Analyzing the frequency shift of physiadsorbed CO ₂ in metal organic framework materials

Combining first-principles density functional theory simulations with IR and Raman experiments, we determine the frequency shift of vibrational modes of CO ₂ when physiadsorbed in the isostructural metal organic framework materials Mg-MOF74 and Zn-MOF74. Surprisingly, we find that the resulting change in shift is rather different for these two systems and we elucidate possible reasons. We explicitly consider three factors responsible for the frequency shift through physiabsorption, namely, (i) the change in the molecule length, (ii) the asymmetric distortion of the CO ₂ molecule, and (iii) the direct influence of the metal center. The influence of each factor is evaluated separately through different geometry considerations, providing a fundamental understanding of the frequency shifts observed experimentally.