Symmetry spin functions

IT. Total Molecular Wave Functdon TIT. Group Theoretical Considerations TV. Permutational Symmetry of Total Wave Function V. Permutational Symmetry of Nuclear Spin Function VT. Permutational Symmetry of Electronic Wave Function VIT. Permutational Symmetry of Rovibronic and Vibronic Wave Functions VIIT. Permutational Symmetry of Rotational Wave Function IX. Permutational Symmetry of Vibrational Wave Function X. Case Studies Lis and Other Systems... 

Since the total wave function must have the correct symmetry under the permutation of identical nuclei, we can determine the symmetiy of the rovi-bronic wave function from consideration of the corresponding symmetry of the nuclear spin function. We begin by looking at the case of a fermionic system for which the total wave function must be antisynmiebic under permutation of any two identical particles. If the nuclear spin function is symmetric then the rovibronic wave function must be antisymmetric conversely, if the nuclear spin function is antisymmebic, the rovibronic wave function must be symmetric under permutation of any two fermions. Similar considerations apply to bosonic systems The rovibronic wave function must be symmetric when the nuclear spin function is symmetric, and the rovibronic wave function must be antisymmetiic when the nuclear spin function is antisymmetric. This warrants... 

However, drastic consequences may arise if the nuclear spin is 0 or In these cases, some rovibronic states cannot be observed since they are symmetry forbidden. For example, in the case of C 02, the nuclei are spinless and the nuclear spin function is symmetric under permutation of the oxygen nuclei. Since the ground electronic state is only even values of J exist for the ground vibrational level (vj, V3) = (OO O), where (vi,V2,V3) are the... 

As discussed in preceding sections, FI and have nuclear spin 5, which may have drastic consequences on the vibrational spectra of the corresponding trimeric species. In fact, the nuclear spin functions can only have A, (quartet state) and E (doublet) symmetries. Since the total wave function must be antisymmetric, Ai rovibronic states are therefore not allowed. Thus, for 7 = 0, only resonance states of A2 and E symmetries exist, with calculated states of Ai symmetry being purely mathematical states. Similarly, only -symmetric pseudobound states are allowed for 7 = 0. Indeed, even when vibronic coupling is taken into account, only A and E vibronic states have physical significance. Table XVII-XIX summarize the symmetry properties of the wave functions for H3 and its isotopomers. 

The notation < i j k 1> introduced above gives the two-electron integrals for the g(r,r ) operator in the so-called Dirac notation, in which the i and k indices label the spin-orbitals that refer to the coordinates r and the j and 1 indices label the spin-orbitals referring to coordinates r. The r and r denote r,0,( ),a and r, 0, ( ), a (with a and a being the a or P spin functions). The fact that r and r are integrated and hence represent dummy variables introduces index permutational symmetry into this list of integrals. For example,... 

Spatial function Spin function Symmetry Configuration... 

BalKSO Balasubramanian, K. Graph theoretical characterization of NMR groups, non-rigid nuclear spin species and the construction of symmetry adapted NMR spin functions. J. Chem. Phys. 73 (1980) 3321-3337. 

The wave fiinetion for a system of N identical particles is either symmetric or antisymmetric with respect to the interchange of any pair of the N particles. Elementary or eomposite particles with integral spins (s = 0, 1,2,. ..) possess symmetrie wave functions, while those with half-integral spins (s = 1. .)... 

Spin-degenerate systems, geometric phase theory, conical intersections, 6-8 Spin function, permutational symmetry, group theoretical properties,... 

Gv( f) covering symmetry67. For orientations of B0 in the mirror plane S, the symmetry group of the spin Hamiltonian is < 9f = C2h(e2f). The direct product base of the nuclear spin functions of two geometrically equivalent nuclei reduces to two classes, containing six A-type and three B-type functions, respectively. Second order perturbation theory applied to H = UtHU, where U symmetrizes the base functions of the Hamil-... 

This argument is not restricted to spatial symmetry and in fact the most familiar example of the phenomenon is the Different Orbitals for Different Spins (DODS) technique for open electronic shells where the total spin function S2 takes the role of our G (in the one-electron-group model). 

So far, we have seen how to use the character tables of the point symmetry groups to interpret the optical spectra of some ions. When dealing with spin functions of ions, we have the possibility of half-odd integer values for the spin (or for the... 

The calculated state energies, the transition moments, and the symmetry classification are given in Table 3. The symmetry species of the triplet functions is obtained by taking the direct product of irreducible representation of the space and the spin functions Fx, Fy, Fz, which transform as the rotations Rx, Ry, and Rz-... 

The function F(l,2) is in fact the space part of the total wave function, since a non-relativistic two-electron wave function can always be represented by a product of the spin and space parts, both having opposite symmetries with respect to the electrons permutations. Thus, one may skip the spin function and use only the space part of the wave function. The only trace that spin leaves is the definite per-mutational symmetry and sign in Eq.(14) refers to singlet as "+" and to triplet as Xi and yi denote cartesian coordinates of the ith electron. A is commonly known angular projection quantum number and A is equal to 0, 1, and 2 for L, II and A symmetry of the electronic state respectively. The linear variational coefficients c, are found by solving the secular equations. The basis functions i(l,2) which possess 2 symmetry are expressed in elliptic coordinates as ... 

To generate the proper Aj, A2, and E wavefunctions of singlet and triplet spin symmetry (thus far, it is not clear which spin can arise for each of the three above spatial symmetries however, only singlet and triplet spin functions can arise for this two-electron example), one can apply the following (un-normalized) symmetry projection operators (see Appendix E where these projectors are introduced) to all determinental wavefunctions arising from the e2 configuration ... 

The hydrogen nucleus is classified as a Eermi particle with nuclear spin I = 1/2. Because of Pauli exclusion principle, hydrogen molecule is classified into two species, ortho and para. Erom the symmetry analysis of the wave functions, para-hydrogen is defined to have even rotational quantum number J with a singlet nuclear spin function, and ortho-hydrogen is defined to have odd J with a triplet nuclear spin function. The interconversion between para and ortho species is extremely slow without the existence of external magnetic perturbation. 

For dissimilar pairs, the parameter ys equals zero and we have Eq. 5.36. Like pairs of zero spin are bosons and all odd-numbered partial waves are ruled out by the requirement of even wavefunctions of the pair this calls for ys = 1. In general, for like pairs, the symmetry parameter ys will be between -1 and 1, depending on the monomer spins (fermions or bosons) and the various total spin functions of the pair. A simple example is considered below (p. 288ff.). If vibrational states are excited, the radial wavefunctions xp must be obtained from the vibrationally averaged potential, Fq(R). The functions gf(R) and gM(R) are similar to the pair distribution function, namely [294]... 

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