Self‐Consistent Convolutional Density Functional Approximations: Application to Adsorption at Metal Surfaces

Sahoo, Sushree Jagriti; Xu, Qimen; Lei, Xiangyun; Staros, Daniel; Iyer, Gopal R.; Rubenstein, Brenda; Suryanarayana, Phanish; Medford, Andrew J.

doi:10.1002/cphc.202300688

DOE OSTI · 2345797

Self‐Consistent Convolutional Density Functional Approximations: Application to Adsorption at Metal Surfaces

Sahoo, Sushree Jagriti·Xu, Qimen·Lei, Xiangyun·Staros, Daniel·Iyer, Gopal R.·Rubenstein, Brenda·Suryanarayana, Phanish·Medford, Andrew J.

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Abstract

The exchange-correlation (XC) functional in density functional theory is used to approximate multi-electron interactions. A plethora of different functionals are available, but nearly all are based on the hierarchy of inputs commonly referred to as “Jacob's ladder.” This paper introduces an approach to construct XC functionals with inputs from convolutions of arbitrary kernels with the electron density, providing a route to move beyond Jacob's ladder. We derive the variational derivative of these functionals, showing consistency with the generalized gradient approximation (GGA), and provide equations for variational derivatives based on multipole features from convolutional kernels. A proof-of-concept functional, PBEq, which generalizes the PBEα framework with mathematical equation being a spatially-resolved function of the monopole of the electron density, is presented and implemented. It allows a single functional to use different GGAs at different spatial points in a system, while obeying PBE constraints. Analysis of the results underlines the importance of error cancellation and the XC potential in data-driven functional design. After testing on small molecules, bulk metals, and surface catalysts, the results indicate that this approach is a promising route to simultaneously optimize multiple properties of interest.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Chemistry Density Functional Theory Exchange-correlation Generalized gradient approximation Multipole expansion Physics

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Sahoo, Sushree Jagriti, Xu, Qimen, Lei, Xiangyun, Staros, Daniel, Iyer, Gopal R., Rubenstein, Brenda, Suryanarayana, Phanish, Medford, Andrew J.. 2024-02-29. Self‐Consistent Convolutional Density Functional Approximations: Application to Adsorption at Metal Surfaces. https://doi.org/10.1002/cphc.202300688

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