[en] Graphite is laser vaporized into a He carrier gas containing various simple molecules such as H₂, H₂O, NH₃, and CH₃CN, supersonically expanded, and skimmed into a molecular beam, and the beam is interrogated by photoionization time-of-flight mass spectrometry. Without added reactants in the He carrier gas, C/sub n/ species up to n = 130 are readily observed. Two distributions separated at about n = 40 appear to be present with the low n species the focus of this work. In the presence of added reagents, new species appear as a result of reaction. These are satisfactorily explained on the basis that a significant proportion of the C/sub n/ species initially formed are reactive radicals with linear carbon chain structures which can readily add H, N, or CN at the ends to form relatively stable polyynes or cyanopolyynes. Some of the cyanopolyynes detected have also been observed in the interstellar medium, and circumstellar carbon condensation processes in the atmospheres of carbon-rich stars similar to those studied here are suggested as possible synthetic sources