In our laboratory a novel and convenient technique has been developed to generate an intense pulsed cyano radical beam to be employed in crossed molecular beam experiments investigating the chemical dynamics of bimolecular reactions. CN radicals in their ground electronic state 2 ⌺ ϩ are produced in situ via laser ablation of a graphite rod at 266 nm and 30 mJ output power and subsequent reaction of the ablated species with molecular nitrogen, which acts also as a seeding gas. A chopper wheel located after the ablation source and before the collision center selects a 9 s segment of the beam. By changing the delay time between the pulsed valve and the choppper wheel, we can select a section of the pulsed CN͑X 2 ⌺ ϩ ͒ beam choosing different velocities in the range of 900-1920 ms Ϫ1 with speed ratios from 4 to 8. A high-stability analog oscillator drives the motor of the chopper wheel ͑deviations less than 100 ppm of the period͒, and a high-precision reversible motor driver is interfaced to the rotating carbon rod. Both units are essential to ensure a stable cyanogen radical beam with velocity fluctuations of less than 3%. The high intensity of the pulsed supersonic CN beam of about 2-3ϫ10 11 cm Ϫ3 is three orders of magnitude higher than supersonic cyano radical beams employed in previous crossed molecular beams experiments. This data together with the tunable velocity range clearly demonstrate the unique power of our newly developed in situ production of a supersonic CN radical beam. This versatile concept is extendible to generate other intense, pulsed supersonic beams of highly unstable diatomic radicals, among them BC, BN, BO, BS, CS, SiC, SiN, SiO, and SiS, which are expected to play a crucial role in interstellar chemistry, chemistry in the solar system, and/or combustion processes.

The photophysics, including radiative and nonradiative quantum yields and decay rates, of regioregular poly-(3-dodecylthiophene) (P3DT) in benzene were studied by means of UV-visible spectroscopy, photoluminescence spectroscopy, photothermal beam deflection (PBD), photoacoustic calorimetry (PAC), and timeresolved photoluminescence spectroscopy. We observe the fluorescence quantum efficiency to be 0.30 ( 0.01 and the internal conversion (from S 1 to S 0 ) quantum yield of 0.59 ( 0.02 as well as the intersystem crossing (from S 1 to T 1 ) quantum yield of 0.11 ( 0.01. By measuring the fluorescence lifetime of ca. 490 ps, we estimate a radiative lifetime of 1.64 ns for the singlet excitons and nonradiative decay rate constants of k ic ) 1.21 ns -1 and k isc ) 0.22 ns -1 for internal conversion and intersystem crossing, respectively. The nature and photophysics of triplet states in poly(3-dodecylthiophene) are well characterized using PBD and PAC, and the result suggests that internal conversion plays a major role in energy depletion.