Symmetry operators function operation

The character of a class depends on the space spanned by the basis of functions on which the symmetry operations act. Above we used (Sn,S 1,82,83) as a basis. 

These six matrices can be verified to multiply just as the symmetry operations do thus they form another three-dimensional representation of the group. We see that in the Ti basis the matrices are block diagonal. This means that the space spanned by the Tj functions, which is the same space as the Sj span, forms a reducible representation that can be decomposed into a one dimensional space and a two dimensional space (via formation of the Ti functions). Note that the characters (traces) of the matrices are not changed by the change in bases. 

For a function to transform according to a specific irreducible representation means that the function, when operated upon by a point-group symmetry operator, yields a linear combination of the functions that transform according to that irreducible representation. For example, a 2pz orbital (z is the C3 axis of NH3) on the nitrogen atom... 

A property such as a vibrational wave function of, say, H2O may or may not preserve an element of symmetry. If it preserves the element, carrying out the corresponding symmetry operation, for example (t , has no effect on the wave function, which we write as... 

Here /, are the three moments of inertia. The symmetry index a is the order of the rotational subgroup in the molecular point group (i.e. the number of proper symmetry operations), for H2O it is 2, for NH3 it is 3, for benzene it is 12 etc. The rotational partition function requires only information about the atomic masses and positions (eq. (12.14)), i.e. the molecular geometry. 

For nondegenerate vibrations all symmetry operations change Qj into 1 times itself. Hence Q/ is unchanged by all symmetry operations. In other words, Q and consequently y(O) behave as totally symmetric functions (i.e. the function is independent of symmetry). However, the wavefunction of the first excited state 3(1) has the same symmetry as Qj. For example, the wavefunction of a totally symmetric vibration (e.g. Qi of C02) is itself a totally symmetric function. 

The subsets of d orbitals in Fig. 3-4 may also be labelled according to their symmetry properties. The d ildxi y2 pair are labelled and the d yldxMyz trio as t2g. These are group-theoretical symbols describing how these functions transform under various symmetry operations. For our purposes, it is sufficient merely to recognize that the letters a ox b describe orbitally i.e. spatially) singly degenerate species, e refers to an orbital doublet and t to an orbital triplet. Lower case letters are used for one-electron wavefunctions (i.e. orbitals). The g subscript refers to the behaviour of... 

It is important to distinguish between mmetiy properties of wave functions on one hand and those of density matrices and densities on the other. The symmetry properties of wave functions are derived from those of the Hamiltonian. The "normal" situation is that the Hamiltonian commutes with a set of symmetry operations which form a group. The eigenfunctions of that Hamiltonian must then transform according to the irreducible representations of the group. Approximate wave functions with the same symmetry properties can be constructed, and they make it possible to simplify the calculations. 

For any symmetry operator T = T 0) (rewritten r when operating on the domain of basis functions x)) for instance, the rotation-reflexion about the z-axis, with matrix representation... 

Fast methods for evaluating these integrals for the case of gaussian basis functions are known [12], Also, Hall has described how to get the symmetry operators (B) 1SjB, r, for any crystal space group [13]. The parameters account for thermal smearing of the charge density. In this work I use the form recommended by Stewart [14],... 

An example of the application of Eq. (47) is provided by the group < 3v whose symmetry operations are defined by Eqs. (18). If the same arbitrary function,

symmetry operation can be worked out, as shown in the last column of Table 13. With the use of the projection operator defined by Eq. (47) and the character table (Table 6), it is found (problem 16) that the coordinate z is totally symmetric (representation Ai). However, it is the sum xy + zx that is preserved in the doubly degenerate representation, E. It should not be surprising that the functions xy and zx are projected as the sum, because it was the sum of the diagonal elements (the trace) of the irreducible representation that was employed in each case in the... 

If o is chosen as the generating function, it yields the other two members of the set (as well as itself) under the symmetry operations of the point group. The function o is obviously the result of the identity operation, while Cj and Cy produce 02 and <73, respectively. These three symmetry operations are in fact sufficient to resolve the problem, although the reader can verify that if all of file operations of the group are employed, the same expression will be obtained (problem 17). 

Table 13 The effect of each symmetry operation of riS 011 function... 

The hfs (or quadrupole) tensors of geometrically (chemically) equivalent nuclei can be transformed into each other by symmetry operations of the point group of the paramagnetic metal complex. For an arbitrary orientation of B0 these nuclei may be considered as nonequivalent and the ENDOR spectra are described by the simple expressions in (B 4). If B0 is oriented in such a way that the corresponding symmetry group of the spin Hamiltonian is not the trivial one (Q symmetry), symmetry adapted base functions have to be used in the second order treatment for an accurate description of ENDOR spectra. We discuss the C2v and D4h covering symmetry in more detail. 

Proceeding in the spirit above it seems reasonable to inquire why s is equal to the number of equivalent rotations, rather than to the total number of symmetry operations for the molecule of interest. Rotational partition functions of the diatomic molecule were discussed immediately above. It was pointed out that symmetry requirements mandate that homonuclear diatomics occupy rotational states with either even or odd values of the rotational quantum number J depending on the nuclear spin quantum number I. Heteronuclear diatomics populate both even and odd J states. Similar behaviors are expected for polyatomic molecules but the analysis of polyatomic rotational wave functions is far more complex than it is for diatomics. Moreover the spacing between polyatomic rotational energy levels is small compared to kT and classical analysis is appropriate. These factors appreciated there is little motivation to study the quantum rules applying to individual rotational states of polyatomic molecules. 

