1,721,114 research outputs found
Electronic Dynamics of a Molecular System Coupled to a Plasmonic Nanoparticle Combining the Polarizable Continuum Model and Many-Body Perturbation Theory
Full text linkThe 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
Studying SERS from metal nanoparticles and nanoparticle aggregates with continuum models
No full textSurface enhanced Raman scattering from a single molecule adsorbed on a metal particle aggregate: a theoretical study
No full textIncluding image charge effects in the molecular dynamics simulations of molecules on metal surfaces
No full textTheoretical evaluation of Raman spectra and enhancement factors for a molecule adsorbed on a complex shape metal particle
No full textTime Resolved Raman Scattering of Molecules: A Quantum Mechanics Approach with Stochastic Schroedinger Equation
Full text linkRaman 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
Time-dependent surface-enhanced Raman scattering: A theoretical approach
Full text linkA 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
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