Matrix Isolation Fourier Transform Infrared and Ab Initio Studies of the 193-nm-Induced Photodecomposition of Formamide

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 102; no. 33; pp. 6643 - 6650
• Main Authors: Lundell, J, Krajewska, M, Räsänen, M
• Format: Journal Article
• Language: English
• Published: American Chemical Society 13-08-1998
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp9810724

Ultraviolet irradiation of formamide in solid argon forms hydrogen-bonded, carbon- and oxygen-attached complexes NH3−CO and NH3−OC. Computationally, the carbon-attached complex is 1.2 kJ mol-1 more stable than the oxygen-attached complex. However, a thermal equilibrium of the two structures is found experimentally in the matrices. Moreover, the oxygen-attached complex dominates in the 193-nm-induced photolytic complex formation from formamide. In xenon matrices, the photochemistry of formamide increasingly yield the HNCO+H2 binary system. The change in photochemistry of formamide between the argon and xenon enviroments can be attributed to an external heavy-atom effect, where xenon enhances the rate of intersystem crossing from a singlet to a triplet surface.