Experimental evidence of extremely high spatial resolution of tip-enhanced Raman scattering (TERS) has been recently demonstrated. Here, we present a full quantum chemical description (at the density functional level of theory) of the non-resonant chemical effects on the Raman spectrum of an adenine molecule mapped by a tip, modeled as a single silver atom or a small silver cluster. We show pronounced changes in the Raman pattern and its intensities depending on the conformation of the nanoparticle–substrate system, concluding that the spatial resolution of the chemical contribution of TERS can be in the sub-nm range.

Predicting the energetics of chemical transformations requires localizing stationary points on a potential energy surface. While educts and products of a chemical reaction may be known, transition state optimization is challenging as good guesses may be unavailable. Extending stationary point searches to the excited state leads to additional difficulties as several states may be close in energy, requiring efficient state tracking. Here, we report the implementation of pysisyphus, an external optimizer, that allows localization of stationary points not only in the ground state but also for excited state by providing several state‐tracking algorithms. pysisyphus offers all necessary tools for calculating reaction paths, starting from the optimization of the reactants, running chain‐of‐states methods such as the nudged elastic band or the growing string method with subsequent transition state optimization, and a concluding intrinsic reaction coordinate calculation.

The sunlight-driven reduction of CO₂ into carbonaceous fuels can lower the atmospheric CO₂ concentration and provide renewable energy simultaneously, attracting scientists to design photocatalytic systems for facilitating this process. Significant progress has been made in designing high-performance photosensitizers and catalysts in this regard, and further improvement can be realized by installing additional interactions between the abovementioned two components, however, the design strategies and mechanistic investigations on such interactions remain challenging. Here, we present the construction of molecular models for intermolecular π–π interactions between the photosensitizer and the catalyst, via the introduction of pyrene groups into both molecular components. The presence, types, and strengths of diverse π–π interactions, as well as their roles in the photocatalytic mechanism, have been examined by ¹H NMR titration, fluorescence quenching measurements, transient absorption spectroscopy, and quantum chemical simulations. We have also explored the rare dual emission behavior of the pyrene-appended iridium photosensitizer, of which the excited state can deliver the photo-excited electron to the pyrene-decorated cobalt catalyst at a fast rate of 2.60 × 10⁶ s^–1 via co-facial π–π interaction, enabling a remarkable apparent quantum efficiency of 14.3 ± 0.8% at 425 nm and a high selectivity of 98% for the photocatalytic CO₂-to-CO conversion. This research demonstrates non-covalent interaction construction as an effective strategy to achieve rapid CO₂ photoreduction besides a conventional photosensitizer/catalyst design.