Correction to “Going Beyond the Limits of Classical Atomistic Modeling of Plasmonic Nanostructures”

This corrects the article DOI: 10.1021/acs.jpcc.1c04716

Effective fully polarizable QM/MM approaches to compute Raman and Raman Optical Activity spectra in aqueous solution

Raman and Raman Optical Activity (ROA) signals are amply affected by solvent effects, especially in the presence of strongly solute-solvent interactions such as Hydrogen Bonding (HB). In this work, we extend the fully atomistic polarizable Quantum Mechanics/Molecular Mechanics approach, based on the Fluctuating Charges and Fluctuating Dipoles force field to the calculation of Raman and ROA spectra. Such an approach is able to accurately describe specific HB interactions, by also accounting for anisotropic contributions due to the inclusion of fluctuating dipoles. To highlight the potentiality of the novel approach, Raman and ROA spectra of L-Serine and L-Cysteine dissolved in aqueous solution are computed and compared both with alternative theoretical approaches and experimental measurements

UV-Resonance Raman Spectra of Systems in Complex Environments: A Multiscale Modeling Applied to Doxorubicin Intercalated into DNA

UV-Resonance Raman (RR) spectroscopy is a valuable tool to study the binding of drugs to biomolecular receptors. The extraction of information at the molecular level from experimental RR spectra is made much easier and more complete thanks to the use of computational approaches, specifically tuned to deal with the complexity of the supramolecular system. In this paper, we propose a protocol to simulate RR spectra of complex systems at different levels of sophistication, by exploiting a quantum mechanics/molecular mechanics (QM/MM) approach. The approach is challenged to investigate RR spectra of a widely used chemotherapy drug, doxorubicin (DOX) intercalated into a DNA double strand. The computed results show good agreement with experimental data, thus confirming the reliability of the computational protocol

QM/Classical Modeling of Surface Enhanced Raman Scattering Based on Atomistic Electromagnetic Models

We present quantum mechanics (QM)/frequency dependent fluctuating charge (QM/ωFQ) and fluctuating dipoles (QM/ωFQFμ) multiscale approaches to model surface-enhanced Raman scattering spectra of molecular systems adsorbed on plasmonic nanostructures. The methods are based on a QM/classical partitioning of the system, where the plasmonic substrate is treated by means of the atomistic electromagnetic models ωFQ and ωFQFμ, which are able to describe in a unique fashion and at the same level of accuracy the plasmonic properties of noble metal nanostructures and graphene-based materials. Such methods are based on classical physics, i.e. Drude conduction theory, classical electrodynamics, and atomistic polarizability to account for interband transitions, by also including an ad-hoc phenomenological correction to describe quantum tunneling. QM/ωFQ and QM/ωFQFμ are thus applied to selected test cases, for which computed results are compared with available experiments, showing the robustness and reliability of both approaches

Fully Atomistic Modeling of Plasmonic Bimetallic Nanoparticles: Nanoalloys and Core-Shell Systems

The recently developed ωFQFμ model (ACS Photonics, 9, 3,025–3,034) is extended to bimetallic nanoparticles, such as nanoalloys and core-shell systems. The method finds its grounds in basic physical concepts, such as Drude conduction theory, electrostatics, interband transitions, and quantum tunneling. The approach, which is parametrized on ab initio simulations of Ag-Au nanoalloys, is challenged against complex Ag-Au nanostructures (spheres, nanorods, and core-shell nanoparticles). Remarkable agreement with available experimental data is found, thus demonstrating the reliability of the newly developed approach

Effective yet Reliable Computation of EPR Spectra in Solution by a QM/MM Approach: Interplay between Electrostatics and Non-electrostatic Effects

