Breaking the curse of dimension in heavy-element chemistry
Funding Resources
Funding Resources
This project has been funded by a Marie-Skłodowska-Curie Individual Fellowship European Fellowship project no. 702635-PCCDX
Our goal
Our goal
An essential element of actinide-based research is focused on the prediction of the stability and properties of actinide compounds. Unfortunately, their acute toxicity, radioactivity, and instability complicate experimental studies. Theoretical approaches can be used to determine molecular properties and can provide a fundamental understanding of actinide reactivity and reaction mechanisms. Unfortunately, conventional computational models are difficult, primarily because the computational resources required grow exponentially with the size of the system, an effect known as the curse of dimension. Thus, innovative new approaches must be developed that break the curse of dimension. One such approach models many- electron molecules as collections of noninteracting electron pairs, called geminals. Standard geminal-based methods are inappropriate for actinide chemistry, however, and will be extended to include (i) computationally efficient ways to account for relativistic effects, (ii) correlations between electrons beyond electron-pairing effects, also referred to as weak electron correlation, (iii) the modeling of electronically excited states, and (iv) the description of unpaired (open-shell) electrons. Specifically, weak electron correlation effects will be captured using Coupled Cluster-type approaches, excited states are accessible through an Equation-of-Motion formalism, and the open-shell extension will use generalized one-particle functions and generalized quasi-particles as fundamental building blocks for the electronic wavefunction. The developed models should be robust, computationally cheap, reliable, and black-box-like, requiring minimal user-software interplay. These technical advantages compared to standard approaches will facilitate theoretical modeling of actinide-containing materials out of reach of present-day quantum chemistry methods and will be of crucial importance for a theoretical understanding of actinide chemistry.
Key Publications
Key Publications
published in:
J. Chem. Theory Comput., 2017, 13 (12), pp 5966–5983.
published in:
Leszczyk A., Tecmer P., Boguslawski K. (2019) New Strategies in Modeling Electronic Structures and Properties with Applications to Actinides. In: Broclawik E., Borowski T., Radoń M. (eds) Transition Metals in Coordination Environments. Challenges and Advances in Computational Chemistry and Physics, vol 29. Springer, Cham.