Cavity Ringdown Absorption Spectrum of the T_1 (n,π^{*}) ← S_0 Transition of 2-CYCLOHEXEN-1-ONE
Abstract
The cavity ringdown (CRD) absorption spectrum of 2-cyclohexen-1-one (CHO) was recorded over the range 401.5-410.5 nm in a room-temperature gas cell.
The very weak band system (ɛ ≤ 0.02 dm^3 mol^{-1} {cm}^{-1}) in this region is due to the T_1(n, π*) ← S_0 electronic transition. The 0^0_0 origin band was assigned to the feature observed at {24,558.6 ± 0.3 {cm}^{-1}}. We have assigned about 25 vibronic transitions in a region extending from {-200 to +350 cm^{-1}} relative to the origin band. From these assignments we determined fundamental frequencies for several vibrational modes in the T_1 excited state. The table below compares their frequencies to corresponding values measured for CHO vapor in the S_0 electronic ground state (via far-IR spectroscopy) and the S_1(n, π*) excited state (via near-UV CRD spectroscopy). Low-frequency fundamentals (cm^{-1}) of CHO vapor Mode Description S_0 S_1(n,π^*) T_1(n,π^*) 39 ring twist 99.2 122.1 99.5 38 bend (inversion of C-5) 247 251.9 253.2 37 C=C twist 304.1 303.3 247.8 36 C=O wag 485 343.9 345.5 For ν_{39} and ν_{37}, the differences between S_1 and T_1 frequencies are noteworthy. These differences suggest that the electron delocalization associated with the π^* ← n chromophore in CHO is substantially different for singlet vs. triplet excitation. T. L. Smithson and H. Wieser, J. Chem. Phys. {73}, 2518 (1980) M. Z. M. Rishard and J. Laane, J. Molec. Struct. {976}, 56 (2010). M. Z. M. Rishard, E. A. Brown, L. K. Ausman, S. Drucker and J. Laane, J. Phys. Chem. A {112}, 38 (2008).- Publication:
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68th International Symposium on Molecular Spectroscopy
- Pub Date:
- June 2013
- Bibcode:
- 2013mss..confEMI06Z
- Keywords:
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- ELECTRONIC