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Character table

In group theory, a character table is a square array that displays the values of the irreducible characters of a finite group G, arranged with rows corresponding to the distinct irreducible characters and columns corresponding to the conjugacy classes of G. The entry in the row for an irreducible character \chi and the column for a conjugacy class C is the value \chi(g) for any g \in C, which equals the trace of the matrix representing the action of g in the corresponding irreducible representation. The number of rows and columns in the table equals the number of conjugacy classes in G, which also equals the number of irreducible representations up to isomorphism. Character tables are constructed using the fact that characters are class functions—constant on conjugacy classes—and satisfy relations that form the basis for much of . The column orthogonality relation states that for conjugacy classes C_i and C_j, the sum over all irreducible characters \chi_k of \overline{\chi_k(g_i)} \chi_k(g_j) equals |G| / |C_i| if i = j and 0 otherwise, where g_i \in C_i. Similarly, the row orthogonality relation implies that the inner product \langle \chi, \psi \rangle = \frac{1}{|G|} \sum_{g \in G} \overline{\chi(g)} \psi(g) is 1 if \chi = \psi and 0 otherwise for distinct irreducible characters. These relations enable the decomposition of any representation into irreducibles via character projections and provide a complete encoding of the representation theory of G. The development of , including character tables, traces back to the late , building on earlier work with characters of abelian groups by Gauss in the early 1800s; the modern framework for non-abelian groups was established by Frobenius in 1896 and further advanced by Schur. Character tables play a central role in reducing complex problems about finite groups—such as counting subgroups or determining normal subgroups—to linear algebra over the complex numbers. They also facilitate applications in related fields, including the study of symmetries in physics and chemistry through point groups, though their foundational importance lies in .

Basics of Character Tables

Definition

A character table in group theory is a square array that organizes the irreducible representations of a , with rows corresponding to the irreducible representations and columns corresponding to the conjugacy classes of the group elements, where each entry is the , defined as the of the matrix representing the group element in that representation. Characters are class functions, meaning they remain invariant under conjugation, so χ(x^{-1}gx) = χ(g) for any group elements x and g, which allows the table to be structured by conjugacy classes rather than individual elements. In standard notation, the of a group g with respect to a is denoted χ(g), and for the e, χ(e) gives the of the . The relations among these ensure the uniqueness and completeness of the irreducible listed in the table. In , are applied to point groups, which describe the operations of molecules, enabling the classification of molecular orbitals, vibrations, and other symmetry-adapted functions to predict properties such as spectroscopic transitions./04:_Symmetry_and_Group_Theory/4.03:_Properties_and_Representations_of_Groups/4.3.03:_Character_Tables) For instance, by assigning molecular features to irreducible via the table, chemists can determine which modes are - or Raman-active based on their transformation properties under the group's operations./04:_Symmetry_and_Group_Theory/4.03:_Properties_and_Representations_of_Groups/4.3.03:_Character_Tables)

Construction

The construction of a character table for a or involves a systematic process to determine the characters of its irreducible representations organized by conjugacy classes. The first step is to identify all conjugacy classes of the group, which are the equivalence classes of elements under conjugation: two elements h and k are conjugate if there exists g \in G such that k = g^{-1} h g. These classes form the columns of the character table (aside from the row indicating group order and class sizes), and the number of classes equals the number of irreducible representations. The second step is to find the irreducible representations by constructing explicit matrix representations \rho(g) for each group element g that satisfy the group's multiplication relations, ensuring the matrices are unitary or orthogonal as appropriate for the field (typically complex numbers for characters). The characters are then the traces \chi(g) = \operatorname{tr}(\rho(g)), which are constant on conjugacy classes. Irreducibility of each representation is verified using , which asserts that the representation is irreducible if the only matrices A commuting with all \rho(g) (i.e., A \rho(g) = \rho(g) A for all g \in G) are scalar multiples of the . The third step is to compute the characters for each conjugacy class using the representation matrices or projection operators to isolate irreducible components from a known reducible representation, such as the . For the C_3 = \langle r \mid r^3 = e \rangle, the conjugacy classes are \{e\}, \{r\}, and \{r^2\} since the group is abelian. The irreducible representations are one-dimensional, parameterized by k = 0, 1, 2, with \rho_k(r) = \omega^k where \omega = e^{2\pi i / 3} is a primitive of unity satisfying \omega^3 = 1 and $1 + \omega + \omega^2 = 0. The characters are thus \chi_k(r^s) = \omega^{k s} for s = 0, 1, 2:
  • For k=0 (trivial representation): \chi_0(e) = 1, \chi_0(r) = 1, \chi_0(r^2) = 1.
  • For k=1: \chi_1(e) = 1, \chi_1(r) = \omega, \chi_1(r^2) = \omega^2.
  • For k=2: \chi_2(e) = 1, \chi_2(r) = \omega^2, \chi_2(r^2) = \omega.
These are verified as irreducible by Schur's lemma, as one-dimensional representations over \mathbb{C} are always irreducible. For common point groups like C_{2v}, which consists of the identity E, a 180° rotation C_2 about the z-axis, and reflections \sigma_{xz} and \sigma_{yz}, the construction begins similarly: the group is abelian with four singleton conjugacy classes due to all elements commuting and having order 2 (except E). The irreducible representations are one-dimensional, constructed by assigning values \pm 1 to the non-identity operations consistent with the relations (e.g., C_2 \sigma_{xz} = \sigma_{yz}), yielding four representations whose characters are the products of these assignments on each class. Irreducibility follows from the one-dimensional nature, and traces are simply the assigned values.

