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Stefano Paolo Villani

Publications and source records attributed to Stefano Paolo Villani.

5 recordsLinked to original sources

The WEST code for large-scale excited-state materials simulations

We present WEST, an open-source plane-wave pseudopotential code for large-scale excited-state materials simulations, and describe its theoretical foundations, software architecture, and capabilities. WEST implements full-frequency GW, quantum defect embedding theory, the Bethe-Salpeter equation, and time-dependent density functional theory within a common algorithmic framework that avoids the explicit computation of virtual electronic states. By combining density functional and density matrix perturbation theory, low-rank representations of the dielectric screening and exact exchange, and localization techniques, WEST achieves favorable computational scaling with system size. The code supports the calculation of quasi-particle and neutral excitation energies, optical and photoluminescence spectra, excited-state forces, and non-adiabatic couplings, with interoperable workflows connecting to quantum chemistry, vibronic coupling, and quantum computing packages. A hierarchical parallelization strategy and GPU acceleration deliver near-ideal strong scaling to thousands of GPUs, enabling accurate excited-state simulations of systems with more than a thousand atoms. Representative applications, spanning the full optical cycle of solid-state spin defects, self-trapped excitons in metal-halide perovskites, and the optical response of liquid water and ice, demonstrate the accuracy and versatility of the code across diverse material classes. The capabilities implemented in WEST establish the code as a scalable platform for predictive excited-state simulations, high-throughput materials discovery, and the generation of high-fidelity datasets for machine learning in computational materials science.

cond-mat.mtrl-sci↗

First-principles calculations of internal conversion processes in spin defects

Optically active spin defects are foundational for quantum technologies, yet common approximations underestimate their internal conversion (IC) rates by orders of magnitude. We propose a broad, predictive framework to compute IC rates that incorporates multi-configurational effects via many-body wavefunctions in TDDFT, and includes all-phonon-mode contributions via analytical non-adiabatic couplings. Our approach resolves discrepancies with experiment, achieving quantitative agreement for the NV$^-$ center in diamond, and identifying a previously overlooked non-radiative channel in the divacancy triplet lifetime in SiC.

cond-mat.mtrl-sci↗

Role of ionic quantum-anharmonic fluctuations on the bond length alternation and giant piezoelectricity of conjugated polymers

Functionalized conjugated polymers are promising materials for electromechanical applications due to predicted giant piezoelectricity, arising from anomalously large dynamical effective charges and an enhanced response in the proximity of the dimerization phase transition. In this work, we assess the impact of quantum ionic fluctuations on piezoelectricity using the stochastic self-consistent harmonic approximation with a Rice-Mele diatomic chain model, parametrized to reproduce hybrid-functional first-principles calculations of prototypical carbyne. The model's accuracy is validated against first-principles calculations both with and without quantum-anharmonic effects. We find that ionic fluctuations strongly impact the structural properties, with the boundary of the dimerization phase transition shifted by $34\%$. Despite quantum fluctuations in the bond length reaching magnitudes comparable to the average, the strong piezoelectric response persists. The topological enhancement of the effective charges remains robust and is even enhanced by about $\sim20\%$ thanks to a quantum-induced shrinking of the electronic gap. The piezoelectric coefficient remains dominated by the internal relaxation and retains a morphotropic-like character, reaching maximum values near the renormalized boundary, with quantum anharmonicity mainly shifting the optimal enhancement window.

cond-mat.mtrl-sci↗

Giant piezoelectricity driven by Thouless pump in conjugated polymers

Piezoelectricity of organic polymers has attracted increasing interest because of several advantages they exhibit over traditional inorganic ceramics. While most organic piezoelectrics rely on the presence of intrinsic local dipoles, a highly nonlocal electronic polarization can be foreseen in conjugated polymers, characterised by delocalized and highly responsive $π$-electrons. These 1D systems represent a physical realization of a Thouless pump, a mechanism of adiabatic charge transport of topological nature which results, as shown in this work, in anomalously large dynamical effective charges, inversely proportional to the band gap energy. A structural (ferroelectric) phase transition further contributes to an enhancement of the piezoelectric response reminiscent of that observed in piezoelectric perovskites close to morphotropic phase boundaries. First-principles Density Functional Theory (DFT) calculations performed in two representative conjugated polymers using hybrid functionals, show that state-of-the-art organic piezoelectric are outperformed by piezoelectric conjugated polymers, mostly thanks to strongly anomalous effective charges of carbon, larger than 5e - ordinary values being of the order of 1e - and reaching the giant value of 30e for band gaps of the order of 1 eV.

cond-mat.mtrl-sci↗

Phonon-Polaritons in Non-Centrosymmetric Systems: Theory of Terahertz Pump-Optical Probe Spectroscopy

Hybrid lattice-light modes, known as phonon-polaritons, represent the backbone of advanced protocols based on THz pumping of infrared modes. Here we provide a theoretical framework able to capture the different roles played by phonon-polaritons in experimental protocols based either on Raman-like pump and probe schemes, typical of four-wave-mixing processes, or on THz pump-visible probe three-wave mixing protocols. By using a many-body description of the nonlinear optical kernel, along with a perturbative solution of nonlinear Maxwell's equations, we highlight the advantages of exploiting broadband THz pumps to enlarge the phase space of the phonon-polariton dispersion accessible in a single experiment. Besides providing a quantitative description of existing and future experiments, our results offer a general framework for the theoretical modeling of the hybridization between light and lattice degrees of freedom in time-resolved experiments.

cond-mat.mtrl-sci↗