The 2-cyclohexen-1-one (2CHO) molecule serves as a prototype for understanding the photochemical properties of conjugated enones. We have recorded the cavity ringdown (CRD) absorption spectrum of 2CHO vapor at room temperature over the 360-380 nm range. This portion of the spectrum encompasses the S(n,π*) ← S vibronic band system in the region of the C═C and C═O stretch fundamentals. We have assigned about 40 vibronically resolved features in the spectrum, affording fundamental frequencies for 7 different vibrational modes in the S(n,π*) state, including the C═C (1554 cm) and OC-CH (1449 cm) stretch modes. The C═O stretch character is spread over at least four different vibrational modes in the S(n,π*) state, with fundamentals spanning the 1340-1430 cm interval. This finding stems from a significant reduction in C═O bond order upon excitation, which leads to near-coincidence of the C═O stretch and several CH wag frequencies. Such complexities make 2CHO an ideal candidate for testing excited-state computational methods. We have used the present spectroscopic results to test EOM-EE-CCSD harmonic-frequency predictions for the S(n,π*) state. We have also benchmarked the performance of less costly computational methods, including CIS(D) and TDDFT. For certain density functionals (e.g., B3LYP and PBE0), we find that the accuracy of TDDFT frequency predictions can approach but not meet that of EOM-EE-CCSD.
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