Wave function permutational symmetry

Wigner rotation/adiabatic-to-diabatic transformation matrices, 92 Electronic structure theory, electron nuclear dynamics (END) structure and properties, 326-327 theoretical background, 324-325 time-dependent variational principle (TDVP), general nuclear dynamics, 334-337 Electronic wave function, permutational symmetry, 680-682 Electron nuclear dynamics (END) degenerate states chemistry, xii-xiii direct molecular dynamics, structure and properties, 327 molecular systems, 337-351 final-state analysis, 342-349 intramolecular electron transfer,... 

Rovibronic wave function, permutational symmetry, 682-683 Rydberg states ... 

Total molecular wave function, permutational symmetry, 661-668, 674-678 Tracing techniques, molecular systems, multidegenerate nonlinear coupling continuous tracing, component phase, 236-241... 

A symmetry that holds for any system is the permutational symmetry of the polyelectronic wave function. Electrons are fermions and indistinguishable, and therefore the exchange of any two pairs must invert the phase of the wave function. This symmetry holds, of course, not only to pericyclic reactions. 

Stabilizing resonances also occur in other systems. Some well-known ones are the allyl radical and square cyclobutadiene. It has been shown that in these cases, the ground-state wave function is constructed from the out-of-phase combination of the two components [24,30]. In Section HI, it is shown that this is also a necessary result of Pauli s principle and the permutational symmetry of the polyelectronic wave function When the number of electron pairs exchanged in a two-state system is even, the ground state is the out-of-phase combination [28]. Three electrons may be considered as two electron pairs, one of which is half-populated. When both electron pahs are fully populated, an antiaromatic system arises ("Section HI). 

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... 

As pointed out in the previous paragraph, the total wave function of a molecule consists of an electronic and a nuclear parts. The electrons have a different intrinsic nature from nuclei, and hence can be treated separately when one considers the issue of permutational symmetry. First, let us consider the case of electrons. These are fermions with spin and hence the subsystem of electrons obeys the Fermi-Dirac statistics the total electronic wave function... 

Let us discuss further the pemrutational symmetry properties of the nuclei subsystem. Since the elechonic spatial wave function t / (r,s Ro) depends parameti ically on the nuclear coordinates, and the electronic spacial and spin coordinates are defined in the BF, it follows that one must take into account the effects of the nuclei under the permutations of the identical nuclei. Of course. 

VII. PERMUTATIONAL SYMMETRY OF ROVIBRONIC AND VIBRONIC WAVE FUNCTIONS... 

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... 

The permutational symmetry of the rotational wave function is determined by the rotational angular momentum J, which is the resultant of the electronic spin S, elecbonic orbital L, and nuclear orbital N angular momenta. We will now examine the permutational symmetry of the rotational wave functions. Two important remarks should first be made. The first refers to the 7 = 0 rotational... 

As discussed above, the permutational symmetry of the total wave function requires the proper combination of its various contributions. These are summarized in Tables V-Xn for all isotopomers of Lis. Note that the conclusions hold provided that the various wave functions have the appropriate symmetries. If, for some reason, one of the components fails to meet such a requirement, then the symmetry of the total wave function will fail too. For example, even if the vibrational wave functions are properly assigned, the total wave... 

The Symmetry Properties of Wave Functions of Li3 Electronically Ground State in [Pg.582]

Symmetry Properties of H3 and H3 Wave Functions in the S3 Permutation Group... 

In this chapter, we discussed the permutational symmetry properties of the total molecular wave function and its various components under the exchange of identical particles. We started by noting that most nuclear dynamics treatments carried out so far neglect the interactions between the nuclear spin and the other nuclear and electronic degrees of freedom in the system Hamiltonian. Due to... 

---