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Volume 221, 2020
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Temperature dependence of the vibrational spectrum of porphycene: a qualitative failure of classical-nuclei molecular dynamics

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Abstract

The temperature dependence of vibrational spectra can provide information about structural changes of a system and also serve as a probe to identify different vibrational mode couplings. Fully anharmonic temperature-dependent calculations of these quantities are challenging due to the cost associated with statistically converging trajectory-based methods, especially when accounting for nuclear quantum effects. Here, we train a high-dimensional neural network potential energy surface for the porphycene molecule based on data generated with DFT-B3LYP, including pairwise van der Waals interactions. In addition, we fit a kernel ridge regression model for the molecular dipole moment surface. The combination of this machinery with thermostatted path integral molecular dynamics (TRPMD) allows us to obtain well-converged, full-dimensional, fully-anharmonic vibrational spectra including nuclear quantum effects, without sacrificing the first-principles quality of the potential-energy surface or the dipole surface. Within this framework, we investigate the temperature and isotopologue dependence of the high-frequency vibrational fingerprints of porphycene. While classical-nuclei dynamics predicts a red shift of the vibrations encompassing the NH and CH stretches, TRPMD predicts a strong blue shift in the NH-stretch region and a smaller one in the CH-stretch region. We explain this behavior by analyzing the modulation of the effective potential with temperature, which arises from vibrational coupling between quasi-classical thermally activated modes and high-frequency quantized modes.

Graphical abstract: Temperature dependence of the vibrational spectrum of porphycene: a qualitative failure of classical-nuclei molecular dynamics

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Article information


Submitted
01 May 2019
Accepted
20 Jun 2019
First published
20 Jun 2019

This article is Open Access

Faraday Discuss., 2020,221, 526-546
Article type
Paper

Temperature dependence of the vibrational spectrum of porphycene: a qualitative failure of classical-nuclei molecular dynamics

Y. Litman, J. Behler and M. Rossi, Faraday Discuss., 2020, 221, 526
DOI: 10.1039/C9FD00056A

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