Peeking into the Femtosecond Hot-Carrier Dynamics Reveals Unexpected Mechanisms in Plasmonic Photocatalysis.

Plasmonic-driven photocatalysis may lead to reaction selectivity that cannot be otherwise achieved. A fundamental role is played by hot carriers, i.e., electrons and holes generated upon plasmonic decay within the metal nanostructure interacting with molecular species. Understanding the elusive microscopic mechanism behind such selectivity is a key step in the rational design of hot-carrier reactions. To accomplish that, we present state-of-the-art multiscale simulations, going beyond density functional theory, of hot-carrier injections for the rate-determining step of a photocatalytic reaction. We focus on carbon dioxide reduction, for which it was experimentally shown that the presence of a rhodium nanocube under illumination leads to the selective production of methane against carbon monoxide. We show that selectivity is due to a (predominantly) direct hole injection from rhodium to the reaction intermediate CHO. Unexpectedly, such an injection does not promote the selective reaction path by favoring proper bond breaking but rather by promoting bonding of the proper molecular fragment to the surface.

Time Evolution of Plasmonic Features in Pentagonal Ag Clusters.

In the present work, we apply recently developed real-time descriptors to study the time evolution of plasmonic features of pentagonal Ag clusters. The method is based on the propagation of the time-dependent Schrödinger equation within a singly excited TDDFT ansatz. We use transition contribution maps (TCMs) and induced density to characterize the optical longitudinal and transverse response of such clusters, when interacting with pulses resonant with the low-energy (around 2-3 eV, A1) size-dependent or the high-energy (around 4 eV, E1) size-independent peak. TCMs plots on the analyzed clusters, Ag25+ and Ag43+ show off-diagonal peaks consistent with a plasmonic response when a longitudinal pulse resonant at A1 frequency is applied, and dominant diagonal spots, typical of a molecular transition, when a transverse E1 pulse is employed. Induced densities confirm this behavior, with a dipole-like charge distribution in the first case. The optical features show a time delay with respect to the evolution of the external pulse, consistent with those found in the literature for real-time TDDFT calculations on metal clusters.

High-Throughput First-Principles Prediction of Interfacial Adhesion Energies in Metal-on-Metal Contacts.

Adhesion energy, a measure of the strength by which two surfaces bind together, ultimately dictates the mechanical behavior and failure of interfaces. As natural and artificial solid interfaces are ubiquitous, adhesion energy represents a key quantity in a variety of fields ranging from geology to nanotechnology. Because of intrinsic difficulties in the simulation of systems where two different lattices are matched, and despite their importance, no systematic, accurate first-principles determination of heterostructure adhesion energy is available. We have developed robust, automatic high-throughput workflow able to fill this gap by systematically searching for the optimal interface geometry and accurately determining adhesion energies. We apply it here for the first time to perform the screening of around a hundred metallic heterostructures relevant for technological applications. This allows us to populate a database of accurate values, which can be used as input parameters for macroscopic models. Moreover, it allows us to benchmark commonly used, empirical relations that link adhesion energies to the surface energies of its constituent and to improve their predictivity employing only quantities that are easily measurable or computable.

Electronic Dynamics of a Molecular System Coupled to a Plasmonic Nanoparticle Combining the Polarizable Continuum Model and Many-Body Perturbation Theory.

The efficiency of plasmonic metallic nanoparticles in harvesting and concentrating light energy in their proximity triggers a wealth of important and intriguing phenomena. For example, spectroscopies are able to reach single-molecule and intramolecule sensitivities, and important chemical reactions can be effectively photocatalyzed. For the real-time description of the coupled dynamics of a molecule's electronic system and of a plasmonic nanoparticle, a methodology has been recently proposed (J. Phys. Chem. C. 120, 2016, 28774-28781) which combines the classical description of the nanoparticle as a polarizable continuum medium with a quantum-mechanical description of the molecule treated at the time-dependent configuration interaction (TDCI) level. In this work, we extend this methodology by describing the molecule using many-body perturbation theory: the molecule's excitation energies, transition dipoles, and potentials computed at the GW/Bethe-Salpeter equation (BSE) level. This allows us to overcome current limitations of TDCI in terms of achievable accuracy without compromising on the accessible molecular sizes. We illustrate the developed scheme by characterizing the coupled nanoparticle/molecule dynamics of two prototype molecules, LiCN and p-nitroaniline.

Koopmans Meets Bethe-Salpeter: Excitonic Optical Spectra without GW.

The Bethe-Salpeter equation (BSE) can be applied to compute from first-principles optical spectra that include the effects of screened electron-hole interactions. As input, BSE calculations require single-particle states, quasiparticle energy levels, and the screened Coulomb interaction, which are typically obtained with many-body perturbation theory, whose cost limits the scope of possible applications. This work tries to address this practical limitation, instead deriving spectral energies from Koopmans-compliant functionals and introducing a new methodology for handling the screened Coulomb interaction. The explicit calculation of the W matrix is bypassed via a direct minimization scheme applied on top of a maximally localized Wannier function basis. We validate and benchmark this approach by computing the low-lying excited states of the molecules in Thiel's set and the optical absorption spectrum of a C60 fullerene. The results show the same trends as quantum chemical methods and are in excellent agreement with previous simulations carried out at the time-dependent density functional theory or G0 W0-BSE level. Conveniently, the new framework reduces the parameter space controlling the accuracy of the calculation, thereby simplifying the simulation of charge-neutral excitations, offering the potential to expand the applicability of first-principles spectroscopies to larger systems of applied interest.

Photo-Induced Bandgap Renormalization Governs the Ultrafast Response of Single-Layer MoS2.

Transition metal dichalcogenides (TMDs) are emerging as promising two-dimensional (2D) semiconductors for optoelectronic and flexible devices. However, a microscopic explanation of their photophysics, of pivotal importance for the understanding and optimization of device operation, is still lacking. Here, we use femtosecond transient absorption spectroscopy, with pump pulse tunability and broadband probing, to monitor the relaxation dynamics of single-layer MoS2 over the entire visible range, upon photoexcitation of different excitonic transitions. We find that, irrespective of excitation photon energy, the transient absorption spectrum shows the simultaneous bleaching of all excitonic transitions and corresponding red-shifted photoinduced absorption bands. First-principle modeling of the ultrafast optical response reveals that a transient bandgap renormalization, caused by the presence of photoexcited carriers, is primarily responsible for the observed features. Our results demonstrate the strong impact of many-body effects in the transient optical response of TMDs even in the low-excitation-density regime.