Double group
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In applied mathematics, double groups are groups composed of rotations and related transformations. More specifically, a double group is a central extension of a finite subgroup of the group of three-dimensional rotations by the two-element cyclic group. These include the binary polyhedral groups. They are employed in the field of physical chemistry.
G. Frobenius derived and listed in 1899 the character tables of the finite subgroups of SU(2), the double cover of the rotation group SO(3). In 1875, F. Klein had already classified these finite "binary" subgroups into the cyclic groups, the binary dihedral groups, the binary tetrahedral group, the binary octahedral group and the binary icosahedral group. Alternative derivations of the character tables were given by I. Schur and H. E. Jordan in 1907; further branching rules and tensor product formulas were also determined.[2][3][4]
In a landmark 1929 article on splitting of atoms in crystals, the physicist H. Bethe coined the term "double group" (Doppelgruppe),[5][6] a concept that allowed double-valued or spinor representations of finite subgroups of the rotation group to be regarded as ordinary linear representations of their double covers.[a][b] In particular, Bethe applied his theory to relativistic quantum mechanics and crystallographic point groups, where a natural physical restriction to 32 point groups occurs. Subsequently, the non-crystallographic icosahedral case has also been investigated more extensively, resulting most recently in groundbreaking advances on carbon 60 and fullerenes in the 1980s and 90s, for which R. Curl, H. Kroto and R. Smalley were jointly awarded a Nobel Prize in Chemistry in 1996.[9][10][11] In 1982–1984, there was another breakthrough involving the icocahedral group, this time through materials scientist Dan Shechtman's remarkable work on quasicrystals, for which he was awarded a Nobel Prize in Chemistry in 2011.[12][13][14][c]
In physical chemistry, double groups are used in the treatment of the magnetochemistry of complexes of metal ions that have a single unpaired electron in the d-shell or f-shell.[16][17] Instances when a double group is commonly used include 6-coordinate complexes of copper(II), titanium(III) and cerium(III).
In these double groups rotation by 360° is treated as a symmetry operation, R, separate from the identity operation, E; the double group is formed by combining the symmetry operations the group {E,R} with the symmetry operations of a point group such as D4 or Oh.
Definition and theory
Let Γ be a finite subgroup of SO(3), the three-dimensional rotation group. There is a natural homomorphism f of SU(2) onto SO(3) which has kernel {±I}.[18] This double cover can be realised using the adjoint action of SU(2) on the Lie algebra of traceless 2-by-2 skew-adjoint matrices or using the action by conjugation of unit quaternions. The double group Γ' is defined as f–1 (Γ). By construction {±I} is a central subgroup of Γ' and the quotient is isomorphic to Γ. Thus Γ' is a central extension of the group Γ by {±1}, the cyclic group of order 2. Ordinary representations of Γ' are just mappings of Γ into the general linear group that are homomorphisms up to a sign; equivalently, they are projective representations of Γ with a factor system or Schur multiplier in {±1}. Two projective representations of Γ are closed under the tensor product operation, with their corresponding factor systems in {±1} multiplying. The central extensions of Γ by {±1} also have a natural product.[19]
The finite subgroups of SU(2) and SO(3) were determined in 1876 by Felix Klein in an article in Mathematische Annalen, later incorporated in his celebrated 1884 "Lectures on the Icosahedron": for SU(2), the subgroups correspond to the cyclic groups, the binary dihedral groups, the binary tetrahedral group, the binary octahedral group, and the binary icosahedral group; and for SO(3), they correspond to the cyclic groups, the dihedral groups, the tetrahedral group, the octahedral group and the icosahedral group. The correspondence can be found in numerous text books, and goes back to the classification of platonic solids. From Klein's classifications of binary subgroups, it follows that, if Γ a finite subgroup of SO(3), then, up to equivalence, there are exactly two central extensions of Γ by {±1}: the one obtained by lifting the double cover Γ' = f–1 (Γ); and the trivial extension Γ x {±1}.[19][2][3][4][20]
