The continuous flowing beams of the triplet state phenylnitrene (PhN) species have been generated by respective pyrolysis of PhN3 at 83(+/-0.5) degreesC and phenylisocyanate (PhNCO) at 105(+/-0.5) degreesC in the quartz inlet tube loosely filled with a 30 A molecular sieve powder supported on the quartz wool. PE spectrum of PhN is recorded in situ for the first time. The ionization energies, corresponding to different ionic states of PhN+, are determined by PES experiment and both G2 and DFT calculations. The study indicates that PhN is a diradical with C-2v symmetry and has a (3)A(2) ground state. (C) 2003 Elsevier B.V. All rights reserved.