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With the objective of understanding microscopic principles governing thermal energy flow in nanojunctions, we study phononic heat transport through metal-molecule-metal junctions using classical molecular dynamics (MD) simulations. Considering a single-molecule gold-alkanedithiol-gold junction, we first focus on aspects of method development and compare two techniques for calculating thermal conductance: (i) The Reverse Nonequilibrium MD (RNEMD) method, where heat is inputted and extracted at a constant rate from opposite metals. In this case, the thermal conductance is calculated from the nonequilibrium temperature profile that is created at the junction. (ii) The Approach-to-Equilibrium MD (AEMD) method, with the thermal conductance of the junction obtained from the equilibration dynamics of the metals. In both methods, simulations of alkane chains of a growing size display an approximate length-independence of the thermal conductance, with calculated values matching computational and experimental studies. The RNEMD and AEMD methods offer different insights, and we discuss their benefits and shortcomings. Assessing the potential application of molecular junctions as thermal diodes, alkane junctions are made spatially asymmetric by modifying their contact regions with the bulk, either by using distinct endgroups or by replacing one of the Au contacts with Ag. Anharmonicity is built into the system within the molecular force-field. We find that, while the temperature profile strongly varies (compared with the gold-alkanedithiol-gold junctions) due to these structural modifications, the thermal diode effect is inconsequential in these systems—unless one goes to very large thermal biases. This finding suggests that one should seek molecules with considerable internal anharmonic effects for developing nonlinear thermal devices.
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Heat conduction in polymer chains: Effect of substrate on the thermal conductance
In standard molecular junctions, a molecular structure is placed between and connected to metal leads. Understanding how mechanical tuning in such molecular junctions can change heat conductance has interesting applications in nanoscale energy transport. In this work, we use nonequilibrium molecular dynamics simulations to address the effect of stretching on the phononic contribution to the heat conduction of molecular junctions consisting of single long-chain alkanes and various metal leads, such as Ag, Au, Cu, Ni, and Pt. The thermal conductance of such junctions is found to be much smaller than the intrinsic thermal conductance of the polymer and significantly depends on the nature of metal leads as expressed by the metal–molecule coupling and metal vibrational density of states. This behavior is expected and reflects the mismatch of phonon spectra at the metal molecule interfaces. As a function of stretching, we find a behavior similar to what was observed earlier [M. Dinpajooh and A. Nitzan, J. Chem. Phys. 153, 164903 (2020)] for pure polymeric structures. At relatively short electrode distances, where the polyethylene chains are compressed, it is found that the thermal conductances of the molecular junctions remain almost constant as one stretches the polymer chains. At critical electrode distances, the thermal conductances start to increase, reaching the values of the fully extended molecular junctions. Similar behaviors are observed for junctions in which several long-chain alkanes are sandwiched between various metal leads. These findings indicate that this behavior under stretching is an intrinsic property of the polymer chain and not significantly associated with the interfacial structures.
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- Award ID(s):
- 1953701
- PAR ID:
- 10365037
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 156
- Issue:
- 14
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- Article No. 144901
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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