Density functional theory studies on the electronic, structural, phonon dynamical and thermo-stability properties of...

The structural, electronic, phonon dispersion and thermodynamic properties of MHCO(3) (M = Li, Na, K) solids were investigated using density functional theory. The calculated bulk properties for both their ambient and the high-pressure phases are in good agreement with available experimental measurements. Solid phase LiHCO(3) has not yet been observed experimentally. We have predicted several possible crystal structures for LiHCO(3) using crystallographic database searching and prototype electrostatic ground state modeling. Our total energy and phonon free energy (F(PH)) calculations predict that LiHCO(3) will be stable under suitable conditions of temperature and partial pressures of CO(2) and H(2)O. Our calculations indicate that the [Formula: see text] groups in LiHCO(3) and NaHCO(3) form an infinite chain structure through O⋯H⋯O hydrogen bonds. In contrast, the [Formula: see text] anions form dimers, [Formula: see text], connected through double hydrogen bonds in all phases of KHCO(3). Based on density functional perturbation theory, the Born effective charge tensor of each atom type was obtained for all phases of the bicarbonates. Their phonon dispersions with the longitudinal optical-transverse optical splitting were also investigated. Based on lattice phonon dynamics study, the infrared spectra and the thermodynamic properties of these bicarbonates were obtained. Over the temperature range 0-900 K, the F(PH) and the entropies (S) of MHCO(3) (M =Li, Na, K) systems vary as F(PH)(LiHCO(3)) > F(PH)(NaHCO(3)) > F(PH)(KHCO(3)) and S(KHCO(3)) > S(NaHCO(3)) > S(LiHCO(3)), respectively, in agreement with the available experimental data. Analysis of the predicted thermodynamics of the CO(2) capture reactions indicates that the carbonate/bicarbonate transition reactions for Na and K could be used for CO(2) capture technology, in agreement with experiments.