Daughter molecules excited states

The greater the number of functions 4 J, belonging to the orthonormal set, the more completely and in more detail the spectrum of the /(-decay-induced excitations of a molecule can be calculated. Consequently, the method for calculating the wave functions of the daughter ion must be such that at a reasonable volume of calculation we would be able to construct a sufficiently large number of multielectron wave functions of excited states. The Hartree Fock method allows one to construct the wave functions of excited states as the combinations of determinants symmetrized in a certain way. Within this method the excitation is considered to be a transition of an electron from an occupied Hartree-Fock molecular orbital into a vacant one. 

The distributions of discrete excitations of daughter molecules versus the excitation energy, W0n = W0n(AE ), are presented in Fig. 4. The excitation energy was calculated according to the well-known formula of Roothaan (1951) for the energy difference of two singlet states... 

Probabilities of Formation of Daughter Molecules in Ground and in Excited Electronic States with Allowance for Electron Correlation... 

The study of the rearrangement of molecular orbitals under the transformation T -> He+ allows one to understand qualitatively the relation between the excitation spectrum of the daughter ion and the features of its chemical structure. If the MOs of the daughter and the parent molecules coincided, the probability [Eq. (44)] of transition into the ground state would be unity, and the excitation probability would be zero. In the sudden-perturbation approximation, it is to the difference in the orbitals of the initial and the final molecules that the excitation of the latter is due. 

The decay-induced fragmentation pattern of a number of representative organic molecules has been determined with appropriate mass spectrometric techniques (7), showing that, in most cases, the daughter organic cation escapes further dissociation, for example, the methyl cation from Equation 1 is obtained with a 82% yield, being formed in its ground electronic state with little or no vibrational excitation. 

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