Q property

Table 61 shows the Dolg et al. (1990a, b) CISD and CISD + Q results on GdO for two electronic states. As seen from table 61, the agreement between the computed SDCI, SDCI + Q properties with experiment is quite good with the exception of the D. ... 

Generally, the observable response to an external perturbation is a mechanical property B p, q). Properties A and B may be identical, although they need not be. 

These moments are related to many physical properties. The Thomas-Kulm-Reiche sum rule says that. S (0) equals the number of electrons in the molecule. Other sum rules [36] relate S(2),, S (1) and. S (-l) to ground state expectation values. The mean static dipole polarizability is md = e-S(-2)/m,.J Q Cauchy expansion... 

Consider a measurable property B p, q) of the system, such as its energy or momentum. When a system is in... 

Q.lb), T = 2,al(21kb). This follows from the property that at the critical point on die P-V plane there is a... 

Hyperspherical coordinates have the properties that q motion is always bound since q = 0 and q = P correspond to cases where two of the three atoms are on top of one another, yielding a very repulsive potential. Also, p —> 0 is a repulsive part of the potential, while large p takes us to the reagent and product valleys. 

For reactions with well defined potential energy barriers, as in figure A3.12.1(a) and figure A3.12.1(b) the variational criterion places the transition state at or very near this barrier. The variational criterion is particularly important for a reaction where there is no barrier for the reverse association reaction see figure A3.12.1(c). There are two properties which gave rise to the minimum in [ - (q,)] for such a reaction. 

Each such nonual mode can be assigned a synuuetry in the point group of the molecule. The wavefrmctions for non-degenerate modes have the following simple synuuetry properties the wavefrmctions with an odd vibrational quantum number v. have the same synuuetry as their nonual mode 2the ones with an even v. are totally symmetric. The synuuetry of the total vibrational wavefrmction (Q) is tlien the direct product of the synuuetries of its constituent nonual coordinate frmctions (p, (2,). In particular, the lowest vibrational state. 

These new quantities allow us to directly relate properties of tire media to E and H. In essence tliey afford us tire opportunity to quantify tire field-matter interaction. The media response to tire fields is described generally in tenns of tire polarization, P and tire magnetization, M. (We note tliat in free space P and M=Q and we recover equation (C2.15.1 ), equation (C2.15.2 ), equation (C2.15.3 ) and equation (C2.15.4 ) above.)... 

U(qJ is referred to as an adiabatic-to-diabatic transformation (ADT) matrix. Its mathematical sbucture is discussed in detail in Section in.C. If the electronic wave functions in the adiabatic and diabatic representations are chosen to be real, as is normally the case, U(q ) is orthogonal and therefore has n n — l)/2 independent elements (or degrees of freedom). This transformation mabix U(qO can be chosen so as to yield a diabatic electronic basis set with desired properties, which can then be used to derive the diabatic nuclear motion Schrodinger equation. By using Eqs. (27) and (28) and the orthonormality of the diabatic and adiabatic electronic basis sets, we can relate the adiabatic and diabatic nuclear wave functions through the same n-dimensional unitary transformation matrix U(qx) according to... 

Equilibrium average properties are calculated using a statistical weighting of the probability Pq(r) of Eq. (3) raised to the power of q as required by the generalized statistical mechanics. The so-called q-expectation value is written... 

Note that, in loeal eoordinates. Step 2 is equivalent to integrating the equations (13). Thus, Step 2 can either be performed in loeal or in eartesian coordinates. We consider two different implicit methods for this purpose, namely, the midpoint method and the energy conserving method (6) which, in this example, coineides with the method (7) (because the V term appearing in (6) and (7) for q = qi — q2 is quadratie here). These methods are applied to the formulation in cartesian and in local coordinates and the properties of the resulting propagation maps are discussed next. 

Approximation Property We assume that the classical wavefunction 4> is an approximate 5-function, i.e., for all times t G [0, T] the probability density 4> t) = 4> q,t) is concentrated near a location q t) with width, i.e., position uncertainty, 6 t). Then, the quality of the TDSCF approximation can be characterized as follows ... 

The last step is to find a symplectic, second order approximation st to exp StL ). In principle, we can use any symplectic integrator suitable for time-dependent Schrddinger equations (see, for example, [9]). Here we focus on the following three different possibilities corresponding to special properties of the spatially truncated operators H q) and V q). 

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