In this paper, we have extended to the calculation of hyperfine coupling constants, the model recently proposed by some of the present authors [Giovannini et al., J. Chem. Theory Comput. 13, 4854\u20134870 (2017)] to include Pauli repulsion and dispersion effects in Quantum Mechanical/ Molecular Mechanics (QM/MM) approaches. The peculiarity of the proposed approach stands in the fact that repulsion/dispersion contributions are explicitly introduced in the QM Hamiltonian. Therefore, such terms not only enter the evaluation of energetic properties but also propagate to molecular properties and spectra. A novel parametrization of the electrostatic fluctuating charge force field has been developed, thus allowing a quantitative reproduction of reference QM interaction energies. Such a parametrization has been then tested against the prediction of EPR parameters of prototypical nitroxide radicals in aqueous solutions

A quasi-energy-based QM/classical approach to calculate enhanced response properties of molecules adsorbed on metal nanoparticles

It has been amply shown experimentally that the Raman scattering intensity of a molecule can be strongly enhanced up to a factor of 10^10 − 10^15 if the system is absorbed on a metal nanoparticle (usually silver or gold). This phenomenon gives rise to the Surface-Enhanced Raman Scattering and Surface-Enhanced Resonance Raman Scattering spectroscopies. SERS in particular has completely revolutionized the field of molecular spectroscopy, giving birth to new and powerful techniques of molecular investigation. An effective theoretical model able to treat the peculiarity of a complex system made of a molecule adsorbed on a nanoparticle, both affected by an external radiation, needs to take into account all possible interactions between the different players. In this thesis we focus on the Corni-Tomasi (CT) model, which up to date it has been coupled with a QM treatment of an abdsorbed molecule which is treated at the Time-Dependent Hartree-Fock (TDHF). We have reformulated the CT model in the quasi-energy formalism: this allowed us to couple the CT model with a DFT Hamiltonian, and, by exploiting the properties of the response theory, the calculation of electric response functions

Going Beyond the Limits of Classical Atomistic Modeling of Plasmonic Nanostructures

Theoretical modeling of plasmonic phenomena is of fundamental importance for rationalizing experimental measurements. Despite the great success of classical continuum modeling, recent technological advances allowing for the fabrication of structures defined at the atomic level require to be modeled through atomistic approaches. From a computational point of view, the latter approaches are generally associated with high computational costs, which have substantially hampered their extensive use. In this work, we report on a computationally fast formulation of a classical, fully atomistic approach, able to accurately describe both metal nanoparticles and graphene-like nanostructures composed of roughly 1 million atoms and characterized by structural defects

A General Route to Include Pauli Repulsion and Quantum Dispersion Effects in QM/MM Approaches

A methodology to account for nonelectrostatic interactions in Quantum Mechanical (QM)/Molecular Mechanics (MM) approaches is developed. Formulations for Pauli repulsion and dispersion energy, explicitly depending on the QM density, are derived. Such expressions are based on the definition of an auxiliary density on the MM portion and the Tkatchenko–Scheffler (TS) approach, respectively. The developed method is general enough to be applied to any QM/MM method and partition, provided an accurate tuning of a small number of parameters is obtained. The coupling of the method with both nonpolarizable and fully polarizable QM/fluctuating charge (FQ) approaches is reported and applied. A suitable parametrization for the aqueous solution, so that its most representative features are well reproduced, is outlined. Then, the obtained parametrization and method are applied to calculate the nonelectrostatic (repulsion and dispersion) interaction energy of nicotine in aqueous solution

Effective Computational Route to Vibrational Optical Activity Spectra of Chiral Molecules in Aqueous Solution

We present a computational methodology based on a polarizable Quantum Mechanical (QM)/Molecular Mechanics (MM) approach to accurately compute the Vibrational Optical Activity (VOA) spectra of chiral systems. This approach is applied for the calculation of Infrared (IR), Vibrational Circular Dichroism (VCD), Raman and Raman Optical Activity (ROA) spectra of aqueous solutions of (L)-methyl lactate and (S)-glycidol. Remarkable agreement between calculations and experiments is reported, showing the reliability and accuracy of the methodology, especially with respect to standard continuum solvation approaches