Scalar theory

The propagation of linear acoustic waves in solids depends on two laws discovered by two of the most illustrious physicists of the seventeenth century, one from Cambridge and the other from Oxford. Consider a volume element of an isotropic solid subjected to shear, as shown in Fig. 6.1. If the displacement in the transverse direction is , and the component of shear stress in that direction is os, then Newton s second law may be written 

Phase velocity is given by v = u /k thus, for shear (or transverse) waves the velocity is 

A fluid cannot support shear waves over any appreciable distance, so only longitudinal waves can propagate in a fluid. In this case the appropriate modulus is the adiabatic bulk modulus B. Extending to three dimensions with the Laplacian operator 

The Helmholtz equation is widely used as the starting point for much theoretical acoustics in fluids (Morse and Ingard 1987). 

If a medium is not perfectly elastic or perfectly fluid, but has viscous properties, then the equation for the acoustic displacement u contains an extra term 

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J. Durnin, "Exact solutions for diffraction free beams 1 the scalar theory" J. Opt. Soc. 

Damour, T. and Nordtvedt, K., General relativity as a cosmological attractor of tensor-scalar theories, Phys. Rev. Lett, 70, 2217, 1993 Tensor-scalar cosmological models and their relaxation toward general relativity, Phys. Rev. D, 48, 3436, 1993. 

A completely difierent approach to scattering involves writing down an expression that can be used to obtain S directly from the wavefunction, and which is stationary with respect to small errors in die waveftmction. In this case one can obtain the scattering matrix element by variational theory. A recent review of this topic has been given by Miller [32]. There are many different expressions that give S as a ftmctional of the wavefunction and, therefore, there are many different variational theories. This section describes the Kohn variational theory, which has proven particularly useftil in many applications in chemical reaction dynamics. To keep the derivation as simple as possible, we restrict our consideration to potentials of die type plotted in figure A3.11.1(c) where the waveftmcfton vanishes in the limit of v -oo, and where the Smatrix is a scalar property so we can drop the matrix notation. 

In an Abelian theory [for which I (r, R) in Eq. (90) is a scalar rather than a vector function, Al=l], the introduction of a gauge field g(R) means premultiplication of the wave function x(R) by exp(igR), where g(R) is a scalar. This allows the definition of a gauge -vector potential, in natural units... 

The earliest appearance of the nonrelativistic continuity equation is due to Schrodinger himself [2,319], obtained from his time-dependent wave equation. A relativistic continuity equation (appropriate to a scalar field and formulated in terms of the field amplitudes) was found by Gordon [320]. The continuity equation for an electron in the relativistic Dirac theory [134,321] has the well-known form [322] ... 

Formal Theory A small neutral particle at equihbrium in a static elecdric field experiences a net force due to DEP that can be written as F = (p V)E, where p is the dipole moment vecdor and E is the external electric field. If the particle is a simple dielectric and is isotropically, linearly, and homogeneously polarizable, then the dipole moment can be written as p = ai E, where a is the (scalar) polarizability, V is the volume of the particle, and E is the external field. The force can then be written as ... 

The normality conditions (5.56) and (5.57) have essentially the same forms as those derived by Casey and Naghdi [1], [2], [3], but the interpretation is very different. In the present theory, it is clear that the inelastic strain rate e is always normal to the elastic limit surface in stress space. When applied to plasticity, e is the plastic strain rate, which may now be denoted e", and this is always normal to the elastic limit surface, which may now be called the yield surface. Naghdi et al. by contrast, took the internal state variables k to be comprised of the plastic strain e and a scalar hardening parameter k. In their theory, consequently, the plastic strain rate e , being contained in k in (5.57), is not itself normal to the yield surface. This confusion produces quite different results. 

In this section, the general inelastic theory of Section 5.2 will be specialized to a simple phenomenological theory of plasticity. The inelastic strain rate tensor e may be identified with the plastic strain rate tensor e . In order to include isotropic and kinematic hardening, the set of internal state variables, denoted collectively by k in the previous theory, is reduced to the set (k, a) where k is a scalar representing isotropic hardening and a is a symmetric second-order tensor representing kinematic hardening. The elastic limit condition in stress space (5.25), now called a yield condition, becomes... 

Of course, k may be taken to be comprised of a number of such tensors, and it is not difficult to extend the theory to include a number of indifferent scalars and vectors, if desired. 

It is possible to assume other transformation properties for k. For example, for some purposes it may be more desirable to attribute strainlike properties obeying a transformation law like (A. 19), in which case the equations of this section will take a somewhat different form. Of course, k may be taken to be comprised of a number of such tensors, and it is not difficult to extend the theory to include a number of indifferent scalars and vectors, if desired. 

