First-Principles Theory of Five- and Six-Phonon Scatterings

Abstract: Higher-order phonon scatterings beyond fourth order remain largely unexplored despite their potential importance in strongly anharmonic materials at elevated temperatures. We develop a theoretical formalism for first-principles calculation of five- and six-phonon scatterings using Green's function techniques based on a diagrammatic formalism, and systematically investigate multi-phonon interactions in Si, MgO, and BaO from room temperature to near melting points. Our calculation reveals dramatically different material-dependent behaviors: while five- and six-phonon processes remain negligible in Si, they become increasingly important in MgO and dominant in BaO near its melting point, where they surpass three- and four-phonon scattering intensity and significantly reduce lattice thermal conductivity. We demonstrate that the strength of higher-order interactions is primarily governed by interatomic force constants, with BaO exhibiting five- and six-phonon scattering rates over one order of magnitude stronger than MgO despite identical crystal structures, due to large scattering phase space arising from softened harmonic interactions. Our work establishes the theoretical foundation for understanding lattice dynamics and thermal transport in strongly anharmonic materials and at elevated temperatures.