The character tables of the finite subgroups of SU(2) and SO(3) were determined and tabulated by F. G. Frobenius in 1898,[1] with alternative derivations by I. Schur and H. E. Jordan in 1907 independently. Branching rules and tensor product formulas were also determined. For each binary subgroup, i.e. finite subgroup of SU(2), the irreducible representations of Γ are labelled by extended Dynkin diagrams of type A, D and E; the rules for tensoring with the two-dimensional vector representation are given graphically by an undirected graph.[2][3][4] By Schur's lemma, irreducible representations of Γ x {±1} are just irreducible representations of Γ multiplied by either the trivial or the sign character of {±1}. Likewise, irreducible representations of Γ' which send –1 to I are just ordinary representations of Γ; while those which send –1 to –I are genuinely double-valued or spinor representations.[19]
Example. For the double icosahedral group, if is the golden ratio with inverse , the character table is given below: spinor characters are denoted by asterisks. The character table of the icosahedral group is also given.[21][22]
Character table: double icosahedral group 1 12C2[5] 12C3[5] 1C4[2] 12C5[10] 12C6[10] 20C7[3] 20C8[6] 30C9[4] 1 1 1 1 1 1 1 1 1 3 3 0 0 –1 3 3 0 0 –1 4 –1 –1 4 –1 –1 1 1 0 5 0 0 5 0 0 –1 –1 0 2 –2 –1 1 0 2 –2 –1 1 0 4 –1 –1 -4 –1 –1 1 0 –1 6 1 1 –6 –1 –1 0 0 0
Character table: icosahedral group 1 20C2[3] 15C3[2] 12C4[5] 12C5[5] 1 1 1 1 1 3 0 –1 3 0 –1 4 1 0 –1 –1 5 –1 1 0 0
The tensor product rules for tensoring with the two-dimensional representation are encoded diagrammatically below:
![](http://upload.wikimedia.org/wikipedia/commons/thumb/9/9b/Affine_E8_diagram.svg/500px-Affine_E8_diagram.svg.png)
The numbering has at the top and then below, from left to right, , , , , , , , and . Thus, on labelling the vertices by irreducible characters, the result of multiplying by a given irreducible character equals the sum of all irreducible characters labelled by an adjacent vertex.[23]
The representation theory of SU(2) goes back to the nineteenth century and the theory of invariants of binary forms, with the figures of Alfred Clebsch and Paul Gordan prominent.[24][8][25][26][27][28][29][30][31] The irreducible representations of SU(2) are indexed by non-negative half integers j. If V is the two-dimensional vector representation, then Vj = S2j V, the 2jth symmetric power of V, a (2j + 1)-dimensional vector space. Letting G be the compact group SU(2), the group G acts irreducibly on each Vj and satisfies the Clebsch-Gordan rules:
In particular for j > 0, and By definition, the matrix representing g in Vj is just S2j ( g ). Since every g is conjugate to a diagonal matrix with diagonal entries and (the order being immaterial), in this case S2j ( g ) has diagonal entries , , ... ,, . Setting this yields the character formula
Substituting , it follows that, if g has diagonal entries then
The representation theory of SU(2), including that of SO(3), can be developed in many different ways:[32]
- using the complexification Gc = SL(2,C) and the double coset decomposition Gc = B · w · B ∐ B, where B denotes upper triangular matrices and ;
- using the infinitesimal action of the Lie algebras of SU(2) and SL(2,C) where they appear as raising and lowering operators E, F, H of angular momentum in quantum mechanics: here E = , F = E* and H = [E,F] so that [H,E] = 2E and [H,F] = –2F;
- using integration of class functions over SU(2), identifying the unit quaternions with 3-sphere and Haar measure as the volume form: this reduces to integration over the diagonal matrices, i.e. the circle group T.
The properties of matrix coefficients or representative functions of the compact group SU(2) (and SO(3)) are well documented as part of the theory of special functions:[33][34] the Casimir operator C = H2 + 2 EF + 2 FE commutes with the Lie algebras and groups. The operator ¼ C can be identified with the Laplacian Δ, so that on a matrix coefficient φ of Vj, Δφ =(j2 + j)φ.
