(September 2021 - August 2025)

This project addresses confined molecular systems, encompassing a concept broader than just the spatial cage-like confinement concept and/or a pressure-exerted situations, including also solid or liquid environments, interfaces, as well as effects of electro-magnetic fields. We are aimed to provide a computationally sound and experimentally tractable foundation for the prediction, control, and modification of the properties and the behavior of specific confined molecular systems towards both their fundamental understanding and their useful technological applications (from clean catalysts and photocatalysts to polaronic 2D materials). Our methods of choice are first-principles modelling, multi-scale computational simulation, atomistic theory and selected experiments on critical molecular systems under  different confinement  environments  such  as the surface of technologically relevant nanomaterials, helium nanodroplets, and the interior of carbon nanotubes,  including  air  exposures  as  a  function of  pressure  and  temperature. A  specific  challenge  will  be  to  properly  characterize  the contact  region  at  the  interface  between a molecule and its local confinement, often an object which necessitates a mesoscopic, yet quantum-mechanical treatment, using first-principle approaches to characterize the underlying intermolecular interactions. We plan to tackle these challenges as follows: (1)  Development of novel computational approaches allowing the description of quantum motion under specific confinement conditions (e.g., de Lara-Castells and Mitrushchenkov, J. Chem. Phys. Lett. 11 (2020) 5081); (2) Screening of interfacial phenomena, using the very cold and practically inert environment provided by superfluid helium nanodroplets as convenient nanolabs (e.g., de Lara-Castells, Hauser, and Mitrushchenkov, J. Phys. Chem. Lett. 8 (2017) 4284); (3)  Development of innovative ab initio-derived potential models allowing the description of intermolecular adsorbate-material interactions (e.g., Hauser, Mitrushchenkov, and de Lara-Castells, J. Phys. Chem. C 121 (2017) 3807); (4) Involvement  of  industry  allowing  an  immediate  transfer  of  the newly  acquired research-derived knowledge for technological applications. The main focus of this project will be on the theoretical modelling of subnanometer-sized coigane metal clusters (either unsupported in air or surface-supported) as the very recent development of highly selective experimental techniques has made its synthesis possible. Pushing our understanding of these, more `molecular' than `metallic', systems far beyond the present knowledge in materials science, we have already been shown how modified TiO2 surfaces with Cu5 and/or Ag5 clusters can be visible-light photo-active materials [de Lara-Castells et al. J. Mat. Chem. A 7 (2019) 7489], potential photocatalysts for CO2 reduction [López-Caballero, Hauser, and de Lara-Castells, J. Phys. Chem. C 123 (2019) 23064], and hosts of multiple surface polarons [López-Caballero et al., J. Mat. Chem. A 8 (2020) 6842]. This research will be carried out through close collaborations with world-class experimental groups as well as an international network of experts on highly specialised theoretical issues. We will leverage all these strengths  to  build  interpretive  physical  models and  do  innovative simulations which will help to shape the modern field of subnanometer science.