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Many Body Response of Benzene at Monolayer MoS2: Van der Waals interactions and spectral broadening
  • Alina Umerbekova,
  • Michele Pavanello
Alina Umerbekova
Rutgers
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Michele Pavanello
Rutgers
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Abstract

Models of surface enhancement of molecular electronic response properties are challenging for two reasons: (1) molecule-surface interactions require the simultaneous solution of the molecular and the surface dynamic response (a daunting task); (2) when solving for the electronic structure of the combined molecule+surface system, it is not trivial to single out the particular physical effects responsible for enhancement. To attack this problem, in this work we apply a formally exact decomposition of the system’s response function into subsystem contributions by employing subsystem DFT which grants access to dynamic polarizabilities and optical spectra. In order to access information about the interactions between the subsystems, we extend a previously developed subsystem-based adiabatic connection fluctuation-dissipation theorem of DFT to separate the additive from the nonadditive correlation energy and identify the nonadditive correlation as the van der Waals interactions. As an example, we choose benzene adsorbed on monolayer MoS2. We isolate the contributions to the benzene’s dynamic response arising from the interaction with the surface and for the first time, we evaluate the enhancements to the effective C6 coefficients as a function of benzene-MoS2 distance and adsorption site. We also quantify the spectral broadening of the benzene’s electronic excited states due to their interaction with the surface. We find that the broadening has a similar decay law with the molecule-surface distance as the leading van der Waals interactions (i.e., R-6) and that the surface enhancement of dispersion interactions between benzene molecules is less than 5\%, but still large enough (0.5 kcal/mol) to likely play a role in the prediction of interface morphologies.

Peer review status:ACCEPTED

20 Jan 2020Submitted to International Journal of Quantum Chemistry
22 Jan 2020Submission Checks Completed
22 Jan 2020Assigned to Editor
24 Jan 2020Reviewer(s) Assigned
09 Feb 2020Review(s) Completed, Editorial Evaluation Pending
10 Feb 2020Editorial Decision: Revise Minor
26 Feb 20201st Revision Received
26 Feb 2020Submission Checks Completed
26 Feb 2020Assigned to Editor
26 Feb 2020Reviewer(s) Assigned
13 Mar 2020Review(s) Completed, Editorial Evaluation Pending
13 Mar 2020Editorial Decision: Accept