The representative functions A form a non-commutative algebra under convolution with respect to Haar measure μ. The analogue for a finite subgroup of Γ of SU(2) is the finite-dimensional group algebra C[Γ] From the Clebsch-Gordan rules, the convolution algebra A is isomorphic to a direct sum of n x n matrices, with n = 2j + 1 and j ≥ 0. The matrix coefficients for each irreducible representation Vj form a set of matrix units. This direct sum decomposition is the Peter-Weyl theorem. The corresponding result for C[Γ] is Maschke's theorem. The algebra A has eigensubspaces a(gζ) = a(g) or a(g)ζ, exhibiting them as direct sum of Vj, summed over j non-negative integers or positive half-integers – these are examples of induced representations. It allows the computations of branching rules from SU(2) to Γ, so that Vj can be decomposed as direct sums of irreducible representations of Γ.[35][36][33][23]
Background
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In magnetochemistry, the need for a double group arises in a very particular circumstance, namely, in the treatment of the magnetic properties of complexes of a metal ion in whose electronic structure there is a single unpaired electron (or its equivalent, a single vacancy) in a metal ion's d- or f- shell. This occurs, for example, with the elements copper, silver and gold in the +2 oxidation state, where there is a single vacancy in the d-electron shell, with titanium(III) which has a single electron in the 3d shell and with cerium(III) which has a single electron in the 4f shell.
In group theory, the character , for rotation, by an angle α, of a wavefunction for half-integer angular momentum is given by
where angular momentum is the vector sum of spin and orbital momentum, . This formula applies with angular momentum in general.
In atoms with a single unpaired electron the character for a rotation through an angle of is equal to . The change of sign cannot be true for an identity operation in any point group. Therefore, a double group, in which rotation by is classified as being distinct from the identity operation, is used. A character table for the double group D'4 is as follows. The new operation is labelled R in this example. The character table for the point group D4 is shown for comparison.
Character table: double group D'4 D'4 C4 C43 C2 2C'2 2C''2 E R C4R C43R C2R 2C'2R 2C''2R A'1 1 1 1 1 1 1 1 A'2 1 1 1 1 1 -1 -1 B'1 1 1 -1 -1 1 1 -1 B'2 1 1 -1 -1 1 -1 1 E'1 2 -2 0 0 -2 0 0 E'2 2 -2 √2 -√2 0 0 0 E'3 2 -2 -√2 √2 0 0 0
Character table: point group D4 D4 E 2 C4 C2 2 C2' 2 C2 A1 1 1 1 1 1 + A2 1 1 1 −1 −1 B1 1 −1 1 1 −1 B2 1 −1 1 −1 1 E 2 0 −2 0 0
In the table for the double group, the symmetry operations such as C4 and C4R belong to the same class but the header is shown, for convenience, in two rows, rather than C4, C4R in a single row .
Character tables for the double groups T', O', Td', D3h', C6v', D6', D2d', C4v', D4', C3v', D3', C2v', D2' and R(3)' are given in Koster et al. (1963), Salthouse & Ware (1972) and Cornwell (1984).[37][38][39][d]
Applications
![](http://upload.wikimedia.org/wikipedia/commons/thumb/1/1a/Octahedral-3D-balls.png/170px-Octahedral-3D-balls.png)
![](http://upload.wikimedia.org/wikipedia/commons/thumb/5/5b/Square-planar-3D-balls.png/170px-Square-planar-3D-balls.png)
![](http://upload.wikimedia.org/wikipedia/commons/thumb/e/e1/Endohedral_fullerene.png/170px-Endohedral_fullerene.png)
The need for a double group occurs, for example, in the treatment of magnetic properties of 6-coordinate complexes of copper(II). The electronic configuration of the central Cu2+ ion can be written as [Ar]3d9. It can be said that there is a single vacancy, or hole, in the copper 3d-electron shell, which can contain up to 10 electrons. The ion [Cu(H2O)6]2+ is a typical example of a compound with this characteristic.
