Experimental and theoretical characterization of the S1–S0 transition of benzo[a]pyrene

Gittins, Christopher M.; Rohlfing, Eric A.; Rohlfing, Celeste M.
November 1996
Journal of Chemical Physics;11/1/1996, Vol. 105 Issue 17, p7323
Academic Journal
We use fluorescence excitation and two-color resonance-enhanced multiphoton ionization (REMPI) spectroscopy to characterize the S1–S0 transition of benzo[a]pyrene, B[a]P. In addition, two-color REMPI with a tunable ionization laser provides an improved measurement of the molecular ionization potential, 7.103±0.004 eV. Ab initio calculations are performed to determine the vibrational frequencies for the 90 vibrational modes in the S1 and S0 electronic states. Our results indicate that the single-excitation configuration interaction (CIS) level of theory provides an excellent representation of excited-state frequencies for this large molecule. Virtually all of the vibronic bands between ∼380 nm and 397 nm, as well as numerous bands between 373 nm and 380 nm, are assigned with the aid of the calculated vibrational frequencies. In total, 27 of the 61 a′ symmetry vibrational modes and 5 of the 29 a″ vibrational modes in the S1 state have now been assigned. © 1996 American Institute of Physics.


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