Abstract
The ab initio nanoreactor has previously been introduced to automate reaction discovery for ground state chemistry. In this work, we present the nonadiabatic nanoreactor, an analogous framework for excited state reaction discovery. We automate the study of nonadiabatic decay mechanisms of molecules by probing the intersection seam between adiabatic electronic states with hyper-real metadynamics, sampling the branching plane for relevant conical intersections, and performing seam-constrained path searches. We illustrate the effectiveness of the nonadiabatic nanoreactor by applying it to benzene, a molecule with rich photochemistry and a wide array of photochemical products. Our study confirms the existence of several types of S0/S1 and S1/S2 conical intersections which mediate access to a variety of ground state stationary points. We elucidate the connections between conical intersection energy/topography and the resulting photoproduct distribution, which changes smoothly along seam space segments. The exploration is performed with minimal user input, and the protocol requires no previous knowledge of the photochemical behavior of a target molecule. We demonstrate that the nonadiabatic nanoreactor is a valuable tool for the automated exploration of photochemical reactions and their mechanisms.
Highlights
The potential of light to promote chemical reactions was rst recognized at the beginning of the 20th century, when Ciamician urged industry to investigate “the photochemistry of the future”.1 light-driven syntheses can allow for milder reaction conditions, shorter synthetic routes and avoidance of protection/deprotection for functional groups.[2]
In this work, taking inspiration from the thermal ab initio nanoreactor, we present the nonadiabatic nanoreactor (NANR), a tool for the automatic exploration of photochemistry that aims at modeling photoreactions with no prior chemical knowledge
We show that the NANR can automate the exploration of excited state systems, predicting which photoproducts are accessible
Summary
The potential of light to promote chemical reactions was rst recognized at the beginning of the 20th century, when Ciamician urged industry to investigate “the photochemistry of the future”.1 light-driven syntheses can allow for milder reaction conditions, shorter synthetic routes and avoidance of protection/deprotection for functional groups.[2]. Light has become increasingly popular as a synthetic tool through systematic multidimensional reaction screening:[4] powerful, high-throughput experimental setups are exploited to experiment with different wavelengths, solvents, sensitizers, and irradiation time. This allows chemists to venture into unexplored territories of both chemical and reaction space, and to discover new synthetic routes. Alternate approaches that rely on chemical heuristics have been explored.[6,17,18,19,20]
Sign-in/Register to view highlights & summary Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