- (1) Six-coordinate complexes of the Cu(II) ion, with the generic formula [CuL6]2+, are subject to the Jahn-Teller effect so that the symmetry is reduced from octahedral (point group Oh) to tetragonal (point group D4h). Since d orbitals are centrosymmetric the related atomic term symbols can be classified in the subgroup D4 .
- (2) To a first approximation spin-orbit coupling can be ignored and the magnetic moment is then predicted to be 1.73 Bohr magnetons, the so-called spin-only value. However, for a more accurate prediction spin-orbit coupling must be taken into consideration. This means that the relevant quantum number is J, where J = L + S.
- (3) When J is half-integer, the character for a rotation by an angle of α + 2π radians is equal to minus the character for rotation by an angle α. This cannot be true for an identity in a point group. Consequently, a group must be used in which rotations by α + 2π are classed as symmetry operations distinct from rotations by an angle α. This group is known as the double group, D4'.
With species such as the square-planar complex of the silver(II) ion [AgF4]2- the relevant double group is also D4'; deviations from the spin-only value are greater as the magnitude of spin-orbit coupling is greater for silver(II) than for copper(II).[40]
A double group is also used for some compounds of titanium in the +3 oxidation state. Compounds of titanium(III) have a single electron in the 3d shell. The magnetic moments of octahedral complexes with the generic formula [TiL6]n+ have been found to lie in the range 1.63 - 1.81 B.M. at room temperature.[41] The double group O' is used to classify their electronic states.
The cerium(III) ion, Ce3+, has a single electron in the 4f shell. The magnetic properties of octahedral complexes of this ion are treated using the double group O'.
When a cerium(III) ion is encapsulated in a C60 cage, the formula of the endohedral fullerene is written as {Ce3+@C603-}.[42][43]
Free radicals
Double groups may be used in connection with free radicals. This has been illustrated for the species CH3F+ and CH3BF2+ which both contain a single unpaired electron.[44]
See also
Notes
- ^ In his 1931 book Gruppentheorie und ihre Anwendung auf die Quantenmechanik der Atomspektren,[7][8] Eugene Wigner describes in detail how SU(2) arises as a double cover of SO(3), following Hermann Weyl. Referring to a 1928 article of von Neumann and Wigner in Zeitschrift für Physik (vol. 49), Bethe (1929) explains why double-valued representations of finite groups are involved.
- ^ In mathematical language, a double group Γ' is defined to be a central extension of the group Γ by {±1}, the cyclic group of order 2: thus ordinary representations of Γ' are just mappings of Γ into the general linear group that are homomorphisms up to a sign; equivalently, they are projective representations of Γ with a factor system or Schur multiplier in {±1}.
- ^ Ted Janssen has outlined how the characters of the double icosahedral group appear to play a role.[15]
- ^ R(3)' refers to SU(2), the double cover of the three-dimensional rotation group SO(3)
References
- ^ a b Frobenius, F. G. (1899). "Über die Composition der Charaktere einer Gruppe". Sitzungsberichte der Königlich Preussischen Akademie der Wissenschaften zu Berlin (in German): 330–339.
- ^ a b c Griffith, J. S. (1961). The Theory of Transition-Metal Ions. Cambridge University Press. ISBN 9780521115995.
- ^ a b c Ramond, Pierre (2010). Group theory. A physicist's survey. Cambridge University Press. ISBN 978-0-521-89603-0. MR 2663568.
- ^ a b c Jacobs, Patrick (2005). Group Theory with Applications in Chemical Physics. Cambridge University Press. doi:10.1017/CBO9780511535390. ISBN 9780511535390.
- ^ Bethe, Hans (1929). "Termaufspaltung in Kristallen" [Splitting of Terms in Crystals]. Ann. Physik (in German). 395 (3): 133–206.
