Comparing B3LYP and B97 dispersion-corrected functionals for studying
adsorption and vibrational spectra in nitrogen reduction
Abstract
Electrochemical ammonia synthesis is being actively studied as a low
temperature, low pressure alternative to the Haber-Bosch process. This
work studied iridium as the electrochemical catalyst, following a
previous study of adsorption characteristics on platinum. The
characteristics studied include bond energies, bond lengths, spin
densities, and free and adsorbed vibrational frequencies for the
molecules N2, N, NH, NH2, and NH3. Overall, these descriptive
characteristics explore the use of dispersion-corrected Density
Functional Theory methods that can model N2 adsorption – the key
reactant for electrochemical ammonia synthesis via transition metal
catalysis. Specifically, three methods were tested: hybrid B3LYP, a
dispersion-corrected form B3LYP-D3, and semi-empirical B97-D3. The
latter semi-empirical method was explored to increase the accuracy
obtained in vibrational analysis as well as reduce computational time.
Two lattice surfaces, (111) and (100), were compared. The adsorption
energies are stronger on (100) and follow the trend EB3LYP
> EB3LYP-D3 > EB97-D3 on both surfaces.