Tuning phonon transmission via single-atom substituents
Source abstract
Abstract
Thermal transport plays a crucial role in many modern electronic, photonic and energy conversion devices. Recent work has provided fundamental insights into the effects of nanostructuring on heat transport. However, the atomic-scale control of phonon transport has barely been explored. Here we present systematic studies of thermal transport in molecular junctions at 77 K, enabled by high-resolution cryogenic-compatible calorimetric scanning probes developed in this work. Our experiments provide direct evidence that atomistic changes to molecular junctions, implemented by substituting an individual hydrogen atom by a halogen atom (-F, -Cl, -Br, -I), tune the thermal conductance of the junctions by a factor of two. Our detailed first-principles modelling elucidates how the interaction between the vibrational eigenmodes of molecular junctions is modified by atomic substituents, resulting in both suppression of resonances and creation of antiresonances in the phonon transmission function. Further, the advances reported here and insights from this work inform how thermal transport in molecular materials can be probed and controlled.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Mechanical and Optical Resonators · Thermal properties of materials · Carbon Nanotubes in Composites
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (54)
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1. Cahill, D. G. et al. Nanoscale thermal transport. II. 2003-2012. Appl. Phys. Rev. 1, 011305 (2014).10.1063/1.4832615 ↗
2. Luckyanova, M. N. et al. Coherent phonon heat conduction in superlattices. Science 338, 936–939 (2012).10.1126/science.1225549 ↗
3. Hochbaum, A. I. et al. Enhanced thermoelectric performance of rough silicon nanowires. Nature 451, 163–167 (2008).10.1038/nature06381 ↗
4. Seol, J. H. et al. Two-dimensional phonon transport in supported graphene. Science 328, 213–216 (2010).10.1126/science.1184014 ↗
5. Qian, X., Zhou, J. W. & Chen, G. Phonon-engineered extreme thermal conductivity materials. Nat. Mater. 20, 1188–1202 (2021).10.1038/s41563-021-00918-3 ↗
6. Gehring, P., Thijssen, J. M. & van der Zant, H. S. Single-molecule quantum-transport phenomena in break junctions. Nat. Rev. Phys. 1, 381–396 (2019).10.1038/s42254-019-0055-1 ↗
7. Garner, M. H. et al. Comprehensive suppression of single-molecule conductance using destructive σ-interference. Nature 558, 415–419 (2018).10.1038/s41586-018-0197-9 ↗
8. Xu, B. & Tao, N. Measurement of single-molecule resistance by repeated formation of molecular junctions. Science 301, 1221–1223 (2003).10.1126/science.1087481 ↗
9. Diercks, C. S. & Yaghi, O. M. The atom, the molecule, and the covalent organic framework. Science 355, 923–931 (2017).10.1126/science.aal1585 ↗
10. Evans, A. M. et al. Thermally conductive ultra-low dielectric layers based on two-dimensional covalent organic frameworks. Nat. Mater. 20, 1142–1148 (2021).10.1038/s41563-021-00934-3 ↗
11. Mohseni, M. M. et al. Metal-organic frameworks (MOF) based heat transfer: a comprehensive review. Chem. Eng. J. 449, 137700 (2022).10.1016/j.cej.2022.137700 ↗
12. Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal-organic frameworks. Science 341, 1230444 (2013).10.1126/science.1230444 ↗
13. Famili, M., Grace, I., Sadeghi, H. & Lambert, C. J. Suppression of phonon transport in molecular Christmas trees. ChemPhysChem 18, 1234–1241 (2017).10.1002/cphc.201700147 ↗