- ^ English translation in Bethe, Hans (1996). Selected Works of Hans A. Bethe with commentary. Translated by Hans Bethe. World Scientific. pp. 1–72. ISBN 9789810228767. Bethe's commentary: "If an atom is placed in a crystal, its energy levels are split. The splitting depends on the symmetry of the location of the atom in the crystal. The splitting is derived here from group theory. This paper has been widely used, especially by physical chemists."
- ^ Wigner, Eugen (1931). Gruppentheorie und ihre Anwendung auf die Quantenmechanik der Atomspektren (PDF) (in German). Vieweg+Teubner Verlag. ISBN 9783663025559.
- ^ a b Wigner, Eugene (1959). Group theory and its application to the quantum mechanics of atomic spectra. Pure and Applied Physics. Vol. 5. Translated by J. J. Griffin (Expanded and improved ed.). New York–London: Academic Press. p. 157. MR 0106711.
- ^ Chung, Fan R. K.; Kostant, Bertram; Sternberg, Shlomo (1994). "Groups and the buckyball". Lie theory and geometry. Progress in Mathematics. Vol. 123. Birkhäuser. pp. 97–126. MR 1327532. (subscription required)
- ^ Yang, C. N. (1994). "Fullerenes and carbon 60". Perspectives in mathematical physics. Conf. Proc. Lecture Notes Math. Phys., III. Int. Press. pp. 303–307. MR 1314673.
- ^ Chancey, C. C.; O'Brien, M. C. M. (1998). The Jahn-Teller Effect in C60 and Other Icosahedral Complexes. Princeton University Press. doi:10.1515/9780691225340. ISBN 9780691225340.
- ^ See:
- Shechtman, D.; Blech, I.; Gratias, D.R.; Cahn, J.W. (1984). "Metallic phase with long-range orientational order and no translational symmetry". Phys. Rev. Lett. 53: 1951–1953.
- Shechtman, D.; Blech, I. (1985). "The microstructure of rapidly solidified Al6Mn". Metall. Trans. A 16: 1005–1012.
- Shechtman, Dan (8 December 2011). "Nobel Lecture: Quasi-Periodic Materials – A Paradigm Shift in Crystallography" (PDF). nobelprize.org. Stockholm. Retrieved 8 June 2022. Video of Shechtman's Nobel Lecture
- ^ Penrose, Roger (1978). "Pentaplexity: a class of non-periodic tilings of the plane". Eureka. 39. University of Cambridge: 16–22. MR 0558670.
- ^ Au-Yang, Helen; Perk, Jacques (2013). "Quasicrystals—the impact of N. G. de Bruijn". Indag. Math. 24: 996–1017. MR 3124814.
- ^ Janssen, Ted (2014). "Development of Symmetry Concepts for Aperiodic Crystals". Symmetry. 6: 171–188. doi:10.3390/sym6020171.
{{cite journal}}
: CS1 maint: unflagged free DOI (link) - ^ Cotton, F. Albert (1971). Chemical Applications of Group Theory. New York: Wiley. pp. 289–294, 376. ISBN 0 471 17570 6.
- ^ Tsukerblat, Boris S. (2006). Group Theory in Chemistry and Spectroscopy. Mineola, New York: Dover Publications Inc. pp. 245–253. ISBN 0-486-45035-X.
- ^ Wigner 1959.
- ^ a b c Bethe 1929.
- ^ Wolf, Joseph A. (1967). Spaces of constant curvature. New York-London-Sydney: McGraw-Hill. pp. 83–88. MR 0217740.
- ^ Griffith 1961, pp. 383, 385
- ^ Ramond 2010, p. 351
- ^ a b Ramond 2010.
- ^ Weyl, Hermann (1946). The Classical Groups. Their Invariants and Representations. Princeton Landmarks in Mathematics (2nd ed.). Princeton University Press. ISBN 0-691-05756-7. MR 0000255. Archive, Institut Fourier
- ^ Weyl, Hermann (1950). The theory of groups and quantum mechanics [Gruppentheorie und Quantenmechanik]. Translated by H. P. Robertson (Second revised ed.). New York: Dover Books. JFM 54.0954.03. First edition in 1928 from notes of von Neumann; second edition (in German), expanded and simplified in 1931.
