Ultrafast spontaneous exciton dissociation via phonon emission in <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msub> <mml:mi>BiVO</mml:mi> <mml:mn>4</mml:mn> </mml:msub> </mml:math>

Monoclinic bismuth vanadate ( <a:math xmlns:a="http://www.w3.org/1998/Math/MathML"> <a:mrow> <a:mi mathvariant="normal">m</a:mi> <a:mtext>−</a:mtext> <a:msub> <a:mi>BiVO</a:mi> <a:mn>4</a:mn> </a:msub> </a:mrow> </a:math> ) is a promising indirect band gap semiconductor for photoelectrochemical water splitting, yet the characteristics of its low-lying photoexcitations, or excitons, remain poorly understood. Here, we use an Bethe-Salpeter equation approach that incorporates phonon screening to compute the nature and lifetimes of the low-lying excitons of <c:math xmlns:c="http://www.w3.org/1998/Math/MathML"> <c:mrow> <c:mi mathvariant="normal">m</c:mi> <c:mtext>−</c:mtext> <c:msub> <c:mi>BiVO</c:mi> <c:mn>4</c:mn> </c:msub> </c:mrow> </c:math> . Our calculations indicate that at 0 K, the lowest-lying exciton energy exceeds the indirect band gap, enabling spontaneous dissociation into free carriers via phonon emission within picoseconds. At 300 K, both phonon emission and absorption effects reduce this timescale to only a few femtoseconds. Phonon screening also greatly reduces the binding energy of the lowest-lying exciton, leading to an optical absorption spectrum that better reproduces experimental measurements. Overall, our findings establish the general conditions under which phonon emission-driven exciton dissociation can occur in indirect gap semiconductors, and they emphasize the critical role phonon screening can play in predictive calculations of photophysical properties of complex materials.