14. Klöckner, J.-C., Cuevas, J. C. & Pauly, F. Tuning the thermal conductance of molecular junctions with interference effects. Phys. Rev. B 96, 245419 (2017).10.1103/PhysRevB.96.245419 ↗
15. Bro-Jørgensen, W., Bay-Smidt, A. J., Donadio, D. & Solomon, G. C. Heavy solution for molecular thermal management: phonon transport suppression with heavy atoms. ACS Phys. Chem. Au. 5, 162–170 (2024).10.1021/acsphyschemau.4c00084 ↗
16. Blaschke, M. & Pauly, F. Revealing molecule-internal mechanisms that control phonon heat transport through single-molecule junctions by a genetic algorithm. ACS Nano 19, 32093–32107 (2025).10.1021/acsnano.5c03690 ↗
17. Cui, L. et al. Thermal conductance of single-molecule junctions. Nature 572, 628–633 (2019).10.1038/s41586-019-1420-z ↗
18. Mosso, N. et al. Thermal transport through single-molecule junctions. Nano Lett. 19, 7614–7622 (2019).10.1021/acs.nanolett.9b02089 ↗
19. Greenwald, J. E. et al. Highly nonlinear transport across single-molecule junctions via destructive quantum interference. Nat. Nanotechnol. 16, 313–317 (2021).10.1038/s41565-020-00807-x ↗
20. Guédon, C. M. et al. Observation of quantum interference in molecular charge transport. Nat. Nanotechnol. 7, 305–309 (2012).10.1038/nnano.2012.37 ↗
21. Frisenda, R., Janssen, V. A., Grozema, F. C., van der Zant, H. S. & Renaud, N. Mechanically controlled quantum interference in individual π-stacked dimers. Nat. Chem. 8, 1099–1104 (2016).10.1038/nchem.2588 ↗
22. Yelishala, S. C. et al. Phonon interference in single-molecule junctions. Nat. Mater. 24, 1258–1264 (2025).10.1038/s41563-025-02195-w ↗
23. Li, Y. et al. Gate controlling of quantum interference and direct observation of anti-resonances in single molecule charge transport. Nat. Mater. 18, 357–363 (2019).10.1038/s41563-018-0280-5 ↗
24. Bai, J. et al. Anti-resonance features of destructive quantum interference in single-molecule thiophene junctions achieved by electrochemical gating. Nat. Mater. 18, 364–369 (2019).10.1038/s41563-018-0265-4 ↗
25. Markussen, T. & Thygesen, K. S. Temperature effects on quantum interference in molecular junctions. Phys. Rev. B 89, 085420 (2014).10.1103/PhysRevB.89.085420 ↗
26. Dubi, Y. & Di Ventra, M. Colloquium: heat flow and thermoelectricity in atomic and molecular junctions. Rev. Mod. Phys. 83, 131–155 (2011).10.1103/RevModPhys.83.131 ↗
27. Gotsmann, B., Gemma, A. & Segal, D. Quantum phonon transport through channels and molecules—a perspective. Appl. Phys. Lett. 120, 160503 (2022).10.1063/5.0088460 ↗
28. Cui, L. et al. Quantized thermal transport in single-atom junctions. Science 355, 1192–1195 (2017).10.1126/science.aam6622 ↗
29. Nguyen, T. et al. Niobium nitride thin films for very low temperature resistive thermometry. J. Low Temp. Phys. 197, 348–356 (2019).10.1007/s10909-019-02222-6 ↗
30. Bourgeois, O., André, E., Macovei, C. & Chaussy, J. Liquid nitrogen to room-temperature thermometry using niobium nitride thin films. Rev. Sci. Instrum. 77, 126108 (2006).10.1063/1.2403934 ↗
31. Dechaumphai, E. & Chen, R. Sub-picowatt resolution calorimetry with niobium nitride thin-film thermometer. Rev. Sci. Instrum. 85, 094903 (2014).10.1063/1.4895678 ↗
32. López-Nebreda, R. et al. Heat transfer in metallic nanometre-sized gaps. Nat. Commun. 16, 7342 (2025).10.1038/s41467-025-62672-3 ↗
33. Gemma, A. et al. Full thermoelectric characterization of a single molecule. Nat. Commun. 14, 3868 (2023).10.1038/s41467-023-39368-7 ↗
