Matrix element off-diagonal

In solving the secular equation it is important to know which of the off-diagonal matrix elements " I wanish since this will enable us to simplify the equation. 

Since the vibrational eigenstates of the ground electronic state constitute an orthonomial basis set, tire off-diagonal matrix elements in equation (B 1.3.14) will vanish unless the ground state electronic polarizability depends on nuclear coordinates. (This is the Raman analogue of the requirement in infrared spectroscopy that, to observe a transition, the electronic dipole moment in the ground electronic state must properly vary with nuclear displacements from... 

Symmetry considerations forbid any nonzero off-diagonal matrix elements in Eq. (68) when f(x) is even in x, but they can be nonzero if f x) is odd, for example,/(x) = x. (Note that x itself hansforms as B2 [284].) Figure 3 shows the outcome for the phase by the continuous phase tracing method for cycling... 

The first and second terras contain phase factors identical to those previously met in Eq. (82). The last term has the new phase factor [Though the power of q in the second term is different from that in Eq. (82), this term enters with a physics-based coefficient that is independent of k in Eq. (82), and can be taken for the present illustration as zero. The full expression is shown in Eq. (86) and the implications of higher powers of q are discussed thereafter.] Then a new off-diagonal matrix element enlarged with the third temi only, multiplied by a (new) coefficient X, is... 

To see that this phase has no relation to the number of ci s encircled (if this statement is not already obvious), we note that this last result is true no matter what the values of the coefficients k, X, and so on are provided only that the latter is nonzero. In contrast, the number of ci s depends on their values for example, for some values of the parameters the vanishing of the off-diagonal matrix elements occurs for complex values of q, and these do not represent physical ci s. The model used in [270] represents a special case, in which it was possible to derive a relation between the number of ci s and the Berry phase acquired upon circling about them. We are concerned with more general situations. For these it is not warranted, for example, to count up the total number of ci s by circling with a large radius. 

Note that the exact adiabatic functions are used on the right-hand side, which in practical calculations must be evaluated by the full derivative on the left of Eq. (24) rather than the Hellmann-Feynman forces. This forai has the advantage that the R dependence of the coefficients, c, does not have to be considered. Using the relationship Eq. (78) for the off-diagonal matrix elements of the right-hand side then leads directly to... 

The remaining combinations vanish for symmetry reasons [the operator transforms according to B (A") hreducible representation]. The nonvanishing of the off-diagonal matrix element fl+ is responsible for the coupling of the adiabatic electronic states. 

Thus in the lowest order approximation the angle x is eliminated from the off-diagonal matrix elements of [second and third of Eqs. (60)] it solely determines the selection rules for matrix elements of Hg with respect to nuclear basis functions. 

Thus, the neglect of the off-diagonal matrix elements allows the change from mixed states of the nuclear subsystem to pure ones. The motion of the nuclei leads only to the deformation of the electronic distribution and not to transitions between different electronic states. In other words, a stationary distribution of electrons is obtained for each instantaneous position of the nuclei, that is, the elechons follow the motion of the nuclei adiabatically. The distribution of the nuclei is described by the wave function x (R i) in the potential V + Cn , known as the proper adiabatic approximation [41]. The off-diagonal operators C n in the matrix C, which lead to transitions between the states v / and t / are called operators of nonadiabaticity and the potential V = (R) due to the mean field of all the electrons of the system is called the adiabatic potential. 

The ti eatment of the Jahn-Teller effect for more complicated cases is similar. The general conclusion is that the appearance of a linear term in the off-diagonal matrix elements H+- and H-+ leads always to an instability at the most symmetric configuration due to the fact that integrals of the type do not vanish there when the product < / > / has the same species as a nontotally symmetiic vibration (see Appendix E). If T is the species of the degenerate electronic wave functions, the species of will be that of T, ... 

Xv reside on neighboring atoms that are ehemieally bonded. If X i and Xv reside on atoms that are not bonded neighbors, then the off-diagonal matrix element is set equal to zero. 

The simplest scheme that accounts for the destruction of phase coherence is the so-called stochastic interruption model [Nikitin and Korst 1965 Simonius 1978 Silbey and Harris 1989]. Suppose the process of free tunneling is interrupted by a sequence of collisions separated by time periods vo = to do After each collision the system forgets its initial phase, i.e., the off-diagonal matrix elements of the density matrix p go to zero, resulting in the density matrix p ... 

The potential surfaces Eg, Hn, and H22 of the HF molecule are described in Fig. 1.6. These potential surfaces provide an instructive example for further considerations of our semiempirical strategy (Ref. 5). That is, we would like to exploit the fact that Hn and H22 represent the energies of electronic configurations that have clear physical meanings (which can be easily described by empirical functions), to obtain an analytical expression for the off-diagonal matrix element H12. To accomplish this task we represent Hn, H22, and Eg by the analytical functions... 

Because we are concerned only with the analysis of the absorption spectra of P band and B band, we consider the excitonic interactions among P, BL, and BM shown in Fig. 8. Here (oti, ot2,0C3,014) represent the diagonal matrix elements, while (p, (314, P23, P34) represent the off-diagonal matrix elements [67]. As shown in Introduction, a main feature of the P band is that its absorption maximum shows a pronounced temperature shift [42,52], According to the displaced oscillator model, the absorption maximum is independent of T. Although the distortion effect of potential surfaces will introduce some temperature shift, the effect cannot be as large as that shown in Fig. 2. 

The obstacle to simultaneous quantum chemistry and quantum nuclear dynamics is apparent in Eqs. (2.16a)-(2.16c). At each time step, the propagation of the complex coefficients, Eq. (2.11), requires the calculation of diagonal and off-diagonal matrix elements of the Hamiltonian. These matrix elements are to be calculated for each pair of nuclear basis functions. In the case of ab initio quantum dynamics, the potential energy surfaces are known only locally, and therefore the calculation of these matrix elements (even for a single pair of basis functions) poses a numerical difficulty, and severe approximations have to be made. These approximations are discussed in detail in Section II.D. In the case of analytic PESs it is sometimes possible to evaluate these multidimensional integrals analytically. In either case (analytic or ab initio) the matrix elements of the nuclear kinetic energy... 

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