Coordinates asymptotic

We have expressed P in tenns of Jacobi coordinates as this is the coordmate system in which the vibrations and translations are separable. The separation does not occur in hyperspherical coordinates except at p = oq, so it is necessary to interrelate coordinate systems to complete the calculations. There are several approaches for doing this. One way is to project the hyperspherical solution onto Jacobi s before perfonning the asymptotic analysis, i.e. 

The conceptually simplest approach to solve for the -matrix elements is to require the wavefimction to have the fonn of equation (B3.4.4). supplemented by a bound function which vanishes in the asymptote [32, 33, 34 and 35] This approach is analogous to the fiill configuration-mteraction (Cl) expansion in electronic structure calculations, except that now one is expanding the nuclear wavefimction. While successfiti for intennediate size problems, the resulting matrices are not very sparse because of the use of multiple coordinate systems, so that this type of method is prohibitively expensive for diatom-diatom reactions at high energies. 

Figure B3.4.3. A schematic figure showing, for the DH2 collinear system, a reaction-path coordmate Q coimecting continuously the reactants and the single products asymptote. Also shown are the cuts denoting the coordinate perpendicular to Q.

Single surface calculations with a vector potential in the adiabatic representation and two surface calculations in the diabatic representation with or without shifting the conical intersection from the origin are performed using Cartesian coordinates. As in the asymptotic region the two coordinates of the model represent a translational and a vibrational mode, respectively, the initial wave function for the ground state can be represented as. 

A convenience of electronic basis functions (53) is that they reduce at infinitesimal-amplitude bending to (28) with the same meaning of the angle 9 we may employ these asymptotic forms in the computation of the matrix elements of the kinetic energy operator and in this way avoid the necessity of carrying out calculations of the derivatives of the electronic wave functions with respect to the nuclear coordinates. The electronic part of the Hamiltonian is represented in the basis (53) by... 

Asymptotic Solution Rate equations for the various mass-transfer mechanisms are written in dimensionless form in Table 16-13 in terms of a number of transfer units, N = L/HTU, for particle-scale mass-transfer resistances, a number of reaction units for the reaction kinetics mechanism, and a number of dispersion units, Np, for axial dispersion. For pore and sohd diffusion, q = / // p is a dimensionless radial coordinate, where / p is the radius of the particle, if a particle is bidisperse, then / p can be replaced by the radius of a suoparticle. For prehminary calculations. Fig. 16-13 can be used to estimate N for use with the LDF approximation when more than one resistance is important. 

In other words, the exact wave function behaves asymptotically as a constant 4- l/2ri2 when ri2 is small. It would therefore seem natural that the interelectronic distance would be a necessary variable for describing electron correlation. For two-electron systems, extremely accurate wave functions may be generated by taking a trial wave function consisting of an orbital product times an expansion in electron coordinates such as... 

Symmetry 50. Intercepts 50. Asymptotes 50. Equations of Slope 51. Tangents 51. Equations of a Straight Line 52. Equations of a Circle 53. Equations of a Parabola 53. Equations of an Ellipse of Eccentricity e 54. Equations of a Hyperbola 55. Equations of Three-Dimensional Coordinate Systems 56. Equations of a Plane 56. Equations of a Line 57. Equations of Angles 57. Equation of a Sphere 57. Equation of an Ellipsoid 57. Equations of Hyperboloids and Paraboloids 58. Equation of an Elliptic Cone 59. Equation of an Elliptic Cylinder 59. 

Rate of change of observables, 477 Ray in Hilbert space, 427 Rayleigh quotient, 69 Reduction from functional to algebraic form, 97 Regula fold method, 80 Reifien, B., 212 Relative motion of particles, 4 Relative velocity coordinate system and gas coordinate system, 10 Relativistic invariance of quantum electrodynamics, 669 Relativistic particle relation between energy and momentum, 496 Relativistic quantum mechanics, 484 Relaxation interval, 385 method of, 62 oscillations, 383 asymptotic theory, 388 discontinuous theory, 385 Reliability, 284... 

Fig. 2. Schematic configuration space for the reaction AB + CD — A + BCD. R is the radial coordinate between the center-of-mass of the two diatoms, and r is the vibrational coordinate of the reactive AB diatom. I denotes the interaction region and II denotes the asymptotic region. The shaded regions are the absorption zones for the time-dependent wavefunction to avoid boundary reflections. The reactive flux is evaluated at the r = rB surface.

The NRT formalism will be used to describe the interacting species along the entire reaction coordinate. Such a continuous representation allows the TS complex to be related both to asymptotic reactant and product species and to other equilibrium bonding motifs (e.g., 3c/4e hypervalent bonding Section 3.5). A TS complex can thereby be visualized as intermediate between two distinct chemical bonding arrangements, emphasizing the relationship between supramolecular complexation and partial chemical reaction. 

As seen in Fig. 5.35, the highest TS barrier to proton transfer along the reaction coordinate lies significantly (>7 kcal mol 1) below the energy of either reactant or product asymptote. Thus, unless trapped in the deep H H20 well, an H- ion impinging on a water molecule will undergo spontaneous proton transfer to form H2 + OH-, without an apparent barrier. 

The motion on the PES corresponds to an interchange of potential and kinetic energies and asymptotically rearrangement of particles in a reactive collision. For a given / , we can plot the time variation of the coordinates on the top of the PE contours as shown in Fig. 9.25. These are called the trajectories and their behavior would tell as about molecular collisions. 

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