Cyanoacetylene Adsorption on Amorphous and Crystalline Water Ice Films: Investigation through Matrix Isolation and Quantum Study

Abstract

The structure and energy properties of the 1:1 complexes formed between cyanoacetylene and H2O (D2O) are investigated using FT-IR matrix isolation spectroscopy and ab initio calculations at the MP2/ 6-31G(d,p) level. Cyanoacetylene adsorption and desorption on amorphous ice film are monitored by FT-IR using the temperature-programmed desorption method. In an argon matrix, two types of 1:1 complexes are observed. The first one corresponds to the NH structure, which involves a hydrogen bond with the terminal nitrogen of cyanoacetylene. The second corresponds to the HO form, which involves a hydrogen bond from the cyanoacetylene to the oxygen of water. This last complex is the more stable (DeltaE = -8.1 kJ/mol.). As obtained in argon matrixes, two kinds of adsorption site are observed between HC3N and ice. The first one, stable between 25 and 45 K is characterized by a nu(OH) shift similar to the one observed in matrix for the NH complex. The second, stable at higher temperatures (between 45 and 110 K), corresponds to an interaction with the dangling oxygen site of ice and is similar to the HO complex observed in matrix. From theoretical calculations (DFT method combined with a plane wave basis set and ultrasoft pseudopotentials), it is shown that, for this adsorption site, the HC3N moiety is flattened on the ice surface and stabilized by a long-distance interaction ( approximately 3 A) between one dangling OH and the pi system of the C triple bond C triple bond. The HC3N desorption occurs between 110 and 140 K, and the associated desorption energy is 39 kJ/mol. This value is in good agreement with the first principle calculation based on density functional theory and ultrasoft pseudopotentials (34 kJ/mol). These calculations confirm the electrostatic nature of the interaction forces. A small amount of cyanoacetylene is incorporated into the bulk and desorbs at the onset of the ice crystallization near 145 K. In these two kinds of experiments, HC3N acts as both an electrophilic and a nucleophilic molecule.