Splitting CO2 with Electric Fields: A Computational Investigation

Quantum chemical calculations at the B3LYP/aug-cc-PVTZ level show that CO2 can spontaneously break in the presence of an electric field above 40 Wnm. The energetics of the reaction was further assessed by single-point CCSD(T) calculations, which show that the electric field transforms the reaction from endothermic to exothermic. The rupture occurs when the potential energy curves of the singlet and tripletmanifolds cross each other and is caused by the fast decrease of the energy of the lowest unoccupied molecular orbital. The process was present in recent experiments carried out with atomic force microscopy at room temperature in the presence of low-to-moderate voltages (Appl. Phys. Lett. 2010, 96, 143110). The simulation of the electric field-dependent infrared spectra show the process could be monitored spectroscopically since the symmetric CO stretch becomes infrared-allowed and downshifts in the presence of the field, while the bending acquires further intensity.