Probability of phase

The a priori probability of phase a may thus be related to its free energy by... 

Direct methods Aim for no negative areas in electron-density map. Probabilities of phases analyzed. Used for small molecules. 

We consider especially ensembles of systems in which the index (or logarithm) of probability of phase is a linear function of the energ>. This distribution on account of its unique importance in the theory of statistical equilibrium, I have ventured to call... 

The most frequent application of phase-equilibrium calculations in chemical process design and analysis is probably in treatment of equilibrium separations. In these operations, often called flash processes, a feed stream (or several feed streams) enters a separation stage where it is split into two streams of different composition that are in equilibrium with each other. 

Typical shapes of the orientation distribution function are shown in figure C2.2.10. In a liquid crystal phase, the more highly oriented the phase, the moreyp tends to be sharjDly peaked near p=0. However, in the isotropic phase, a molecule has an equal probability of taking on any orientation and then/P is constant. 

In this chapter, we discussed the significance of the GP effect in chemical reactions, that is, the influence of the upper electronic state(s) on the reactive and nonreactive transition probabilities of the ground adiabatic state. In order to include this effect, the ordinary BO equations are extended either by using a HLH phase or by deriving them from first principles. Considering the HLH phase due to the presence of a conical intersection between the ground and the first excited state, the general fomi of the vector potential, hence the effective... 

Experimentally, phases can be obtained by measurements of occupation probabilities of states using Eq. (9). (We have calculationally verified this for the case treated in [264].)... 

In the full quantum mechanical picture, the evolving wavepackets are delocalized functions, representing the probability of finding the nuclei at a particular point in space. This representation is unsuitable for direct dynamics as it is necessary to know the potential surface over a region of space at each point in time. Fortunately, there are approximate formulations based on trajectories in phase space, which will be discussed below. These local representations, so-called as only a portion of the FES is examined at each point in time, have a classical flavor. The delocalized and nonlocal nature of the full solution of the Schtddinger equation should, however, be kept in mind. 

To return to the simple picture of vertical excitation, the question remains as to how a wavepacket can be simulated using classical trajectories A classical ensemble can be specified by its distribution in phase space, Pd(p,Q), which gives the probability of finding the system of particles with momentum p and position q. In conUast, it is strictly impossible to assign simultaneously a position and momentum to a quantum particle. 

Note that despite the form this cannot be interpreted as the probability of finding a particle at a point in phase space, and in fact the function can become negative. Obtaining for a system is also not straightforward. For a hamionic... 

Pq r) may be negative or even imaginary. We then say that the probability of the system accessing that point in phase space is zero. This may be the case even when the energy is finite. 

We consider a two state system, state A and state B. A state is defined as a domain in phase space that is (at least) in local equilibrium since thermodynamic variables are assigned to it. We assume that A or B are described by a local canonical ensemble. There are no dark or hidden states and the probability of the system to be in either A or in B is one. A phenomenological rate equation that describes the transitions between A and B is... 

B(A) is the probability of observing the system in state A, and B(B) is the probability of observing state B. In this model, the space is divided exactly into A and B. The dividing hyper-surface between the two is employed in Transition State Theory for rate calculations [19]. The identification of the dividing surface, which is usually assumed to depend on coordinates only, is a non-trivial task. Moreover, in principle, the dividing surface is a function of the whole phase space - coordinates and velocities, and therefore the exact calculation of it can be even more complex. Nevertheless, it is a crucial ingredient of the IVansition State Theory and variants of it. 

An individual point in phase space, denoted by F, corresponds to a particular geometry of all the molecules in the system. There are many points in this phase space that will never occur in any real system, such as configurations with two atoms in the same place. In order to describe a real system, it is necessary to determine what configurations could occur and the probability of their occurrence. 

The characteristic feature of valence bond theory is that it pictures a covalent bond between two atoms in terms of an m phase overlap of a half filled orbital of one atom with a half filled orbital of the other illustrated for the case of H2 m Figure 2 3 Two hydrogen atoms each containing an electron m a Is orbital combine so that their orbitals overlap to give a new orbital associated with both of them In phase orbital overlap (con structive interference) increases the probability of finding an electron m the region between the two nuclei where it feels the attractive force of both of them... 

For the evaporation process we mentioned above, the thermodynamic probability of the gas phase is given by the number of places a molecule can occupy in the vapor. This, in turn, is proportional to the volume of the gas (subscript g) 12- oc V In the last chapter we discussed the free volume in a liquid. The total free volume in a liquid is a measure of places for molecules to occupy in the liquid. The thermodynamic probability of a liquid (subscript 1) is thus V, oc V, frgg. Based on these ideas, the entropy of the evaporation process can be written as... 

To obtain thermodynamic averages over a canonical ensemble, which is characterized by the macroscopic variables (N, V, T), it is necessary to know the probability of finding the system at each and every point (= state) in phase space. This probability distribution, p(r, p), is given by the Boltzmann distribution function. 

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