- ^ van der Waerden, B. L. (1974). Group theory and quantum mechanics (translated from the 1932 German original). Die Grundlehren der mathematischen Wissenschaften. Vol. 214. , New York-Heidelberg: Springer-Verlag. MR 0479090.
- ^ Tinkham, Michael (1964). Group Theory and Quantum Mechanics. McGraw-Hill. MR 0198828.
- ^ Cracknell, Arthur P. (1968). Applied group theory. Oxford University Press. Zbl 0176.55101.
- ^ Hochschild, G. (1965). The Structure of Lie Groups. San Francisco, London, Amsterdam: Holden-Day. MR 0207883.
- ^ Vilenkin, N. Ja. (1968). Special functions and the theory of group representations. Translations of Mathematical Monographs. Vol. 22. Translated by V. N. Singh. Providence: American Mathematical Society.
- ^ Želobenko, D. P. (1973). Compact Lie groups and their representations. Translations of Mathematical Monographs. Vol. 40. American Mathematical Society.
- ^ Weyl 1946.
- ^ a b Vilenkin 1968.
- ^ Želobenko 1973.
- ^ Hochschild 1965.
- ^ Griffith 1961.
- ^ Salthouse, J.A.; Ware, M.J. (1972). Point group character tables and related data. Cambridge: Cambridge University Press. pp. 55–57. ISBN 0 521 081394.
- ^ Koster, George F.; Dimmock, John O.; Wheeler, Robert G.; Statz, Hermann (1963). Properties of the thirty-two point groups. Cambridge, Mass.: The M.I.T. Press. MR 0159664.
- ^ Cornwell, J. F. (1984). "The double crystallographic point groups". Group theory in physics. Vol. I. Academic Press. pp. 342–355. ISBN 0-12-189801-6. MR 0751778.
- ^ Foëx, D.; Gorter, C. J.; Smits, L.J. (1957). Constantes Sélectionées Diamagnetism et Paramagnetism. Paris: Masson et Cie.
- ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 971. ISBN 978-0-08-037941-8.
- ^ Heath, J.R.; O'Brien, S.C.; Zhang, Q.; Liu, Y.; Curl, R.F.; Kroto, H.W.; Tittel, F.K.; Smalley, R.E. (1985). "Lanthanum complexes of spheroidal carbon shells". Journal of the American Chemical Society. 107 (25): 7779–7780.
- ^ Chai, Yan; Guo, Ting; Jin, Changming; Haufler, Robert E.; Chibante, L. P. Felipe; Fure, Jan; Wang, Lihong; Alford, J. Michael; Smalley, Richard E. (1991). "Fullerenes with metals inside". The Journal of Physical Chemistry. 95 (20): 7564–7568. doi:10.1021/j100173a002.
- ^ Bunker, P.R. (1979), "The Spin Double Groups of Molecular Symmetry Groups", in Hinze, J. (ed.), The Permutation Group in Physics and Chemistry, Lecture Notes in Chemistry, vol. 12, Springer, pp. 38–56, doi:10.1007/978-3-642-93124-6_4, ISBN 978-3-540-09707-5
Further reading
- Lipson, R.H. "Spin-orbit coupling and double groups". (web site)
- Earnshaw, Alan (1968). Introduction to Magnetochemistry. Academic Press.
- Figgis, B.N.; Lewis, J. (1960). "The Magnetochemistry of Complex Compounds". In Lewis. J. and Wilkins. R.G. (ed.). Modern Coordination Chemistry. New York: Wiley.
- Orchard, A.F. (2003). Magnetochemistry. Oxford Chemistry Primers. Oxford University Press. ISBN 0-19-879278-6.
- Vulfson, Sergey G.; Arshinova, Rose P. (1998). Molecular Magnetochemistry. Taylor & Francis. ISBN 90-5699-535-9.