Coefficient, expansion

Glass has a very low thermal expansion coefficient the materials joined with glass have to be similar in expansion or must be duetile, while staying vacuum tight. Even with best-matched materials skilled craftsmanship is asked for the joining process. 

When a molecule is isolated from external fields, the Hamiltonian contains only kinetic energy operators for all of the electrons and nuclei as well as temis that account for repulsion and attraction between all distinct pairs of like and unlike charges, respectively. In such a case, the Hamiltonian is constant in time. Wlien this condition is satisfied, the representation of the time-dependent wavefiinction as a superposition of Hamiltonian eigenfiinctions can be used to detemiine the time dependence of the expansion coefficients. If equation (Al.1.39) is substituted into the tune-dependent Sclirodinger equation... 

Now consider die case where Ais itself a time-independent operator, such as that for the position, momenPiin or angidar momenPiin of a particle or even the energy of the benzene molecule. In these cases, the time-dependent expansion coefficients are unaffected by application of the operator, and one obtains... 

It is worthwhile, albeit tedious, to work out the condition that must satisfied in order for equation (A1.1.117) to hold true. Expanding the trial fiinction according to equation (A1.1.113). assuming that the basis frmctions and expansion coefficients are real and making use of the teclmiqiie of implicit differentiation, one finds... 

Two other important quantities are the isobaric expansivity ( coefficient of themial expansion ) and the isothermal compressibility k, defined as... 

Resonance states in the spectra, which are assignable in temis of zero-order basis will have a predominant expansion coefficient c.. Hose and Taylor [ ] have argued that for an assignable level r /,j>0.5... 

Some initial guess is made for the LCAO-KS expansion coefficients C. a a... 

The density is computed as p(r) = 2. n i ). (/ )p. Often, p(r) is expanded in an AO basis, which need not be the same as the basis used for the and the expansion coefficients of p are computed in tenns of those of the It is also connnon to use an AO basis to expand p (r) which, together with p, is needed to evaluate the exchange-correlation fiinctionaTs contribution toCg. 

The time dependence of the molecular wave function is carried by the wave function parameters, which assume the role of dynamical variables [19,20]. Therefore the choice of parameterization of the wave functions for electronic and nuclear degrees of freedom becomes important. Parameter sets that exhibit continuity and nonredundancy are sought and in this connection the theory of generalized coherent states has proven useful [21]. Typical parameters include molecular orbital coefficients, expansion coefficients of a multiconfigurational wave function, and average nuclear positions and momenta. We write... 

If the PES are known, the time-dependent Schrbdinger equation, Eq. (1), can in principle be solved directly using what are termed wavepacket dynamics [15-18]. Here, a time-independent basis set expansion is used to represent the wavepacket and the Hamiltonian. The evolution is then carried by the expansion coefficients. While providing a complete description of the system dynamics, these methods are restricted to the study of typically 3-6 degrees of freedom. Even the highly efficient multiconfiguration time-dependent Hartree (MCTDH) method [19,20], which uses a time-dependent basis set expansion, can handle no more than 30 degrees of freedom. 

For bound state systems, eigenfunctions of the nuclear Hamiltonian can be found by diagonalization of the Hamiltonian matiix in Eq. (11). These functions are the possible nuclear states of the system, that is, the vibrational states. If these states are used as a basis set, the wave function after excitation is a superposition of these vibrational states, with expansion coefficients given by the Frank-Condon overlaps. In this picture, the dynamics in Figure 4 can be described by the time evolution of these expansion coefficients, a simple phase factor. The periodic motion in coordinate space is thus related to a discrete spectrum in energy space. 

The gradient of the PES (force) can in principle be calculated by finite difference methods. This is, however, extremely inefficient, requiring many evaluations of the wave function. Gradient methods in quantum chemistiy are fortunately now very advanced, and analytic gradients are available for a wide variety of ab initio methods [123-127]. Note that if the wave function depends on a set of parameters X], for example, the expansion coefficients of the basis functions used to build the orbitals in molecular orbital (MO) theory. 

The eigenvalues of this mabix have the form of Eq. (68), but this time the matrix elements are given by Eqs. (84) and (85). The symmetry arguments used to determine which nuclear modes couple the states, Eq. (81), now play a cracial role in the model. Thus the linear expansion coefficients are only nonzero if the products of symmebies of the electronic states at Qq and the relevant nuclear mode contain the totally symmebic inep. As a result, on-diagonal matrix elements are only nonzero for totally symmebic nuclear coordinates and, if the elecbonic states have different symmeby, the off-diagonal elements will only... 

As usual there is the question of the initial conditions. In general, more than one frozen Gaussian function will be required in the initial set. In keeping with the frozen Gaussian approximation, these basis functions can be chosen by selecting the Gaussian momenta and positions from a Wigner, or other appropriate phase space, distribution. The initial expansion coefficients are then defined by the equation... 

All m oleciilar orbitals are com biiiations of the same set of atom ic orbitals they differ only by their LCAO expansion coefficients. HyperC hem computes these coefficients, C p. and the molecular orbital energies by requiring that the ground-state electronic energy beat a minimum. That is, any change in the computed coefficients can only increase the energy. 

The expansion coefficients C . are determined by solving the Cl secular equation... 

Stem correction (in degrees) = KN(t — t ) where K = the apparent expansion coefficient of mercury in glass ... 

Fig. II, 56, 6 is a simple distillation head when this is fitted into a flask with a ground glass socket, the assembly is virtually a distillation flask. The bottom cone is usually 19, 24 or 29 the side cone is generafly B19 but may be 24 the thermometer socket is 14. For many purposes, a thermometer is fitted into a one-hole rubber stopper of correct taper and then inserted into the 14 socket the area of rubber which is exposed to the action of the organic vapour is relatively so small that the amount of contamination thus introduced is negligible. If, however, all rubber stoppers must be absent because of the highly corrosive character of the vapour, a thermometer with a 14 cone is employed. It is important to have the thermometer of the same glass as the distillation head, otherwise difficulties may arise owing to the different expansion coefficients of the two kinds of glass.

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