34. Chen, W. et al. Highly conducting π-conjugated molecular junctions covalently bonded to gold electrodes. J. Am. Chem. Soc. 133, 17160–17163 (2011).10.1021/ja208020j ↗
35. Venkataraman, L. et al. Electronics and chemistry: varying single-molecule junction conductance using chemical substituents. Nano Lett. 7, 502–506 (2007).10.1021/nl062923j ↗
36. Marder, M. P. Condensed Matter Physics (John Wiley & Sons, 2010).10.1002/9780470949955 ↗
37. Cuevas, J. C. & Scheer, E. Molecular Electronics: An Introduction To Theory And Experiment 2nd edn (World Scientific, 2017).10.1142/10598 ↗
38. Li, N. et al. Colloquium: phononics: manipulating heat flow with electronic analogs and beyond. Rev. Mod. Phys. 84, 1045–1066 (2012).10.1103/RevModPhys.84.1045 ↗
39. Wang, J. J., Gong, J., McGaughey, A. J. H. & Segal, D. Simulations of heat transport in single-molecule junctions: investigations of the thermal diode effect. J. Chem. Phys. 157, 174105 (2022).10.1063/5.0125714 ↗
40. Klöckner, J. C., Cuevas, J. C. & Pauly, F. Transmission eigenchannels for coherent phonon transport. Phys. Rev. B 97, 155432 (2018).10.1103/PhysRevB.97.155432 ↗
41. Kwon, J. et al. Thermal conductivity of covalent-organic frameworks. ACS Nano 17, 15222–15230 (2023).10.1021/acsnano.3c03518 ↗
42. Gemma, A. & Gotsmann, B. A roadmap for molecular thermoelectricity. Nat. Nanotechnol. 16, 1299–1301 (2021).10.1038/s41565-021-01012-0 ↗
43. Wang, J.-S., Wang, J. & Lü, J. Quantum thermal transport in nanostructures. Eur. Phys. J. B 62, 381–404 (2008).10.1140/epjb/e2008-00195-8 ↗
44. Bürkle, M., Hellmuth, T. J., Pauly, F. & Asai, Y. First-principles calculation of the thermoelectric figure of merit for [2, 2] paracyclophane-based single-molecule junctions. Phys. Rev. B 91, 165419 (2015).10.1103/PhysRevB.91.165419 ↗
45. Klöckner, J. C., Matt, M., Nielaba, P., Pauly, F. & Cuevas, J. C. Thermal conductance of metallic atomic-size contacts: phonon transport and Wiedemann-Franz law. Phys. Rev. B 96, 205405 (2017).10.1103/PhysRevB.96.205405 ↗
46. Franzke, Y. J. et al. TURBOMOLE: today and tomorrow. J. Chem. Theory Comput. 19, 6859–6890 (2023).10.1021/acs.jctc.3c00347 ↗
47. Schäfer, A., Horn, H. & Ahlrichs, R. Fully optimized contracted Gaussian basis sets for atoms Li to Kr. J. Chem. Phys. 97, 2571–2577 (1992).10.1063/1.463096 ↗
48. Eichkorn, K., Weigend, F., Treutler, O. & Ahlrichs, R. Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials. Theor. Chem. Acta. 97, 119–124 (1997).10.1007/s002140050244 ↗
49. Eichkorn, K., Treutler, O., Öhm, H., Häser, M. & Ahlrichs, R. Auxiliary basis sets to approximate Coulomb potentials. Chem. Phys. Lett. 240, 283–290 (1995).10.1016/0009-2614(95)00621-A ↗
50. Perdew, J. P. & Wang, Y. Accurate and simple analytic representation of the electron-gas correlation energy. Phys. Rev. B 45, 13244 (1992).10.1103/PhysRevB.45.13244 ↗
51. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).10.1103/PhysRevLett.77.3865 ↗
52. Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).10.1002/jcc.21759 ↗
53. Pauly, F. et al. Cluster-based density-functional approach to quantum transport through molecular and atomic contacts. New J. Phys. 10, 125019 (2008).10.1088/1367-2630/10/12/125019 ↗
54. Luan Y. et al. Tuning phonon transmission via single-atom substituents. figshare https://doi.org/10.6084/m9.figshare.31383004 (2026).10.6084/m9.figshare.31383004 ↗