Matrix and tensor notation is useful when dealing with systems of equations. Matrix theory is a straightforward set of operations for linear algebra and is covered in Section A.I. Tensor notation, treated in Section A.2, is a classification scheme in which the complexity ranges upward from scalars (zero-order tensors) and vectors (first-order tensors) through second-order tensors and beyond. 

A few comments on the layout of the book. Definitions or common phrases are marked in italic, these can be found in the index. Underline is used for emphasizing important points. Operators, vectors and matrices are denoted in bold, scalars in normal text. Although I have tried to keep the notation as consistent as possible, different branches in computational chemistry often use different symbols for the same quantity. In order to comply with common usage, I have elected sometimes to switch notation between chapters. The second derivative of the energy, for example, is called the force constant k in force field theory, the corresponding matrix is denoted F when discussing vibrations, and called the Hessian H for optimization purposes. 

Scalar Fields Consider a continuous field theory in Euclidean space with action... 

The Linear Algebraic Problem.—Familiarity with the basic theory of finite vectors and matrices—the notions of rank and linear dependence, the Cayley-Hamilton theorem, the Jordan normal form, orthogonality, and related principles—will be presupposed. In this section and the next, matrices will generally be represented by capital letters, column vectors by lower case English letters, scalars, except for indices and dimensions, by lower case Greek letters. The vectors a,b,x,y,..., will have elements au f it gt, r) . .. the matrices A, B,...,... 

The proof takes different forms in different representations. Here we assume that quantum states are column vectors (or spinors ) iji, with n elements, and that the scalar product has the form ft ip. If ip were a Schrodinger function, J ftipdr would take the place of this matrix product, and in Dirac s theory of the electron, it would be replaced by J fttpdr, iji being a four-component spinor. But the work goes through as below with only formal changes. Use of the bra-ket notation (Chapter 8) would cover all these cases, but it obscures some of the detail we wish to exhibit here. 

The quantum states of Schrodinger s theory constitute an example of Hilbert space, and their scalar product has a direct physical meaning. Any such example of Hilbert space, where we can actually evaluate the scalar products numerically, is called a representation of Hilbert space. We shall continue discussing the properties of abstract Hilbert space, so that all our conclusions will apply to any and every representation. 

The form of the scalar product in terms of Schrddinger amplitudes indicates that if we want to introduce into the theory a probability density it is x(x,f)la which must play this role. In fact, the reason for introducing the Schrddinger amplitude stems precisely from the circumstances that in terms of the latter the scalar product takes the ample form (9-95), and as a consequence of this jY (x.QPd3 may directly be interpreted as the probability of finding the particle within the volume V at (hue K... 

Here u is a unit vector oriented along the rotational symmetry axis, while in a spherical molecule it is an arbitrary vector rigidly connected to the molecular frame. The scalar product u(t) (0) is cos 0(t) in classical theory, where 6(t) is the angle of u reorientation with respect to its initial position. It can be easily seen that both orientational correlation functions are the average values of the corresponding Legendre polynomials ... 

Assuming that substituted Sb at the surface may work as catalytic active site as well as W, First-principles density functional theory (DFT) calculations were performed with Becke-Perdew [7, 9] functional to evaluate the binding energy between p-xylene and catalyst. Scalar relativistic effects were treated with the energy-consistent pseudo-potentials for W and Sb. However, the binding strength with p-xylene is much weaker for Sb (0.6 eV) than for W (2.4 eV), as shown in Fig. 4. 

The perturbed energies and wavefunctions for the i-th system state can be expressed in a similar way as in scalar perturbation theory ... 

The wavefunction corrections can be obtained similarly through a resolvent operator technique which will be discussed below. The n-th wavefunction correction for the i-th state of the perturbed system can be written in the same marmer as it is customary when developing some scalar perturbation theory scheme by means of a linear combination of the unperturbed state wavefunctions, excluding the i-th unperturbed state. That is ... 

Suzumura, T., Nakajima, T. and Hirao, K. (1999) Ground-state properties of MH, MCI, and M2 (M—Cu, Ag, and Au) calculated by a scalar relativistic density functional theory International Journal of Quantum Chemistry, 75, lVJ-1. ... 

However, there also exists a third possibility. By using a famous relation due to Dirac, the relativistic effects can be (in a nonunique way) divided into spin-independent and spin-dependent terms. The former are collectively called scalar relativistic effects and the latter are subsumed under the name spin-orbit coupling (SOC). The scalar relativistic effects can be straightforwardly included in the one-electron Hamiltonian operator h. Unless the investigated elements are very heavy, this recovers the major part of the distortion of the orbitals due to relativity. The SOC terms may be treated in a second step by perturbation theory. This is the preferred way of approaching molecular properties and only breaks down in the presence of very heavy elements or near degeneracy of the investigated electronic state. 

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