Can we use on-the-fly quantum simulations to connect molecular structure and sunscreen action?

Faraday Discuss. 2019 Jul 11;216(0):476-493. doi: 10.1039/c8fd00228b.

Abstract

The ground-up design of new molecular sunscreens, with improved photostability, absorbance and spectral coverage, stands as a challenge to fundamental chemical science. Correlating sunscreen molecular structure and function requires detailed insight into the relaxation pathways available following photoexcitation; however, the complex coupled electron/nuclear dynamics in these systems stands as a tough challenge to computational chemistry. To address this challenge, we have recently developed efficient and accurate simulation methods to model non-adiabatic dynamics of general molecular systems as a route to correlating photoinduced dynamics and potential sunscreen activity. Our approach, combining the multi-configuration time-dependent Hartree (MCTDH) method with PESs generated using machine-learning, represents a new "on-the-fly" strategy for accurate wavefunction propagation, with the potential to provide a new "black box" strategy for interrogating ultrafast dynamics in general photoinduced energy transport processes. Here, we illustrate our attempts to apply this methodology to study the ultrafast photochemistry of four compounds derived from mycosporine-like amino acids (MAAs), compounds which are believed to act as microbial sunscreens in micro-organisms such as algae. Specifically, we investigate how the choice of active vibrational space and diabatic electronic states in MCTDH strongly influences the predictions of ultrafast dynamic relaxation in representative MAAs. Our results serve to demonstrate that "on-the-fly" quantum dynamics using MCTDH is increasingly viable, but important barriers relating to coordinate choices and diabatisation remain.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acids / chemistry*
  • Machine Learning
  • Molecular Structure
  • Quantum Theory*
  • Sunscreening Agents / chemistry*

Substances

  • Amino Acids
  • Sunscreening Agents