Example

A representative example of a character table is that for the C_{2v} point group, which is commonly encountered in molecular symmetry analysis. The C_{2v} group consists of four symmetry operations: the identity E, a twofold rotation C_2 about the principal axis, and two vertical reflection planes \sigma_v (typically the xz-plane) and \sigma_v' (typically the yz-plane). All irreducible representations (irreps) of C_{2v} are one-dimensional, as the group is abelian. The complete character table is as follows:
C_{2v}EC_2\sigma_v\sigma_v'
A_11111
A_211-1-1
B_11-11-1
B_21-1-11
In this table, each entry \chi_i(g) denotes the character of the g (a representative) in the i-th irrep, defined as the of the corresponding \rho_i(g). For the E, the character is always equal to the of the , which is 1 for all irreps here since they are one-dimensional. The values are \pm 1, reflecting how the basis functions transform under each : +1 for unchanged (symmetric) and -1 for sign-reversed (antisymmetric). The rows of the table represent class functions, constant on conjugacy classes, and satisfy orthogonality relations derived from the group's representation theory. Specifically, the sum of the characters across a row for an irrep equals the group order (4 for C_{2v}) if the irrep is the trivial one (A_1: $1 + 1 + 1 + 1 = 4), and 0 otherwise (e.g., A_2: $1 + 1 - 1 - 1 = 0); this follows from the inner product of the character with the trivial representation being 1 or 0, respectively. This C_{2v} table applies to molecules like (H_2O), where the C_2 axis bisects the H-O-H angle and the \sigma_v planes include the molecular plane and the perpendicular bisector plane.

Mathematical Properties

Orthogonality Relations

The orthogonality relations for characters of irreducible representations of a finite group G are fundamental properties that establish the characters as an for the space of class functions on G. The inner product of two class functions \chi and \psi is defined as \langle \chi, \psi \rangle = \frac{1}{|G|} \sum_{g \in G} \chi(g) \overline{\psi(g)}, where the bar denotes complex conjugation, and this inner product is Hermitian with respect to the space of class functions. Row orthogonality states that for distinct irreducible characters \chi^i and \chi^j of G, the inner product satisfies \langle \chi^i, \chi^j \rangle = \delta_{ij}, where \delta_{ij} is the (equal to 1 if i = j and 0 otherwise). Equivalently, without , \sum_{g \in G} \chi^i(g) \overline{\chi^j(g)} = |G| \delta_{ij}. This relation implies that the irreducible characters are pairwise orthogonal and each has norm 1 under the inner product. Column orthogonality concerns the values of characters on conjugacy classes. For conjugacy classes C_k and C_l of G, \sum_i \chi^i(C_k) \overline{\chi^i(C_l)} = \frac{|G|}{|C_k|} \delta_{kl}, where the sum is over all irreducible characters \chi^i, and \delta_{kl} = 1 if C_k = C_l and 0 otherwise. Since characters are class functions, \chi^i(C_k) denotes the common value of \chi^i on elements of C_k, and this relation holds because \overline{\chi^i(g)} = \chi^i(g^{-1}) for g \in G. Equivalently, \sum_i \chi^i(g) \chi^i(h^{-1}) = |C_G(g)| \delta_{g \sim h}, where C_G(g) is the centralizer of g, |C_G(g)| = |G| / |C(g)| with C(g) the conjugacy class of g, and \delta_{g \sim h} = 1 if g and h are conjugate. These relations arise from the completeness of the irreducible characters as a basis for the class functions, a consequence of and the decomposition of the into irreducibles. Specifically, the proof of row orthogonality involves showing that the inner product corresponds to the multiplicity of one irreducible in the with the of another, yielding via representation uniqueness; column orthogonality follows by considering the character table as a matrix and applying row orthogonality to its adjusted for class sizes. The irreducible characters thus form a complete for the of class functions, which has dimension equal to the number of conjugacy classes. As implications, the orthogonality relations ensure that the number of irreducible representations equals the number of conjugacy classes, making the character table a square matrix. They also provide a practical tool for verifying the consistency and completeness of character tables by checking that the rows and columns satisfy these equations.

