CAVITY RINGDOWN ABSORPTION SPECTRUM OF THE $T_1(n,\pi^{*}) \leftarrow S_0$ TRANSITION OF \\ ACROLEIN: ANALYSIS OF THE $0^0_0$ BAND ROTATIONAL CONTOUR

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Acrolein (propenal, CH2=CH---CH=O) is the simplest conjugated enal molecule and serves as a prototype for investigating the photochemical properties of larger enals and enones. Acrolein has a coplanar arrangement of heavy atoms in its ground electronic state. Much of the photochemistry is mediated by the T1(π,π) state, which has a CH2--twisted equilibrium structure. In solution, the T1(π,π) state is typically accessed via intersystem crossing from an intially prepared planar S1(n,π) state. An intermediate in this photophysical transformation is the lowest 3(n,π) state, a planar species with adiabatic excitation energy below S1 and above T1(π,π). The present work focuses on this 3(n,π) intermediate state; it is designated T1(n,π) as the lowest-energy triplet state of acrolein having a planar equilibrium structure. \hspace{0.2in}The T1(n,π)←S0 band system, with origin near 412 nm, was first recorded in the 1970s at medium (0.5 cm−1) resolution using a long-path absorption cell. Here we report the cavity ringdown spectrum of the 000 band, recorded using a pulsed dye laser with 0.1 cm−1 spectral bandwidth. The spectrum was measured under both bulk-gas (room-temperature) and jet-cooled conditions. The band contour in each spectrum was analyzed by using a computer program developed, \emph{J.~Chem.~Phys.}~\textbf{103}, 5343 (1995).} for simulating and fitting the rotational structure of singlet-triplet transitions. The assignment of several resolved sub-band heads in the room-temperature spectrum permitted approximate fitting of the inertial constants for the T1(n,π) state. The determined values (cm−1) are A=1.662, B=0.1485, C=0.1363. For the parameters A and (B+C)/2, estimated uncertainties of ±0.003 cm−1 and ±0.0004 cm−1, respectively, correspond to a range of values that produce qualitatively satisfactory global agreement with the observed room-temperature contour. The fitted inertial constants were used to simulate the rotational contour of the 000 band under jet-cooled conditions. Agreement with the observed jet-cooled spectrum was optimized by varying the homogeneous linewidth of the rovibronic transitions as well as the rotational temperature. The optimal FWHM was about 0.20 cm−1, leading to an estimate of 25 ps for the lifetime of the T1(n,π) state of acrolein (v=0) under isolated-molecule conditions.

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Author Institution: Department of Chemistry, University of Wisconsin-Eau Claire; Eau Claire, WI 54702

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