QM/ELMO: A Multi-Purpose Fully Quantum Mechanical Embedding Scheme Based on Extremely Localized Molecular Orbitals

The development of computationally advantageous methods for the study of large systems is a long-standing research topic in theoretical chemistry. Among these techniques, a prominent place is certainly occupied by the multiscale embedding strategies, from the well-known QM/MM (quantum mechanics/molecular mechanics) methods to the latest and promising fully quantum mechanical approaches. In this Feature Article, we will briefly review the recently proposed QM/ELMO (quantum mechanics/extremely localized molecular orbital) scheme, namely a new multiscale embedding strategy in which the most chemically relevant region of the investigated system is treated at fully quantum chemical level, while the remaining part (namely, the environment) is described by means of transferred extremely localized molecular orbitals that remain frozen throughout the computation. Other than highlighting the theoretical bases, here we will also review the main results obtained through all the currently available variants of the novel method. In particular, we will show how the QM/ELMO embedding scheme has been successfully exploited to perform both ground and excited state calculations, reproducing the results of corresponding fully quantum mechanical computations but with a much lower computational cost. A first application to crystallography will be also discussed, and we will describe how the QM/ELMO approach has been recently coupled with the Hirshfeld atom refinement technique to accurately determine the positions of hydrogen atoms from X-ray diffraction data. Given the reliability and quality of the obtained results, future applications of the current versions of the QM/ELMO embedding strategy to different types of chemical problems are to be expected in the near future. Moreover, further algorithmic improvements and methodological developments are also envisaged, such as the development of a polarizable QM/ELMO scheme accounting for the effects of the QM region on the ELMO subsystem or the use of the new embedding approach in the context of quantum crystallography to perform unprecedented accurate refinements of macromolecular crystal structures.