Dr Joseph Prentice

Abstract:

Quantum embedding schemes have the potential to significantly reduce the computational cost of first principles calculations, whilst maintaining accuracy, particularly for calculations of electronic excitations in complex systems. In this work, I combine time-dependent embedded mean field theory (TD-EMFT) with linear-scaling density functional theory and implicit solvation models, extending previous work within the ONETEP code. This provides a way to perform multi-level calculations of electronic excitations on very large Systems, where long-range environmental effects, both quantum and classical in nature, are important. I demonstrate the power of this method by performing simulations on a variety of systems, including a molecular dimer, a chromophore in solution, and a doped molecular crystal. This work paves the way for high accuracy calculations to be performed on large-scale systems that were previously beyond the reach of quantum embedding schemes.

Abstract:

We demonstrate the capability of embedded mean-field theory (EMFT) within the linear-scaling density-functional-theory code ONETEP, which enables DFT-in-DFT quantum embedding calculations on systems containing thousands of atoms at a fraction of the cost of a full calculation. We perform simulations on a wide range of systems from molecules to complex nanostructures to demonstrate the performance of our implementation with respect to accuracy and efficiency. This work paves the way for the application of this class of quantum embedding method to large-scale systems that are beyond the reach of existing implementations.

Abstract:

We present an overview of the onetep program for linear-scaling density functional theory (DFT) calculations with large basis set (plane-wave) accuracy on parallel computers. The DFT energy is computed from the density matrix, which is constructed from spatially localized orbitals we call Non-orthogonal Generalized Wannier Functions (NGWFs), expressed in terms of periodic sinc (psinc) functions. During the calculation, both the density matrix and the NGWFs are optimized with localization constraints. By taking advantage of localization, onetep is able to perform calculations including thousands of atoms with computational effort, which scales linearly with the number or atoms. The code has a large and diverse range of capabilities, explored in this paper, including different boundary conditions, various exchange-correlation functionals (with and without exact exchange), finite electronic temperature methods for metallic systems, methods for strongly correlated systems, molecular dynamics, vibrational calculations, time-dependent DFT, electronic transport, core loss spectroscopy, implicit solvation, quantum mechanical (QM)/molecular mechanical and QM-in-QM embedding, density of states calculations, distributed multipole analysis, and methods for partitioning charges and interactions between fragments. Calculations with onetep provide unique insights into large and complex systems that require an accurate atomic-level description, ranging from biomolecular to chemical, to materials, and to physical problems, as we show with a small selection of illustrative examples. onetep has always aimed to be at the cutting edge of method and software developments, and it serves as a platform for developing new methods of electronic structure simulation. We therefore conclude by describing some of the challenges and directions for its future developments and applications.

Abstract:

Superconductivity of iron chalocogenides is strongly enhanced under applied pressure yet its underlying pairing mechanism remains elusive. Here, we present a quantum oscillations study up to 45 T in the high-T_c phase of tetragonal FeSe_0.82S_0.18 up to 22 kbar. Under applied pressure, the quasi-two-dimensional multi-band Fermi surface expands and the effective masses remain large, whereas the superconductivity displays a threefold enhancement. Comparing with chemical pressure tuning of FeSe_1−xS_x, the Fermi surface expands in a similar manner but the effective masses and T_c are suppressed. These differences may be attributed to the changes in the density of states influenced by the chalcogen height, which could promote stronger spin fluctuations pairing under pressure. Furthermore, our study also reveals unusual scattering and broadening of superconducting transitions in the high-pressure phase, indicating the presence of a complex pairing mechanism.