Electronic spectra of linear isoelectronic species HC6H+, C6H, HC5N+

Literature Information

Publication Date 2001-03-19
DOI 10.1039/B009604K
Impact Factor 3.676
Authors

Sigrid D. Peyerimhoff


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Abstract

Multireference configuration interaction calculations have been used to determine term energies of low-lying doublet electronic states of isoelectronic carbon chains HC6H+, C6H and HC5N+. Calculations on relevant excited states in the energy range up to 6 eV show that 2Π and 2Φ excited states due to the π–π excitation are comparable in energy pattern among such species, but that there are significant differences in the properties of 2Σ and 2Δ excited state series of these isoelectronic species. Similarities and discrepancies are discussed based on molecular orbital energy patterns and electron correlation. The strongest transitions for HC6H+, C6H and HC5N+ are predicted to correspond to X2Π → 22Π transitions at 2.22, 2.56 and 2.17 eV, respectively. For HC6H+, no 2Σ or 2Δ states arising from σ–π electron promotion are found in the energy range up to 6 eV. However, in C6H the first excited state 12Σ+ due to the 13σ → 3π excitation is found to be only slightly higher (0.22 eV) than the ground state X2Π. Calculated transition energies in the present study show good agreement with available experimental results.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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