RESUMEN
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.
RESUMEN
A new procedure for computing the time-dependent Raman scattering of molecules in the proximity of plasmonic nanoparticles (NPs) is proposed, drawing inspiration from the pioneering Lee and Heller's theory. This strategy is based on a preliminary simulation of the molecular vibronic wavefunction in the presence of a plasmonic nanostructure and an incident light pulse. Subsequently, the Raman signal is evaluated through an inverse Fourier Transform of the coefficients' dynamics. Employing a multiscale approach, the system is treated by coupling the quantum mechanical description of the molecule with the polarizable continuum model for the NP. This method offers a unique advantage by providing insights into the time evolution of the plasmon-enhanced Raman signal, tracking the dynamics of the incident electric field. It not only provides for the total Raman signal at the process's conclusion but also gives transient information. Importantly, the flexibility of this approach allows for the simulation of various incident electric field profiles, enabling a closer alignment with experimental setups. This adaptability ensures that the method is relevant and applicable to diverse real-world scenarios.
RESUMEN
We present a multiscale method coupling the theory of open quantum systems with real-time ab initio treatment of electronic structure to study hot-carrier dynamics in photoexcited plasmonic systems. We combine the Markovian Stochastic Schrödinger equation with an ab initio GW coupled to the Bethe-Salpeter (BSE) equation description of the electronic degrees of freedom, interacting with a metallic nanoparticle modeled classically according to the polarizable continuum model. We apply this methodology to study the effect of relaxation (T1) and pure dephasing (T2) times on the hot-carrier dynamics in a system composed of a quantum portion described at GW/BSE level, i.e., a CHO fragment adsorbed on a vertex of a rhodium nanocube, and of the rest of the nanocube, treated classically, when irradiated with a 2.7 eV light pulse, inspired by the experimental results on plasmon-driven CO2 photoreduction. A net hole injection from rhodium to CHO is observed, with and without the classical portion of the nanocube. The nanocube effect is to enhance the generated charge population by two orders of magnitude. The nonradiative decay, via a relaxation time T1 based on the energy-gap law, produces a rapid decrease of the charge population. Results with T2 only show that a charge injection retarded with respect to the pulse, which is present in the coherent dynamics, disappears when coherence is erased.
RESUMEN
Molecules close to a metal nanoparticle (NP) have significantly different photophysical properties from those of the isolated one. In order to harness the potential of the molecule-NP system, appropriate design guidelines are required. Here, we propose an inverse design method of the optimal molecule-NP systems and incident electric field for desired photophysical properties. It is based on a gradient-based optimization search within the time-dependent quantum chemical description for the molecule and the continuum model for the metal NP. We designed the optimal molecule, relative molecule-NP spatial conformation, and incident electric field of a molecule-NP system to maximize the population transfer to the target electronic state of the molecule. The design results were presented and discussed. The present method is promising as the basis for designing molecule-NP systems and incident fields and accelerates discoveries of efficient molecular plasmonics systems.
RESUMEN
Raman scattering is a very powerful tool employed to characterize molecular systems. Here we propose a novel theoretical strategy to calculate the Raman cross-section in time domain, by computing the cumulative Raman signal emitted during the molecular evolution in time. Our model is based on a numerical propagation of the vibronic wave function under the effect of a light pulse of arbitrary shape. This approach can therefore tackle a variety of experimental setups. Both resonance and nonresonance Raman scattering can be retrieved, and also the time-dependent fluorescence emission is computed. The model has been applied to porphyrin considering both resonance and nonresonance conditions and varying the incident field duration. Moreover the effect of the vibrational relaxation, which should be taken into account when its time scale is similar to that of the Raman emission, has been included through the stochastic Schroedinger equation approach.
RESUMEN
Tip-enhanced photoluminescence (TEPL) experiments have recently reached the ability to investigate single molecules exploiting resolution at the submolecular level. Localized surface plasmon resonances of metallic nanostructures have the capability of enhancing an impinging electromagnetic radiation in the proximity of their surface, with evident consequences both on absorption and emission of molecules placed in the same region. We propose a theoretical analysis of these phenomena in order to interpret TEPL experiments on single molecules, including a quantum mechanical description of the target molecule equilibrated with the presence of two nanostructures representative of the nanocavity usually employed in STMs. The approach has been applied to the zinc phthalocyanine molecule, previously considered in recent TEPL experiments [Yang et al., Nat. Photonics 14, 693-699 (2020)]. This work has the aim of providing a comprehensive theoretical understanding of the experimental results, particularly focusing on the investigation of the tip features that majorly influence the excitation and fluorescence processes of the molecule, such as the geometry, the dielectric function, and the tip-molecule distance.
RESUMEN
Ultrafast two-pulse experiments on single molecules are invaluable tools to investigate the microscopic dynamics of a fluorophore. The first pulse generates electronic or vibronic coherence and the second pulse probes the time-evolution of the coherence. A protocol that is able to simulate ultrafast experiments on single molecules is applied in this study. It is based on a coupled quantum-mechanical description of the fluorophore and real-time dynamics of the system vibronic wave packet interacting with an electric field, described by means of the stochastic Schrödinger equation within the Markovian limit. This approach is applied to the DNQDI fluorophore, previously investigated experimentally [D. Brinks et al., Nature, 2010, 465, 905-908]. We find this to be in good agreement with the experimental outcomes and provide microscopic and atomistic interpretation.
RESUMEN
Investigating nanoplasmonics in an explicit time-dependent perspective is a natural choice when light pulses are used and may also reveal aspects that are hidden in a frequency-based picture. In the past, we proposed a method time domain-boundary element method (TD-BEM) to simulate the time dependent polarization of nanoparticles based on a boundary element method that is particularly suitable to interface with a quantum atomistic description of nearby molecules. So far, however, metal dielectric functions in TD-BEM have been modeled through analytic expressions, such as those of Debye and Drude-Lorentz, which cannot account for multiple electronic resonances. Our approach allows us to include in the TD-BEM framework also the description of metals with complicate dielectric function profiles in the frequency domain. Particularly, among all metals, gold is a challenging case due to the presence of many transition frequencies. We applied our methods to different metals (gold, silver, and the less commonly investigated rhodium) and different shaped nanoparticles (spheres, ellipsoids, and cubes), the approach has been tested comparing TD-BEM and frequency domain BEM absorption spectra, and it has been used to investigate the time-dependent field acting locally close to nanoparticle vertices.
RESUMEN
Electronic Energy Transfer (EET) between chromophores is fundamental in many natural light-harvesting complexes, serving as a critical step for solar energy funneling in photosynthetic plants and bacteria. The complicated role of the environment in mediating this process in natural architectures has been addressed by recent scanning tunneling microscope experiments involving EET between two molecules supported on a solid substrate. These measurements demonstrated that EET in such conditions has peculiar features, such as a steep dependence on the donor-acceptor distance, reminiscent of a short-range mechanism more than of a Förster-like process. By using state of the art hybrid ab initio/electromagnetic modeling, here we provide a comprehensive theoretical analysis of tip-enhanced EET. In particular, we show that this process can be understood as a complex interplay of electromagnetic-based molecular plasmonic processes, whose result may effectively mimic short range effects. Therefore, the established identification of an exponential decay with Dexter-like effects does not hold for tip-enhanced EET, and accurate electromagnetic modeling is needed to identify the EET mechanism.