Irreducible representations nuclear spin function

Here, only the deuteron spin projections (z-components) of the nuclear spin fuction ( i) are given in the expression for simplicity. These three anti-symmetric nuclear spin functions belong to B irreducible representation in the C2 symmetry (point group) of CHD2 and are only allowed to couple with the rotational function ( r) at the lowest level of 7 = 0 (even) by the Pauli principle. 

For the rotational 7=1 (odd) level of CHD2 the Pauli principle requires the following six possible deuteron nuclear spin functions with A irreducible representation (total symmetry) [75] ... 

Separability between electronic and nuclear states is fundamental to get a description in terms of a hierarchy of electronic and subsidiary nuclear quantum numbers. Physical quantum states, i.e. wavefiinctions 0(q,Q), are non-separable. On the contrary, there is a special base set of functions Pjt(q,Q) that can be separable in a well defined mode, and used to represent quantum states as linear superpositions over the base of separable molecular states. For the electronic part, the symmetric group offers a way to assign quantum numbers in terms of irreducible representations [17]. Space base functions can hence be either symmetric or anti-symmetric to odd label permutations. The spin part can be treated in a similar fashion [17]. The concept of molecular species can be introduced this is done at a later stage [10]. Molecular states and molecular species are not the same things. The latter belong to classical chemistry, the former are base function in molecular Hilbert space. 

The presence of two nuclear spins means that there is considerable choice in the selection of basis functions the reader who wishes to practice virtuosity in irreducible tensor algebra is invited to calculate the matrix elements in the different coupled representations that are possible In fact the sensible choice, particularly when a strong magnetic field is to be applied, is the nuclear spin-decoupled basis set t], A N, S, J, Mj /N, MN /H, MH). Again note the possible source of confusion here MN is the space-fixed component of the nitrogen nuclear spin /N, not the space-fixed component of N. This nuclear spin-decoupled basis set was the one chosen by Wayne and Radford in their analysis of the NH spectrum. 

Symmetry properties of the nuclear wavefunction are different in the diabatic and adiabatic representations. The pair of adiabatic electronic states (see (1)) belong to the Al and A2 irreducible representations of the double group of S3. The diabatic states obtained from the adiabatic ones by applying the U matrix form a basis for the two dimensional irreducible representation E of S3. For quartet nuclear spin states, the electronuclear wavefunction, nuclear spin part excluded, must belong to the A2 irreducible representation. This requires the nuclear wavefunction (without nuclear spin) to be of the same E symmetry as the electronic one, because of the identity E x E = Ai + A2 + E. For doublet spin states, the E electronuclear wave-function (nuclear spin excluded) is obtained with an Ai or A2 nuclear wavefunction, combined with the E electronic ones. 

Symmetrised density-functionals, which have been proposed recently [88] as the correct solution of the symmetry dilemma in Kohn-Sham theory, also naturally lead to fractional occupations. The symmetry dilemma occurs because the density or spin-density of KS theory may exhibit lower symmetry them the external potential due to the nuclear conformation. This in turn leads to a KS Hamiltonian with broken symmetry, leading to electronic orbitals that cannot be assigned to an irreducible representation... 

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