of average radius r, then from the Laplace equation (II-7) it follows that... 

A simple law, known as Darcy s law (1936), states that the volume flow rate per unit area is proportional to the pressure gradient if applied to the case of viscous flow through a porous medium treated as a bundle of capillaries,... 

Wang ZLetal 1998 Bundling and interdigitation of adsorbed thiolate groups in self-assembled nanoorystal superlattioes J. Phys. Chem. B 102 3068... 

For the case of intramolecular energy transfer from excited vibrational states, a mixed quantum-classical treatment was given by Gerber et al. already in 1982 [101]. These authors used a time-dependent self-consistent field (TDSCF) approximation. In the classical limit of TDSCF averages over wave functions are replaced by averages over bundles of trajectories, each obtained by SCF methods. 

Conformational free energy simulations are being widely used in modeling of complex molecular systems [1]. Recent examples of applications include study of torsions in n-butane [2] and peptide sidechains [3, 4], as well as aggregation of methane [5] and a helix bundle protein in water [6]. Calculating free energy differences between molecular states is valuable because they are observable thermodynamic quantities, related to equilibrium constants and... 

E. M. Boczko and C. L. Brooks III. First principles calculation of the folding free energy of a three helix bundle protein. Science, 269 393-396, 1995. 

Caustics The above formulae can only be valid as long as Eq. (9) describes a unique map in position space. Indeed, the underlying Hamilton-Jacobi theory is only valid for the time interval [0,T] if at all instances t [0, T] the map (QOi4o) —> Q t, qo,qo) is one-to-one, [6, 19, 1], i.e., as long as trajectories with different initial data do not cross each other in position space (cf. Fig. 1). Consequently, the detection of any caustics in a numerical simulation is only possible if we propagate a trajectory bundle with different initial values. Thus, in pure QCMD, Eq. (11), caustics cannot be detected. 

Referring to Thm. 1 we can conclude that—excluding caustics—QCMD (and QCMD bundles) approximates full QD up to an error of order 0(6- -e). These... 

A particularly convenient notation for trajectory bundle system can be introduced by using the classical Liouville equation which describes an ensemble of Hamiltonian trajectories by a phase space density / = f q, q, t). In textbooks of classical mechanics, e.g. [12], it is shown that Liouville s equation... 

We will refer to this model as to the semiclassical QCMD bundle. Eqs. (7) and (8) would suggest certain initial conditions for /,. However, those would not include any momentum uncertainty, resulting in a wrong disintegration of the probability distribution in g as compared to the full QD. Eor including an initial momentum uncertainty, a Gaussian distribution in position space is used... 

Can QCMD describe non-adiabatic processes , is there any situation in which BO fails but QCMD or its bundle variants are still useful ... 

In a way, the limit set is thus the entire funnel between the two extreme cases qlc, and g o, Fig. 5. This effect is called Takens-chaos, [21, 5, 7]. As a consequence of this theorem each momentum uncertainty effects a kind of disintegration" process at the crossing. Thus, one can reasonably expect to reproduce the true excitation process by using QCMD trajectory bundles for sampling the funnel. To realize this idea, we have to study the full quantum solution and compare it to suitable QCMD trajectory bundles. 

Unfortunately, the semiclassical QCMD bundles, Eq. (14) in 2.3, are only of limited use here. To understand this, let us consider the g-expectation [g] of its solution Recall that the expectation of a classical observable... 

Since QCMD reproduces the BO solution, we again have [g] = q o ignoring the non-adiabatic excitation process at the crossing. Consequently, we have to modify the very concept of QCMD bundles. 

Actually, Fig. 4 has been obtained using the following modification of the QCMD bundle one propagates an ensemble of independent, single QCMD trajectories qk,qk, -tpk), k = 1,...,N ... 

A comparison of Fig. 4 and Fig. 3 shows that this uncoupled QCMD bundle reproduces the disintegration of the full QD solution. However, there are minor quantitative differences of the statistical distribution. Fig. 5 depicts... 

Pig. 5. Comparison of the qi expectation value of the uncoupled QCMD bundle ([g]e o) and full QD ( q)qd) for the test system for e = 1/100 (pictures on top) and e = 1/500 (below). Initial data as in Fig. 3. The shaded domain indicates the funnel between the two curves Qbo and geo (cf. Thm. 5). The light dashed line shows Hagedorn s limit solution qna and the dense lines (q )Qo (left hand pictures) and [ ]e s (right hand pictures). 

Geankoplis [54] fabricated a porous medium for which the values of K, and are known a priori. This was accomplished by sealing a bundle of identical parallel cylindrical capillary tubes between the two chambers of a Wlcke-Kallenbach apparatus. Then the relevant flux relations are those which apply to a single cylindrical capillary, rather than a porous medium, and these are obtained by setting... 

Remick and Geankoplis made flux measurements for both species in the isobaric diffusion of nitrogen and helium through their tube bundle. Pressures spanned the interval from 0.444 nim, Hg to 300,2 ram Hg, which should cover the whole range between the limits of Knudsen streaming and bulk diffusion control. Then, since K and K, are known in this case, the form of the proposed flux relations could be tested immediately by plotting the left hand side of equation (10.15) against... 

Some of these software packages also have semiempirical or molecular mechanics functionality. However, the primary strength of each is ah initio calculation. There are also ah initio programs bundled with the Unichem, Spartan, and Hyperchem products discussed previously in this appendix. 

There are also semiempirical programs bundled with the Unichem, Spartan, and Hyperchem products discussed previously in this appendix. 

A semiempirical crystal band structure program, called BZ, is bundled with MOPAC 2000. There is also a utility, referred to as MAKPOL, for generating the input for band structure calculations with BZ. With the use of MAKPOL, the input for band-structure computations is only slightly more complicated than that for molecular calculations. 

Price category free (older versions), production, departmental, bundled with other programs... 

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