Abstract
An alcohol (ROH) solution of p-haloaniline, p-NH2C6H4X (X = Cl, Br, I), was introduced into vacuum as a continuous liquid flow (liquid beam) and was irradiated with a UV nanosecond laser having a pulse width of ∼5 ns or a UV femtosecond laser having a pulse width of ∼200 fs. Ions produced by multiphoton ionization in the liquid beam and ejected from it were analyzed by a time-of-flight mass spectrometer. The mass spectrum of ions ejected from the liquid beam exhibits peaks assignable to H(−NHC6H4−)nH+, H(−NHC6H4−)nOR+, and H(−NHC6H4−)nX+. The spectral features change significantly when the pulse width of the excitation laser is elongated from the femtosecond to the nanosecond range: (1) significant reduction of the H(−NHC6H4−)nBr+ intensities and (2) increase of the degree of polymerization in H(−NHC6H4−)nH+ and H(−NHC6H4−)nOC2H5+. These findings indicate that a sequential polymerization of p-NH2C6H4X is driven by photoabsorption. The degree of polymerization is explained in terms of rate equations of th...
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