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

Abstract

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, kIC 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 kISC = 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 τrad = 12 ns, the fluorescence quantum yield of 1ECyt is Φfl ∼ 7% and the intersystem crossing yield is ΦISC ∼ 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.