American Chemical Society, The Journal of Physical Chemistry A, 46(115), p. 13281-13290, 2011
DOI: 10.1021/jp207213c
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We report the analysis of the S1<--S0 rotational band contours of jet-cooled 5-methyl-2-hydroxypyrimidine (5M2HP), the enol form of deoxythymine. Unlike thymine, which exhibits a structureless spectrum, the vibronic spectrum of 5M2HP is well structured, allowing us to determine the rotational constants and the methyl group torsional barriers in the S0 and S1 states. The 0(0)(0), 6a(0)(1), 6b(0)(1), and 14(0)(1) band contours were measured at 900 MHz (0.03 cm(-1)) resolution using mass-specific two-color resonant two-photon ionization (2C-R2PI) spectroscopy. All four bands are polarized perpendicular to the pyrimidine plane (>90% c type), identifying the S1<--S0 excitation of 5M2HP as a 1nπ* transition. All contours exhibit two methyl rotor subbands that arise from the lowest 5-methyl torsional states 0A" and 1E". The S0 and S1 state torsional barriers were extracted from fits to the torsional subbands. The 3-fold barriers are V3" = 13 cm(-1) and V3' = 51 cm(-1); the 6-fold barrier contributions V6" and V6' are in the range of 2-3 cm(-1) and are positive in both states. The changes of A, B, and C rotational constants upon S1 <--S0 excitation were extracted from the contours and reflect an “anti-quinoidal” distortion. The 0(0)(0) contour can only be simulated if a 3 GHz Lorentzian line shape is included, which implies that the S1(1nπ*) lifetime is ~55 ps. For the 6a(0)(1) and 6b(0)(1) bands, the Lorentzian component increases to 5.5 GHz, reflecting a lifetime decrease to ~30 ps. The short lifetimes are consistent with the absence of fluorescence from the 1nπ* state. Combining these measurements with the previous observation of efficient intersystem crossing (ISC) from the S1 state to a long-lived T1 (3nπ*) state that lies ~2200 cm(-1) below [S. Lobsiger, S. et al. Phys. Chem. Chem. Phys. 2010, 12, 5032] implies that the broadening arises from fast intersystem crossing with k(ISC) ≈ 2 × 10(10) s(-1). In comparison to 5-methylpyrimidine, the ISC rate is enhanced by at least 10 000 by the additional hydroxy group in position 2.