TY - JOUR

T1 - Heat transport in liquid water from first-principles and deep neural network simulations

AU - Tisi, Davide

AU - Zhang, Linfeng

AU - Bertossa, Riccardo

AU - Wang, Han

AU - Car, Roberto

AU - Baroni, Stefano

N1 - Funding Information:
D.T., R.B., and S.B. are grateful to Federico Grasselli for enlightening discussions throughout the completion of this work. This work was partially funded by the EU through the MaX Centre of Excellence for supercomputing applications (Project No. 824143). L.Z. and R.C. acknowledge support from the Center Chemistry in Solution and at Interfaces funded by the DOE Award No. DE-SC0019394. H.W. is supported by the National Science Foundation of China under Grant No. 11871110.
Publisher Copyright:
© 2021 American Physical Society

PY - 2021/12/1

Y1 - 2021/12/1

N2 - We compute the thermal conductivity of water within linear response theory from equilibrium molecular dynamics simulations, by adopting two different approaches. In one, the potential energy surface (PES) is derived on the fly from the electronic ground state of density functional theory (DFT) and the corresponding analytical expression is used for the energy flux. In the other, the PES is represented by a deep neural network (DNN) trained on DFT data, whereby the PES has an explicit local decomposition and the energy flux takes a particularly simple expression. By virtue of a gauge invariance principle, established by Marcolongo, Umari, and Baroni, the two approaches should be equivalent if the PES were reproduced accurately by the DNN model. We test this hypothesis by calculating the thermal conductivity, at the GGA (PBE) level of theory, using the direct formulation and its DNN proxy, finding that both approaches yield the same conductivity, in excess of the experimental value by approximately 60%. Besides being numerically much more efficient than its direct DFT counterpart, the DNN scheme has the advantage of being easily applicable to more sophisticated DFT approximations, such as meta-GGA and hybrid functionals, for which it would be hard to derive analytically the expression of the energy flux. We find in this way that a DNN model, trained on meta-GGA (SCAN) data, reduces the deviation from experiment of the predicted thermal conductivity by about 50%, leaving the question open as to whether the residual error is due to deficiencies of the functional, to a neglect of nuclear quantum effects in the atomic dynamics, or, likely, to a combination of the two.

AB - We compute the thermal conductivity of water within linear response theory from equilibrium molecular dynamics simulations, by adopting two different approaches. In one, the potential energy surface (PES) is derived on the fly from the electronic ground state of density functional theory (DFT) and the corresponding analytical expression is used for the energy flux. In the other, the PES is represented by a deep neural network (DNN) trained on DFT data, whereby the PES has an explicit local decomposition and the energy flux takes a particularly simple expression. By virtue of a gauge invariance principle, established by Marcolongo, Umari, and Baroni, the two approaches should be equivalent if the PES were reproduced accurately by the DNN model. We test this hypothesis by calculating the thermal conductivity, at the GGA (PBE) level of theory, using the direct formulation and its DNN proxy, finding that both approaches yield the same conductivity, in excess of the experimental value by approximately 60%. Besides being numerically much more efficient than its direct DFT counterpart, the DNN scheme has the advantage of being easily applicable to more sophisticated DFT approximations, such as meta-GGA and hybrid functionals, for which it would be hard to derive analytically the expression of the energy flux. We find in this way that a DNN model, trained on meta-GGA (SCAN) data, reduces the deviation from experiment of the predicted thermal conductivity by about 50%, leaving the question open as to whether the residual error is due to deficiencies of the functional, to a neglect of nuclear quantum effects in the atomic dynamics, or, likely, to a combination of the two.

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U2 - 10.1103/PhysRevB.104.224202

DO - 10.1103/PhysRevB.104.224202

M3 - Article

AN - SCOPUS:85122072821

SN - 2469-9950

VL - 104

JO - Physical Review B

JF - Physical Review B

IS - 22

M1 - 224202

ER -