Formation of CO2 from formic acid through catalytic electron channel

Abstract

Low energy electrons can initiate and control chemical reactions through resonant attachment forming an electron-molecule compound state. Recently, it has been theoretically shown that free electrons can also act as catalysts in chemical reactions. We investigate this novel concept for the case of conversion of formic acid into CO. Resonant production of CO from cold formic acid films by low energy electron impact is observed using Fourier transform infrared spectroscopy. The resonant peak observed at 6 eV is identified as the catalytic electron channel. The experimental results are augmented with the quantum chemical calculations.

Formic Acid Ionization and Fragmentation by Multiphoton Absorption

“…Figure 1 shows the typical spectra. The most abundant detected m / q signals were 1,12,13,16,17,18,28,29,30,32,45 and 46 most of them corresponding to the breakdown of each of the molecular bonds of formic acid proposed previously for various authors using different types of projectiles. In Figure1 the mass spectra as a function of the carrier gas are shown.…”

“…From the comparison with former experiments, were different projectiles were used [photons, photons or electrons], there is still to prove what of the fragmentation paths contribute to the observed ions and to understand the response of such simple molecule to the projectiles. More experiments about the studies of these reactions and their influence on a vast area of research are needed [30]. Moreover [31] recent studies on dissociative electron attachment of formic acid show interesting dissociation pathways leading to negative hydrogen ions.…”

Toward a description of electron-induced dissociative excitation in H2O+ : Investigation of three resonances above the BRabadán1, Gorfinkiel2 2021Phys. Rev. A4070View full textAdd to dashboardCite

“…In order to determine an optimal target model, a number of basis sets (cc-pVDZ, cc-pVTZ, cc-pVQZ, DZP, and TZP), two active spaces [ (7,9) and (7,10)], and different averaging sets of states (including between one and five states of the symmetries 2 A1, 2 B1 and 2 B2 were tested for the equilibrium geometry.…”

“…The model we have chosen uses the TZP basis set [25] for oxygen and the DZP [26] one for H. It includes, in the state averaging, two 2 B1 states (the symmetry of the ground state of H 2 O + ), two 2 A1 states, and one 2 B2 state. In generating the configurations in which the electronic wave functions i are expanded, the two 1s electrons of oxygen are kept frozen (the corresponding molecular orbital is the 1a 1 ) and the (7,10) active space consists of the following orbitals: 2-6 a 1 , 1-2 b 1 , and 1-3 b 2 . A total of 11 target states, ten of them doublets and a quartet, were included in the scattering calculations.…”

“…This latter process, however, also contributes reactive species to the medium, not only when the target is a cation but also for neutral molecules, and is therefore of relevance in other environments (e.g., irradiated biological matter where this process can lead to the formation of, for example, highly reactive OH radicals known to damage DNA [1]). The scarcity of experimental or theoretical studies of DE for neutral targets is also apparent (see [2] for a review of data for oxygen containing molecules, [3,4] for CH 4 , and [5] for simplified calculations for NF x targets), but interesting mechanisms have been identified: the electron can act as a catalyst and induce (without long-term attachment) the breakup of one or more bonds in a process named "bondbreaking by catalytic electron" [6] observed, for example, in formic acid [7].…”