Character Properties

In representation theory of finite groups, the character \chi of a representation \rho: G \to \mathrm{GL}(V) is the trace function \chi(g) = \mathrm{Tr}(\rho(g)) for g \in G, where V is a finite-dimensional complex vector space. One fundamental property is that \chi(e) = \dim V, where e is the identity element of G; this value is a positive integer representing the degree of the representation. Additionally, since the eigenvalues of \rho(g) are roots of unity (as g has finite order), \chi(g) is the sum of \dim V such roots, implying |\chi(g)| \leq \chi(e) for all g \in G, with equality if and only if \rho(g) acts as scalar multiplication by a root of unity on V. Another key property is that the character of the dual representation satisfies \chi_{V^*}(g) = \overline{\chi_V(g^{-1})}, or equivalently \chi(g^{-1}) = \overline{\chi(g)} for the original character, since the eigenvalues of \rho(g^{-1}) are the complex conjugates of those of \rho(g). This follows from the unitarity of representations over \mathbb{C}. For characters of irreducible representations, multiplicativity \chi(gh) = \chi(g) \chi(h) holds unconditionally only for one-dimensional representations (linear characters), which are group homomorphisms to \mathbb{C}^\times; in general groups, all irreducible characters are multiplicative precisely when G is abelian, as all irreducibles are then one-dimensional. A significant relational property, underpinned by the orthogonality of irreducible characters, is that the sum of the squares of the dimensions of all irreducible representations equals the order of the group: \sum_i [\chi^i(e)]^2 = |G|, where the sum runs over a complete set of irreducible characters \chi^i. In the context of point groups arising from physical symmetries (finite subgroups of O(3)), characters are real-valued because the representations can be realized over the reals, with \chi(g) = \overline{\chi(g)} for all g, reflecting the orthogonal nature of the group actions. Finally, the values of any character \chi(g) are algebraic integers in \mathbb{C}, as they are integer linear combinations of roots of unity (with coefficients given by multiplicities in the decomposition into irreducibles). This integrality ensures that character tables consist of entries in cyclotomic fields, facilitating computations in applications like symmetry analysis.

Automorphisms

Outer automorphisms of a finite group G are the cosets in the quotient group \operatorname{Out}(G) = \operatorname{Aut}(G)/\operatorname{Inn}(G), where \operatorname{Aut}(G) is the full group of automorphisms of G and \operatorname{Inn}(G) is the normal subgroup consisting of inner automorphisms induced by conjugation by elements of G. Inner automorphisms preserve conjugacy classes setwise, acting trivially on the set of conjugacy classes themselves, whereas outer automorphisms can permute distinct conjugacy classes and the irreducible representations while maintaining the character values, i.e., \chi(\phi(g)) = \chi(g) for any irreducible character \chi and automorphism \phi. This distinction arises because conjugation maps each class to itself, but general automorphisms may map elements of one class to another of the same size. The action of an outer automorphism on the character table of G permutes the columns (corresponding to conjugacy classes) and rows (irreducible characters) in a way that preserves the entries, resulting in an isomorphic table up to relabeling. Such permutations can lead to fusions or splits of classes when considering quotients, extensions, or related groups, but for G itself, they simply reorder the structure without changing the underlying character values or relations. Since characters are class functions, the table's mathematical properties remain invariant under this action, allowing isomorphic groups to share equivalent tables despite different realizations. A concrete example occurs in the S_6, where \operatorname{Out}(S_6) has order 2 generated by a non-trivial outer . This interchanges the of transpositions (elements like (1\,2), of size 15) with the class of products of three disjoint transpositions (elements like (1\,2)(3\,4)(5\,6), also of size 15), while fixing other classes, and simultaneously permutes the irreducible characters accordingly; the resulting character table is unchanged up to this relabeling. In point groups relevant to , outer automorphisms are uncommon due to the specific geometric constraints, but they manifest in cases like the of order 8, which underlies both the D_4 (422 symmetry) and D_{2d} (42m symmetry) point groups. These isomorphic abstract groups share identical character tables, with four 1-dimensional irreducible representations and one 2-dimensional; outer automorphisms permute the columns for the two classes of reflections (size 2 each) and the corresponding 1-dimensional characters, relating the tables across different geometric interpretations without altering their form.

