MANY-BODY PERTURBATION THEORY CALCULATIONS FOR FLAME INTERMEDIATES. METHYLENE AMIDOGEN, $CH_{2}N$, AND $CH_{2}O^{+}$

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1980

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Ohio State University

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Electronic energies and structural parameters are reported for three electronic states of methylene amidogen, $CH_{2}N$. The ground state, $X^{2}B_{1}$, may be represented schematically as [FIGURE] The two excited states occur by excitation of the non-bonding and pi-electrons on the nitrogen, leading to states with three electrons and one electron in the pi-orbitals. Interestingly, the observed excitation energies for transitions to these states differ by only $545 cm^{-1}$, whereas the same transition energies for the isoelectronic cation, $CH_{2}O^{+}$, differ more than 3 eV. We report adiabatic and vertical excitation energies for methylene amidogen and vertical excitation energies for $CH_{2}O^{+}$. The results of the calculations suggest that polarization of the electron distribution in $CH_{2}O^{+}$ leads to stabilization of the $1\pi$ state and destabilization of the $3\pi$ state, relative to the separation in the neutral molecule.

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