Bound states and Pb <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:mn>6</mml:mn> <mml:mi>p</mml:mi> </mml:mrow> </mml:math> orbital selectivity in orthorhombic <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:

We investigate the orbital-selective electronic structure of orthorhombic <a:math xmlns:a="http://www.w3.org/1998/Math/MathML"> <a:msub> <a:mi>CsPbI</a:mi> <a:mn>3</a:mn> </a:msub> </a:math> bulk perovskite using density functional theory combined with dynamical mean-field theory. By considering realistic values of the on-site Coulomb repulsion and spin–orbit coupling, we reveal characteristic features in the spectral functions of the active Pb- <b:math xmlns:b="http://www.w3.org/1998/Math/MathML"> <b:mrow> <b:mn>6</b:mn> <b:mi>p</b:mi> </b:mrow> </b:math> orbitals, including the formation of spin–orbit–induced low-energy bound states. Our results further demonstrate that electron doping drives a substantial reconstruction of the electronic structure, leading to Pb-orbital selectivity. These findings provide microscopic insights into the interplay between electronic plus spin–orbit interactions and doping in orthorhombic <c:math xmlns:c="http://www.w3.org/1998/Math/MathML"> <c:msub> <c:mi>CsPbI</c:mi> <c:mn>3</c:mn> </c:msub> </c:math> crystal, offering a framework to understand its correlated electronic state.