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.

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

Lafiosca, Piero;Nicoli, Luca;Bonatti, Luca;Giovannini, Tommaso
;
Corni, Stefano;Cappelli, Chiara
2023

Abstract

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.
2023
Settore CHIM/02 - Chimica Fisica
   General Embedding Models for Spectroscopy
   GEMS
   European Commission
   Horizon 2020 Framework Programme
   818064

   Ultrafast Raman Technologies for Protein Identification and Sequencing
   ProID
   European Commission
   Horizon 2020 Framework Programme
   964363

   NATIONAL QUANTUM SCIENCE AND TECHNOLOGY INSTITUTE
   NQSTI
   MUR
   PNRR
   PE0000023
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11384/135482
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