D. Yu, Changwu Dong, Lijuan Zhang
Aug 10, 2011
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Influential Citations
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Journal
Journal of Molecular Structure
Abstract
Abstract The effects of conformation and isotopic substitution on the properties of 3-chloro-4-fluoroanisole (3C4FA) were studied by mass-analyzed resonant two-photon ionization (R2PI) technique and theoretical calculations. In the one color R2PI spectra, the band origins of the S 1 ← S 0 electronic transitions (0 0 bands) of cis 35 Cl–3C4FA and cis 37 Cl–3C4FA were found to be equivalent at 34,703 ± 3 cm −1 , while the 0 0 bands of trans 35 Cl–3C4FA and trans 37 Cl–3C4FA were found to be equivalent at 34,747 ± 3 cm −1 . Assignments of the observed vibrational bands of R2PI spectra were made mainly based on the 10-electron, 8-orbital CASSCF/6-31g calculations and on conformity with the available data of the similar aromatic molecules in the literature. With the two color R2PI technique, the adiabatic ionization energies (IEs) of cis 35 Cl–3C4FA and cis 37 Cl–3C4FA were determined to be equivalently 67,349 ± 15 cm −1 , while the IEs of trans 35 Cl–3C4FA and trans 37 Cl–3C4FA were determined to be equivalently 67,595 ± 15 cm −1 . The conformational effect on the transition energies, ionization energies and vibrational frequencies of 3C4FA is greater than the isotopic effect. The hetero-dihalogen-substitution effect on the transition energies is also discussed.