Excited-state vibrations, lifetimes, and nonradiative dynamics of jet-cooled 1-ethylcytosine

The S₁ excited-state lifetime of jet-cooled 1-ethylcytosine (1ECyt) is ∼1 ns, one of the longest lifetimes for cytosine derivatives to date. Here, we analyze its S₀ → S₁ vibronic spectrum using two-color resonant two-photon ionization and UV/UV holeburning spectroscopy. Compared to cytosine and 1-methylcytosine, the S₀ → S₁ spectrum of 1ECyt shows a progression in the out-of-plane "butterfly" mode ν₁ ^', identified by spin-component scaled-second-order coupled-cluster method ab initio calculations. We also report time-resolved S₁ state nonradiative dynamics at ∼20 ps resolution by the pump/delayed ionization technique. The S₁ lifetime increases with the number of ν₁ ^' quanta from τ = 930 ps at v₁ ^'=0 to 1030 ps at v₁ ^'=2, decreasing to 14 ps at 710 cm^-1 vibrational energy. We measured the rate constants for S₁ ⇝ S₀ internal conversion and S₁ ⇝ T₁ intersystem crossing (ISC): At the v' = 0 level, k_IC is 8 × 10⁸ s^-1 or three times smaller than 1-methylcytosine. The ISC rate constant from v' = 0 to the T₁(³ππ^*) state is k_ISC = 2.4 × 10⁸ s^-1, 10 times smaller than the ISC rate constants of cytosine, but similar to that of 1-methylcytosine. Based on the calculated S₁(¹ππ^*) state radiative lifetime τ_rad = 12 ns, the fluorescence quantum yield of 1ECyt is Φ_fl ∼ 7% and the intersystem crossing yield is Φ_ISC ∼ 20%. We measured the adiabatic ionization energy of 1-ethylcytosine via excitation of the S₁ state as 8.353 ± 0.008 eV, which is 0.38 eV lower than that of amino-keto cytosine. Measurement of the ionization energy of the long-lived T₁(ππ^*) state formed via ISC reveals that it lies 3.2-3.4 eV above the S₀ ground state.