Vibrational Analysis Using Character Tables

General Procedure

The general procedure for analyzing molecular vibrations using character tables involves systematically applying to determine the symmetries of vibrational modes, their multiplicities, and their spectroscopic activity. This method relies on the point group of the molecule and its associated character table, which encodes the irreducible s (irreps) of the symmetry operations. By decomposing the total representation of atomic displacements into irreps, one can isolate the vibrational contributions and predict (IR) and Raman activities without performing detailed quantum mechanical calculations. The process begins with Step 1: Assigning the and identifying symmetry elements. First, examine the to determine its symmetry, such as C_{2v} for or D_{2h} for , by identifying principal axes of rotation, mirror planes, inversion centers, and other elements. Sketching these elements aids in visualizing how the molecule transforms under symmetry operations. This assignment is crucial as it dictates the relevant character table to use. Step 2: Generating the reducible representation \Gamma_\text{red}. Consider the basis of all displacements (3N functions for N atoms, where each atom contributes , z coordinates). For each group g, compute the character \chi_\text{red}(g) as the number of unchanged basis functions under that operation. Typically, this counts the atoms that remain in place (multiplied by 3 for translations) or adjusts for rotations and reflections (e.g., \chi = -1 for 180° rotations about an axis through an atom). Atoms or bonds serve as practical basis sets in some cases, simplifying tracking. The resulting \Gamma_\text{red} spans the total . Step 3: Reducing \Gamma_\text{red} to irreps. Decompose \Gamma_\text{red} into a direct sum of irreps using the reduction formula derived from the orthogonality of characters: a_i = \frac{1}{|G|} \sum_g \chi_\text{red}(g) \, \chi_i(g^{-1})^* Here, a_i is the multiplicity of irrep i, |G| is the group order, the sum is over all group elements g, \chi_\text{red}(g) is the character of the reducible representation, \chi_i is the character of irrep i, and ^* denotes the complex conjugate (often unnecessary for real characters in point groups). This yields \Gamma_\text{total} = \sum a_i \Gamma_i, where the \Gamma_i are irreps from the character table. The formula stems from the orthogonality relations among irreps. Step 4: Isolating vibrational modes. Subtract the representations for translational and rotational to obtain the vibrational representation \Gamma_\text{vib}. Translations correspond to the irreps of the linear functions x, y, z in the character table (3 irreps for nonlinear molecules), while rotations correspond to Rx, Ry, Rz (another 3 irreps). Thus, \Gamma_\text{vib} = \Gamma_\text{total} - \Gamma_\text{trans} - \Gamma_\text{rot}, yielding 3N-6 modes for nonlinear molecules. Reduce \Gamma_\text{vib} if not already done in the previous step. Step 5: Assigning symmetries to modes and checking spectroscopic activity. The irreps in \Gamma_\text{vib} label the symmetries of the normal vibrational modes. For activity, consult the : a mode is IR-active if its irrep matches one of the translational irreps (x, y, or z), as this allows a change. For Raman activity, the mode must match irreps of quadratic forms (e.g., x^2 + y^2, xy), corresponding to changes, often the totally symmetric or even-parity irreps. This step predicts observable bands in spectra.

Water Molecule Application

The water molecule (H₂O) is a nonlinear triatomic molecule belonging to the C_{2v} point group, which includes the symmetry operations E, C_2 (rotation by 180° about the z-axis), \sigma_{xz} (reflection in the xz-plane), and \sigma_{yz} (reflection in the yz-plane). To analyze its vibrational modes, consider the basis of 3N=9 Cartesian displacement coordinates for the three atoms, yielding the reducible representation \Gamma_{3N} with characters \chi(E)=9, \chi(C_2)=-1, \chi(\sigma_{xz})=1, and \chi(\sigma_{yz})=3. This representation reduces to $3A_1 \oplus A_2 \oplus 2B_1 \oplus 3B_2 using the C_{2v} character table and the reduction formula. The translational modes transform as \Gamma_{trans} = A_1 + B_1 + B_2, corresponding to displacements along the z-axis (A_1), x-axis (B_1), and y-axis (B_2). The rotational modes transform as \Gamma_{rot} = A_2 + B_1 + B_2, corresponding to rotations about the z-axis (A_2), x-axis (B_1), and y-axis (B_2). Subtracting these from \Gamma_{3N} gives the vibrational representation \Gamma_{vib} = 2A_1 + B_2, accounting for the three vibrational degrees of freedom ($3N-6=3) in this nonlinear molecule. The two A_1 modes consist of the symmetric stretching vibration (\nu_1, where both O-H bonds lengthen and shorten ) and the bending (scissoring) vibration (\nu_2, where the H-O-H angle varies while maintaining ). The B_2 mode is the asymmetric stretching vibration (\nu_3, where one O-H bond lengthens as the other shortens). For spectroscopic activity, (IR) absorption requires the vibrational mode to match that of the components: A_1 (z), B_1 (x), or B_2 (y). Thus, all three modes are IR active—the two A_1 modes via the z-component and the B_2 mode via the y-component. Raman activity requires matching the symmetries of the tensor components, which span A_1 (x^2+y^2, z^2), A_2 (xy), B_1 (xz), and B_2 (yz) in C_{2v}. Since the vibrational modes (A_1 and B_2) are contained within these, all three are Raman active.

