The vibrational properties of benzene on an ordered water ice surface

TL;DR

This study introduces a hybrid computational approach combining CCSD(T) and PBE-D3 methods to accurately predict the vibrational spectra of benzene on water ice surfaces, emphasizing the importance of surface effects in spectroscopic analysis.

Contribution

The paper presents a novel hybrid CCSD(T)+PBE-D3 approach that improves vibrational spectrum predictions for benzene on water ice, outperforming previous methods in accuracy.

Findings

Hybrid approach achieves RMSD of 21 cm$^{-1}$ for adsorbed benzene

Surface effects significantly alter vibrational modes and intensities

Generated mode correspondence aids spectral assignment

Abstract

We present a hybrid CCSD(T)+PBE-D3 approach to calculating the vibrational signatures for gas phase benzene and benzene adsorbed on an ordered water-ice surface. We compare the results of our method against experimentally recorded spectra and calculations performed using PBE-D3-only approaches (harmonic and anharmonic). Calculations use a proton ordered XIh water-ice surface consisting of 288 water molecules, and results are compared against experimental spectra recorded for an ASW ice surface. We show the importance of including a water ice surface into spectroscopic calculations, owing to the resulting differences in vibrational modes, frequencies and intensities of transitions seen in the IR spectrum. The overall intensity pattern shifts from a dominating $\nu_{11}$ band in the gas-phase to several high-intensity carriers for an IR spectrum of adsorbed benzene. When used for adsorbed benzene, the hybrid approach presented here achieves an RMSD for IR active modes of 21~cm$^{-1}$, compared to 72~cm$^{-1}$ and 49~cm$^{-1}$ for the anharmonic and harmonic PBE-D3 approaches, respectively. Our hybrid model for gaseous benzene also achieves the best results when compared to experiment, with an RMSD for IR active modes of 24~cm$^{-1}$, compared to 55~cm$^{-1}$ and 31~cm$^{-1}$ for the anharmonic and harmonic PBE-D3 approaches, respectively. To facilitate assignment, we generate and provide a correspondence graph between the normal modes of the gaseous and adsorbed benzene molecules. Finally, we calculate the frequency shifts, $\Delta\nu$, of adsorbed benzene relative to its gas phase to highlight the effects of surface interactions on vibrational bands and evaluate the suitability of our chosen dispersion-corrected density functional theory.