It is then possible to represent the above-mentioned symmetry operation by the 3x3 matrix of Equation (7.1). In a more general way, we can associate a matrix M with each specific symmetry operation R, acting over the basic functions x, y, and z of the vector (x,y, z). Thus, we can represent the effect of the 48 symmetry operations of group Oh (ABe center) over the functions (x, y, z) by 48 matrices. This set of 48 matrices constitutes a representation, and the basic functions x, y, and z are called basis functions. 

Obviously, we can examine the effect of the Oh symmetry operations over a different set of orthonormal basis functions, so that another set of 48 matrices (another representation) can be constructed. It is then clear that each set of orthonormal basis functions transformation equation as follows ... 

Now, if a suitable space of basis functions is used (a space of basis functions that is closed under the symmetry operations of the group), we can construct a set of representations (each one consisting of 48 matrices) for this space that is particularly useful for our purposes. It is especially relevant that the matrices of each one of these representations can be made equivalent to matrices of lower dimensions. 

As an example, to construct the character table for the Oh symmetry group we could apply the symmetry operations of the ABg center over a particularly suitable set of basis functions the orbital wavefunctions s, p, d,... of atom (ion) A. These orbitals are real functions (linear combinations of the imaginary atomic functions) and the electron density probability can be spatially represented. In such a way, it is easy to understand the effect of symmetry transformations over these atomic functions. 

These are the characters of the so-called representation of the Oh group. It should be noted that symmetry operations belonging to the same class have the same character, for a given basis function. Here, we obtain a second important simplification it is only necessary to work with classes, instead of invoking all of the symmetry operations (48 in the case of the Oh group). 

The number of multipole parameters is reduced by the requirements of symmetry. As discussed in chapter 3, the only allowed multipolar functions are those having the symmetry of the site, which are invariant under the local symmetry operations. For example, only / = even multipoles can have nonzero populations on a centrosymmetric site, while for sites with axial symmetry the dipoles must be oriented along the symmetry axis. For a highly symmetric site having 6 mm symmetry, the lowest allowed / 0 is d66+ all lower multipoles being forbidden by the symmetry. The index-picking rules listed in appendix D give the information required for selection of the allowed parameters. 

P is a symmetry operator ensuring the proper spatial symmetry of the function, (1,2) stands for the permutation (exchange) of both electrons coordinates and the sign in Eq. (22) determines the multiplicity for (+) Ft, represents the singlet state and for (-) the triplet state. 

Such a set of eigenfunctions must form the basis for a representation of the symmetry group of the Hamiltonian, because for every symmetry operation S, Tipi = pi implies that H Spi) = Sp>i) and hence that the transformed wave function Spi must be a linear combination of the basic set of eigenfunctions (/ ,... Pn-... 

We can define a projection operator to select the even or odd component of F x, y, z), using symmetry operators. Define the effect of a spatial symmetry operator on a function by letting the operator transform the variables in the argument of the function and then evaluating the function. Recall, for example,... 

We first note that spatial symmetry operators and permutations commute when applied to the functions we are interested in. Consider a multiparticle function 0( 1, r2, r ), where each of the particle coordinates is a 3-vector. Applying a permutation to gives... 

In physics and chemistry there are two different forms of spatial symmetry operators the direct and the indirect. In the direct transformation, a rotation by jr/3 radians, e.g., causes all vectors to be rotated around the rotation axis by this angle with respect to the coordinate axes. The indirect transformation, on the other hand, involves rotating the coordinate axes to arrive at new components for the same vector in a new coordinate system. The latter procedure is not appropriate in dealing with the electronic factors of Born-Oppenheimer wave functions, since we do not want to have to express the nuclear positions in a new coordinate system for each operation. 

An example is the (110) plane of III-V semiconductors, such as GaAs(llO). The only nontrivial symmetry operation is a mirror reflection through a line connecting two Ga (or As) nuclei in the COOl] direction, which we labeled as the X axis. The Bravais lattice is orthorhombic primitive (op). In terms of real Fourier components, the possible corrugation functions are... 

By replacing Ga and As atoms with the same species, such as Si or Ge, the symmetry becomes higher. In Fig. E.4 the Si(llO) plane is shown as an example. The additional gliding symmetry operation means that by letting y— y + bl2 and x—> — x simultaneously, the function should not change. The only Fourier components satisfying this condition are... 

One more quantum number, that relating to the inversion (i) symmetry operator can be used in atomic cases because the total potential energy V is unchanged when ah of the electrons have their position vectors subjected to inversion (i r = -r). This quantum number is straightforward to determine. Because each L, S, Ml, Ms, H state discussed above consist of a few (or, in the case of configuration interaction several) symmetry adapted combinations of Slater determinant functions, the effect of the inversion operator on such a wavefunction P can be determined by ... 

The point group symmetry labels of the individual orbitals which are occupied in any determinental wave function can be used to determine the overall spatial symmetry of the determinant. When a point group symmetry operation is applied to a determinant, it acts on all of the electrons in the determinant for example, ov If... 

Here, %r(R) is the character belonging to symmetry T for the symmetry operation R. Applying this projector to a determinental function of the form Ic I generates a sum of determinants with coefficients determined by the matrix representations Rj - ... 

These one-dimensional matrices can be shown to multiply together just like the symmetry operations of the C3v group. They form an irreducible representation of the group (because it is one-dimensional, it can not be further reduced). Note that this one-dimensional representation is not identical to that found above for the Is N-atom orbital, or the Ti function. 

---