Status and perspectives for the multiconfigurational short-range density functional theory method
Hans Jørgen Aagaard Jensen1, Erik R. Kjellgren1, Erik D. Hedegård2
1University of Southern Denmark, Dept. of Chemistry, Physics and Pharmacy, DK-5230 Odense M, Denmark
2 Lund University, Department of Theoretical Chemistry, Kemicentrum P.O. Box 124, SE-221 00 Lund, Sweden
Reliable and cost-effective modeling of multi-reference systems as e.g. open-shell transition metal complexes and enzymes is still a huge challenge for computational quantum chemistry. In many cases Kohn-Sham DFT is not sufficiently reliable, and often state-of-the art methods such as CASPT2 and NEVPT2 are computationally too expensive.
As a promising alternative, we explore Andreas Savin’s idea to combine wave-function theory for the long-range electron-electron repulsion with density functional theory for the shortrange. We have focused on MC-srDFT, a fully variational model combining long-range
multiconfiguration self-consistent field for proper description of near-degeneracies and different spin states with short-range semi-local density functional theory [1-9]. In contrast to CASPT2, NEVPT2 and MC-PDFT, because MC-srDFT is fully variational it is relatively straightforward to develop MC-srDFT for calculations of molecular linear and non-linear response properties as electronic excitations, NMR shielding and spin-spin coupling, twophoton absorption etc. etc.
In this talk current status and future perspectives will be presented. Our first public release of MC-srDFT will be in Dalton2019.
[1] On the universality of the long-/short-range separation in multiconfigurational density functional theory. E. Fromager, J. Toulouse, and H. J. Aa. Jensen, J. Chem. Phys. 126, 074111 (2007).
[2] Merging multireference perturbation and density-functional theories by means of range separation: Potential curves for Be2, Mg2, and Ca2. E. Fromager, R. Cimiraglia, and H. J. Aa. Jensen, Phys. Rev. A 81, 024502 (2010).
[3] Multi-configuration time-dependent density-functional theory based on range separation. E. Fromager, S. Knecht, and H. J.
Aa. Jensen, J. Chem. Phys. 138, 084101 (2013).
[4] On the universality of the long-/short-range separation in multiconfigurational density-functional theory. E. Fromager, J. Toulouse, and H. J. Aa. Jensen, J. Chem. Phys. 126, 074111 (2007).
[5] Density Matrix Renormalization Group with Efficient Dynamical Electron Correlation Through Range Separation. E. D. Hedegård, S. Knecht, J. Skau Kielberg, H. J. Aa. Jensen, and M. Reiher, J. Chem. Phys. 142, 224108 (2015)).
[6] Excitation Spectra of Nucleobases with Multiconfigurational Density Functional Theory. M. Hubert, H. J. Aa. Jensen, and E.D. Hedegård, J. Phys. Chem. A 120, 36–43 (2016).
[7] Investigation of Multiconfigurational short-range Density Functional Theory for Electronic Excitations in Organic Molecules. M. Hubert, E.D. Hedegård, and H. J. Aa. Jensen, J. Chem. Theory Comput. 12, 2203–2213 (2016).
[8] Exploration of H2 binding to the [NiFe]-hydrogenase active site with multiconfigurational density functional theory. G. Dong, U. Ryde, H. J. Aa. Jensen, and E. D. Hedegård. Phys. Chem. Chem. Phys. 20, 794–801 (2018)
[9] Multiconfigurational short-range density-functional theory for open-shell systems. E. D. Hedegård, J. Toulouse, and H. J. Aa. Jensen. J. Chem. Phys. 148, 214103 (2018)