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In a previous letter [J. Chem. Phys. 92, 4622 (1990)] we reported the first observation of the 2 1Ag state of cis-hexatriene in a supersonic jet expansion by using resonance enhanced multiphoton ionization spectroscopy. Here, the vibrational analysis of the 1 1Ag→2 1Ag excitation spectrum of cis-hexatriene is presented. The excitation spectrum shows that cis-hexatriene in the 2 1Ag state deviates slightly from planarity; a conclusion which is corroborated by ab initio calculations indicating that the nonplanarity primarily involves the terminal hydrogen atoms. Except for observable intensity in the low frequency modes associated with the small out of plane distortion, the vibronic development of the 1 1Ag→2 1Ag transition in cis-hexatriene is similar to that observed for other polyenes: the 0–0 transition is the most intense feature and the next most intense band is the C■C stretching fundamental. Thus the general features of the electronic structure of the cis-hexatriene 2 1Ag state are analogous to those of other polyenes.

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Laser-induced copper plasma emission was investigated by time-integrated spatially resolved spectrometry. The comparative work on the plasma emission characteristics—specifically, self-absorption, line broadening, emission intensity, and metal ion formation—was carried out by the use of two different laser systems (XeCl excimer: = 308 nm; Nd:YAG: = 1064 and 532 nm). The characteristics of plasma emission produced by different wavelength radiation on copper atomic and ion lines under various atmospheric gases (argon, neon, and helium) and pressures (760–10 Torr) are presented. The differences in self-absorption and line broadening phenomena in the plasma location were explained by shock wave-driven excitation mechanism for atoms in the outer region in the plasma. The excitation temperatures of the plasma induced by 308- or 532-nm irradiation were also much higher that those induced by 1064-nm irradiation.