  We consider the Br vacancy in CsPbBr3 as a prototype for the impact of
structural dynamics on defect energetics in halide perovskites (HaPs). Using
first-principles molecular dynamics based on density functional theory, we find
that the static picture of defect energetics breaks down; the energy of the Br
vacancy level is found to be intrinsically dynamic, oscillating by as much as 1
eV on the ps time scale at room temperature. These significant energy
fluctuations are correlated with the distance between the neighboring Pb atoms
across the vacancy and with the electrostatic potential at these Pb atomic
sites. We expect this unusually strong coupling of structural dynamics and
defect energetics to bear important implications for both experimental and
theoretical analysis of defect characteristics in HaPs. It may also hold
significant ramifications for carrier transport and defect tolerance in this
class of photovoltaic materials.