Ethylene Molecule Application

The molecule, C₂H₄, exhibits D_{2h} due to its planar configuration, with the C=C bond aligned along the principal axis and the two CH₂ groups symmetrically positioned in the molecular plane. This arises from three mutually C₂ axes, an inversion center, and three orthogonal mirror planes, distinguishing it from lower-symmetry cases like (C_{2v}) by incorporating inversion and additional rotational elements that enforce g/u for modes. To analyze the vibrational modes, the reducible representation Γ_red is constructed for the 3N = 18 basis of Cartesian coordinates, following the general procedure of evaluating characters based on atom permutations and coordinate transformations under each group operation. The resulting characters for the classes , C₂(z), C₂(y), C₂(x), i, σ(xy), σ(xz), σ(yz) are 18, 0, 0, -2, 0, 6, 2, 0, reflecting fixed atoms only for (all 6), C₂(x) (2 carbons, -1 each), σ(xy) (all 6, 1 each), and σ(xz) (2 carbons, 1 each). Reduction of Γ_red using the D_{2h} character table and the formula a_i = \frac{1}{h} \sum_R \chi(\Gamma, R) \chi(i, R)^* (with h = 8) yields the decomposition 3A_g + 3B_{1g} + 2B_{2g} + B_{3g} + A_u + 2B_{1u} + 3B_{2u} + 3B_{3u}. The translational modes Γ_trans span B_{1u} (z-direction), B_{2u} (y), and B_{3u} (x), while the rotational modes Γ_rot span B_{1g} (R_z), B_{2g} (R_x), and B_{3g} (R_y). Subtracting these gives the vibrational representation Γ_vib = 3A_g + 2B_{1g} + B_{2g} + A_u + B_{1u} + 2B_{2u} + 2B_{3u}, corresponding to the 12 fundamental vibrational degrees of freedom (3N - 6). These modes are classified by type and symmetry, emphasizing the role of g/u parity in D_{2h}: the 3A_g modes consist of the symmetric C-H stretch, the C-C stretch, and a symmetric CH₂ scissoring bend; the 2B_{3u} modes include a C-H stretch and an asymmetric CH₂ scissoring deformation; the B_{1u} mode is the out-of-plane CH₂ wagging; the 2B_{2u} modes encompass an antisymmetric C-H stretch and a CH₂ rocking; the 2B_{1g} modes consist of a C-H stretch and a CH₂ rocking deformation; the B_{2g} mode is an out-of-plane CH₂ wagging deformation; and the A_u mode is the torsional (twisting) motion around the C-C bond. This classification highlights how the higher symmetry in ethylene leads to a greater number of distinct symmetry classes for the modes compared to C_{2v} molecules, with clear separation of in-plane stretches/bends and out-of-plane deformations. Spectroscopic selection rules in D_{2h} dictate that infrared (IR) activity requires u symmetry (matching dipole components: B_{1u}, B_{2u}, B_{3u}), yielding 5 active modes (B_{1u} + 2B_{2u} + 2B_{3u}), while Raman activity requires g symmetry (matching polarizability: A_g, B_{1g}, B_{2g}, B_{3g}), yielding 6 active modes (3A_g + 2B_{1g} + B_{2g}). The A_u torsional mode is inactive in both, enforcing the mutual exclusion rule due to inversion. For instance, the symmetric C-C stretch (A_g) is Raman-active only, appearing around 1623 cm⁻¹, whereas the antisymmetric C-H stretch (B_{2u} or B_{3u}) is IR-active near 3100 cm⁻¹. This parity-based selection enables precise assignment of observed bands in ethylene's spectrum, aiding in structural confirmation and isotopic studies.

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