Eigenvalues potential

Finally, the simplest approach to extract resonances is to add to the Hamiltonian an absorbing potential [8, 48. 108. 109], and then look for the complex eigenvalues of the Hamiltonian /7-i Vj. The absorbing potential... 

For large k, the approximate potential minimum lies at r = k and the lower vibronic eigenvalues are given by [2]... 

Figure 3. Floquet band structure for a threefold cyclic barrier (a) in the plane wave case after using Eq. (A.l 1) to fold the band onto the interval —I < and (b) in the presence of a threefold potential barrier. Open circles in case (b) mark the eigenvalues at = 0, 1, consistent with periodic boundary conditions. Closed circles mark those at consistent with sign-changing...

To determine the vibrational motions of the system, the eigenvalues and eigenvectors of a mass-weighted matrix of the second derivatives of potential function has to be calculated. Using the standard normal mode procedure, the secular equation... 

In the spirit of Koopmans theorem, the local ionization potential, IPi, at a point in space near a molecule is defined [46] as in Eq. (54), where HOMO is the highest occupied MO, p( is the electron density due to MO i at the point being considered, and ej is the eigenvalue of MO i. 

The excess energies can be measured for a known by essentially a stopping potential method, giving a spechum. This spectrum is then matched with calculated orbital energies (eigenvalues) derived from molecular orbital calculations. 

For the kind of potentials that arise in atomic and molecular structure, the Hamiltonian H is a Hermitian operator that is bounded from below (i.e., it has a lowest eigenvalue). Because it is Hermitian, it possesses a complete set of orthonormal eigenfunctions ( /j Any function spin variables on which H operates and obeys the same boundary conditions that the ( /j obey can be expanded in this complete set... 

As mentioned earlier, a potential energy surface may contain saddle points , that is, stationary points where there are one or more directions in which the energy is at a maximum. Asaddle point with one negative eigenvalue corresponds to a transition structure for a chemical reaction of changing isomeric form. Transition structures also exist for reactions involving separated species, for example, in a bimolecular reaction... 

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