Potential energy crossing

According to the theory of absolute reaction rates [4-9], the rate is the product of a universal frequency factor and the concentration of the activated complex or transition state, M (the system in the transient state of highest potential energy), crossing the energy barrier in the direction toward the products. The activated complex, in turn, is postulated to be in equilibrium with the reactants. Say, for a single-step reaction A + B — P ... 

There are several possible approaches to simplifying the vibrational Hamiltonian given by Eq. (3.13). Some of these will be outlined here. The first approach consists of removing the harmonic potential energy cross terms and the kinetic energy terms by the equivalent of a normal coordinate transformation. We define a new set of coordinates Q... 

Similarly, the potential energy cross terms may be removed. If we write the total vibrational potential energy... 

Pitzer and Gwinn have considered calculations for molecules having potential energy cross-terms between vibrational and internal rotational motion. Here is not, even to a first approximation, independent... 

Many applications of Kilpatrick and Pitzer s procedure for calculating thermodynamic properties of molecules with compound rotation have been reported. In all cases possible potential energy cross-terms between rotating tops have been neglected. Contributions from internal rotation of symmetric tops have been calculated using the appropriate tables." These tables have also been used in calculations for the internal rotation of asymmetric tops hindered by a simple -fold cosine potential. 3-Fold potential barriers have been assumed in calculations for the —OH rotations in propanol and 1-methylpropanol, the —SH rotations in propane-1-thiol, butane-2-thiol, 2-methylpropane-l-thiol, and 2-methylbutane-2-thiol, the C—S skeletal rotations in ethyl methyl sulphide, diethyl sulphide, isopropyl methyl sulphide, and t-butyl methyl sulphide, and the C—C skeletal rotations in 2,3-dimethylbutane, and 2-methylpropane-l-thiol. 2-Fold cosine potential barriers have been assumed in calculations in the S—S skeletal rotations in dimethyl disulphide and diethyl disulphide. ... 

The symbol used for the bond length at which the intermolecular potential energy crosses zero is usually cr. As indicated in Chapter 3, we have too many uses for a- already, and the traditional notation is sacrificed here for clarity. 

Figure 3 Plot of the LJ and WCA interaction potentials. The LJ potential energy crosses zero at r = a and has a minimum energy of —e. The WCA potential has the same shape as the repulsive part of the LJ potential, but is shifted up in energy by e.

Figure Al.4.6. A cross-section of the potential energy surface of PH. The coordinate p is defined in figure Al.4.5.

Figure B3.3.13. Intersecting stacking faults in a fee crystal at the impact plane induced by collision with a momentum mirror for a square cross section of side 100 unit cells. The shock wave has advanced half way to the rear ( 250 planes). Atom shading indicates potential energy. Thanks are due to B Holian for tliis figure.

Figure B3.4.7. Schematic example of potential energy curves for photo-absorption for a ID problem (i.e. for diatomics). On the lower surface the nuclear wavepacket is in the ground state. Once this wavepacket has been excited to the upper surface, which has a different shape, it will propagate. The photoabsorption cross section is obtained by the Fourier transfonn of the correlation function of the initial wavefimction on tlie excited surface with the propagated wavepacket.

Here the transition state is approximated by the lowest crossing pomt on the seam intersecting the diabatic (non-interacting) potential energy surfaces of the reactant and product. The method was originally developed... 

The vibrationally excited states of H2-OH have enough energy to decay either to H2 and OH or to cross the barrier to reaction. Time-dependent experiments have been carried out to monitor the non-reactive decay (to H2 + OH), which occurs on a timescale of microseconds for H2-OH but nanoseconds for D2-OH [52, 58]. Analogous experiments have also been carried out for complexes in which the H2 vibration is excited [59]. The reactive decay products have not yet been detected, but it is probably only a matter of time. Even if it proves impossible for H2-OH, there are plenty of other pre-reactive complexes that can be produced. There is little doubt that the spectroscopy of such species will be a rich source of infonnation on reactive potential energy surfaces in the fairly near future. 

Figure C3.2.1. A slice tlirough tlie intersecting potential energy curves associated witli tlie K-l-Br2 electron transfer reaction. At tlie crossing point between tlie curves (Afy, electron transfer occurs, tlius Tiarjiooning tlie species,...

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