The Dividing Surface

A schematic picture of how concentrations might vary across a liquid-vapor interface is given in Fig. III-ll. The convention indicated by superscript 1, that is, the F = 0 is illustrated. The dividing line is drawn so that the two areas shaded in full strokes are equal, and the surface excess of the solvent is thus zero. The area shaded with dashed strokes, which lies to the right of the dividing 

An approach developed by Guggenheim [106] avoids the somewhat artificial concept of the Gibbs dividing surface by treating the surface region as a bulk phase whose upper and lower limits lie somewhere in the bulk phases not far from the interface. 

---

It has been pointed out [138] that algebraically equivalent expressions can be derived without invoking a surface solution model. Instead, surface excess as defined by the procedure of Gibbs is used, the dividing surface always being located so that the sum of the surface excess quantities equals a given constant value. This last is conveniently taken to be the maximum value of F. A somewhat related treatment was made by Handa and Mukeijee for the surface tension of mixtures of fluorocarbons and hydrocarbons [139]. 

Two alternative means around the difficulty have been used. One, due to Pethica [267] (but see also Alexander and Barnes [268]), is as follows. The Gibbs equation, Eq. III-80, for a three-component system at constant temperature and locating the dividing surface so that Fi is zero becomes... 

The hypersurface fomied from variations in the system s coordinates and momenta at//(p, q) = /Tis the microcanonical system s phase space, which, for a Hamiltonian with 3n coordinates, has a dimension of 6n -1. The assumption that the system s states are populated statistically means that the population density over the whole surface of the phase space is unifomi. Thus, the ratio of molecules at the dividing surface to the total molecules [dA(qi, p )/A]... 

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. 

Equation (2.2) defines the statistically averaged flux of particles with energy E = P /2m -f V Q) and P > 0 across the dividing surface with Q =0. The step function 6 E — Vq) is introduced because the classical passage is possible only at > Vq. In classically forbidden regions, E < Vq, the barrier transparency is exponentially small and given by the well known WKB expression (see, e.g., Landau and Lifshitz [1981])... 

The identity of (3.97) and (3.98) means that the particle hits the product valley only having crossed the dividing surface x = x from left to right. If we were to use simply the step function 9(x— x ), we would be neglecting the recrossings of the dividing surface. 

Now we make the usual assumption in nonadiabatic transition theory that non-adiabaticity is essential only in the vicinity of the crossing point where e(Qc) = 0- Therefore, if the trajectory does not cross the dividing surface Q = Qc, its contribution to the path integral is to a good accuracy described by adiabatic approximation, i.e., e = ad Hence the real part of partition function, Zq is the same as in the adiabatic approximation. Then the rate constant may be written as... 

The functional B[(2(r)] actually depends only on the velocity dQ/dr at the moment when the non-adiabaticity region is crossed. If we take the path integral by the method of steepest descents, considering that the prefactor B[(2(r)] is much more weakly dependent on the realization of the path than Sad[Q(A]> we shall obtain the instanton trajectory for the adiabatic potential V a, then B[(2(t)] will have to be calculated for that trajectory. Since the instanton trajectory crosses the dividing surface twice, we finally have... 

Once the molecular volume has been divided, the electron density may be integrated within each of the atomic basins to give a net atomic charge. As the dividing surface is... 

The meaning of the surface excess is illustrated in Fig. 1, in which the solid line represents the actual concentration profile of an adsorbate i, when the bulk concentration of i in the phase a (a = O or W) is c . The hatched area corresponds to be the surface excess of i, T,. This quantity depends on the location of the dividing surface. On the other hand, the experimentally accessible quantity should not depend on the location of the artificially introduced dividing surface. The relative surface excess, which is independent of the location of the dividing surface, is defined by relativizing it with respect to those of certain reference components. In oil water interfaces, the mutual solubility of solvents can be significant. The relative surface excess in Eq. (3) is then related to the surface excesses through... 

The geometric version of TST laid out in Section II is centered around the NHIM that defines the dividing surface and its stable and unstable manifolds that act as separatrices. The NHIMs at different energies are in turn organized by the saddle point. It forms a fixed point of the dynamics—that is it is itself an invariant object—and it provides the Archimedean point in which the geometric phase-space structure is anchored. 

From both the time-dependent plot and the time-independent projection, it is clear that the transition path crosses the space-fixed dividing surface qu = 0 several times. These crossings are indicated by thick green dots. As expected, therefore, the fixed surface is not free of recrossings and thus does not satisfy the fundamental requirement for an exact TST dividing surface. The moving surface, by contrast, is crossed only once, at the reaction time head = 8.936 that is marked by the blue cut. The solid blue line in this cut shows the instantaneous position of the dividing surface dotted lines indicate coordinate axes. 

Theorem 2 The probability that a chain of n segments, which originates at and terminates at (both on the interface), will be entirely on one side Of the dividing surface is... 

Let us now consider an interface between two isotropic multi-component phases. The number of moles of a component i in the two phases adjacent to the interface are given as n and nSince the mass balance of the overall system must be obeyed, it is necessary to assume that the dividing surface contains a certain... 

To establish the equilibrium conditions for pressure we will consider a movement of the dividing surface between the two phases a and [i. The dividing surface moves a distance d/ along its normal while the entropy, the total volume and the number of moles n, are kept constant. An infinitesimal change in the internal energy is now given by... 

By subtracting the internal energy of the two homogeneous phases adjacent to the dividing surface from equation (6.76) the internal energy of the dividing surface is obtained ... 

The adsorption T depends on the position of the Gibbs dividing surface and it is therefore convenient to define a new function, the relative adsorption, that is not dependent on the dividing surface. The absorption of component i at the interface is defined by eq. (6.3) as... 

Transition State Theory [1,4] is the most frequently used theory to calculate rate constants for reactions in the gas phase. The two most basic assumptions of this theory are the separation of the electronic and nuclear motions (stemming from the Bom-Oppenheimer approximation [5]), and that the reactant internal states are in thermal equilibrium with each other (that is, the reactant molecules are distributed among their states in accordance with the Maxwell-Boltzmann distribution). In addition, the fundamental hypothesis [6] of the Transition State Theory is that the net rate of forward reaction at equilibrium is given by the flux of trajectories across a suitable phase space surface (rather a hypersurface) in the product direction. This surface divides reactants from products and it is called the dividing surface. Wigner [6] showed long time ago that for reactants in thermal equilibrium, the Transition State expression gives the exact... 

---