Photoionization mass spectrometric study of the prebiotic species formamide in the 10-20 eV photon energy range.

A photoion mass spectrometry study of the prebiotic species formamide was carried out using synchrotron radiation over the photon energy range 10-20 eV. Photoion yield curves were measured for the parent ion and seven fragment ions. The ionization energy of formamide was determined as IE (1(2)A') = 10.220 +/- 0.005 eV, in agreement with a value obtained by high resolution photoelectron spectroscopy. The adiabatic energy of the first excited state of the ion, 1(2)A'', was revised to 10.55 eV. A comparison of the ionization energies of related formamides, amino acids, and polypeptides provides useful information on the varied effects of methylation and shows that polymerization does not substantially alter the ionization properties of the amino acid monomer units. Assignments of the fragment ions and the pathways of their formation by dissociative photoionization were made on the basis of ion appearance energies in conjunction with thermochemical data and the results of earlier electron impact mass spectral studies. Some of the dissociation pathways are considered to involve coupling between the 1(2)A' ground state and the low-lying 1(2)A'' excited state of the cation. Heats of formation are derived for all ions detected and are compared with literature values where they exist. Formation of the HNCO(+) ion occurs by two separate paths, one involving H(2) loss, the other H + H. In the conclusion a brief discussion is given of some astrophysical implications of these results.