IONIZATION ENERGIES OF CONJUGATED HYDROCARBONS

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Date

1960

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Ohio State University

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Abstract

Ionization energy calculations have been made which attempt to include three effects inherently neglected in the application of Koopmans’ Theorem to conjugated hydrocarbons. These effects are: (1) Effect of $\pi$-electron ionization on the $\sigma$-framework. (2) Change in C $2p_{2}$ basis functions upon ionization. (3) Construction of a new Hartree-Fock Hamiltonian for the ionized state and subsequent reminimizatin. The Pariser-Parr formulation in terms of semi-empirical electron repulsion integrals and differential overlap was assumed. For the reminimization of the ionized state $Roothaan’s^{1}$ generalized SCF approach is being used. The results of the change in basis functions are as follows: [FIGURE] The calculated change in $\sigma$-bond energy is $-0.8$ c.v. for the above cases. The effect of reminimization on the ionized state will be discussed.

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$^{1}$ C. C. J. Roothaan, to be published, Revs. Mod. Phys.
Author Institution: Whitmore Chemical Laboratory, The Pennsylvania State University

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