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In this Letter, we report that the fourth-order interatomic force constants (4th-IFCs) are significantly sensitive to the energy surface roughness of exchange-correlation (XC) functionals in density functional theory calculations. This sensitivity, which is insignificant for the second- (2nd-) and third-order (3rd-) IFCs, varies for different functionals in different materials and can cause misprediction of thermal conductivity by several times of magnitude. As a result, when calculating the 4th-IFCs using the finite difference method, the atomic displacement needs to be taken large enough to overcome the energy surface roughness, in order to accurately predict phonon lifetime and thermal conductivity. We demonstrate this phenomenon on a benchmark material (Si), a high-thermal conductivity material (BAs), and a low thermal conductivity material (NaCl). For Si, we find that the LDA, PBE, and PBEsol XC functionals are all smooth to the 2nd- and 3rd-IFCs but all rough to the 4th-IFCs. This roughness can lead to a prediction of nearly one order of magnitude lower thermal conductivity. For BAs, all three functionals are smooth to the 2nd- and 3rd-IFCs, and only the PBEsol XC functional is rough for the 4th-IFCs, which leads to a 40% underestimation of thermal conductivity. For NaCl, all functionals are smooth to the 2nd- and 3rd-IFCs but rough to the 4th-IFCs, leading to a 70% underprediction of thermal conductivity at room temperature. With these observations, we provide general guidance on the calculation of 4th-IFCs for an accurate thermal conductivity prediction. 

Abstract Acting like thermal resistances, ferroelectric domain walls can be manipulated to realize dynamic modulation of thermal conductivity (k), which is essential for developing novel phononic circuits. Despite the interest, little attention has been paid to achieving room‐temperature thermal modulation in bulk materials due to challenges in obtaining a high thermal conductivity switching ratio (k_high/k_low), particularly in commercially viable materials. Here, room‐temperature thermal modulation in 2.5 mm‐thick Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃(PMN–xPT) single crystals is demonstrated. With the use of advanced poling conditions, assisted by the systematic study on composition and orientation dependence of PMN–xPT, a range of thermal conductivity switching ratios with a maximum of ≈1.27 is observed. Simultaneous measurements of piezoelectric coefficient (d₃₃) to characterize the poling state, domain wall density using polarized light microscopy (PLM), and birefringence change using quantitative PLM reveal that compared to the unpoled state, the domain wall density at intermediate poling states (0<d₃₃<d_33,max) is lower due to the enlargement in domain size. At optimized poling conditions (d_33,max), the domain sizes show increased inhomogeneity that leads to enhancement in the domain wall density. This work highlights the potential of commercially available PMN–xPT single crystals among other relaxor‐ferroelectrics for achieving temperature control in solid‐state devices.