Erreichen von chemischer Genauigkeit in der Festkörperelektronenstrukturtheorie: Linear-skalierende periodische lokale Coupled-Cluster-Methode im Zusammenspiel mit explizit korrelierter Møller-Plesset-Störungstheorie

• Antragsteller: Privatdozent Dr. Denis Usvyat
• Fachliche Zuordnung: Theoretische Chemie: Elektronenstruktur, Dynamik, Simulation
• Förderung: Förderung von 2010 bis 2022
• Projektkennung: Deutsche Forschungsgemeinschaft (DFG) - Projektnummer 179161791

• Erstellungsjahr: 2022

Zusammenfassung der Projektergebnisse

The goal of the project was to create a toolbox of methods that allowing for chemical accuracy calculations for non-conducting weakly correlated solids. The approach was based on hybrid scheme implying a low-level treatment plus a high-level correction. This goal has been achieved. At the present stage, for the low level one can use periodic LMP2 (based on PAOs or OSVs), periodic LMP2-F12 or embedded-fragment LdrCCD. The high-level correction can be evaluated using embedded-fragment CCSD(T) or finite-cluster LCCSD(T). In addition to the initial goals of the project, we have developed and implemented a new very accurate pair approximation for molecular local CCSD(T) method and embedded-fragment excited-state and multireference techniques. The implemented methods have been used in numerous applications. In the course of the project we have encountered difficulties with efficiency of the fully periodic coupled cluster treatment due to the expansion of the summation ranges in composite terms. A drastic compression of the virtual space by, e.g. using pair natural orbitals (PNOs), may significantly improve the efficiency, and we plan to explore this possibility. At the same time, an embedded-fragment approach appeared to be an effective alternative to the purely periodic treatment. The developments and results of this project are also seen as a basis for several follow up projects: • Several application projects are planned in collaboration with other groups. • A few technical improvements of current methodology are planned: (i) the periodic F12 treatment will be extended to OSVs, (ii) the embedded-fragment local treatment will be extended to LCCSD(T) level. • As noted above, the long range coupled cluster terms will be implemented in the periodic local PNO format and coupled to the embedded-fragment treatment. This will be instrumental for systems where very long-range contributions beyond MP2 are sizable. • Several new development avenues will be explored, such as (i) embedded-fragment local excited-state methods to study excited states localized on defects, (ii) embedded-fragment local multireference methods to local strongly correlated features in solids.

Projektbezogene Publikationen (Auswahl)

• “Approaching the theoretical limit in periodic local MP2 calculations with atomic-orbital basis sets: The case of LiH”. In: J. Chem. Phys. 134 (2011), p. 214105
  D. Usvyat, B. Civalleri, L. Maschio, R. Dovesi, C. Pisani, and M. Schütz
  
• Geometrical frustration of an argon monolayer adsorbed on the MgO (100) surface: An accurate periodic ab initio study”. In: Phys. Rev. B 86 (2012), p. 045412
  D. Usvyat, K. Sadeghian, L. Maschio, and M. Schütz
  
• “Incrementally corrected periodic local MP2 calculations: I. The cohesive energy of molecular crystals”. In: J. Chem. Theory Comput. 9 (2013), p. 5590
  C. Müller and D. Usvyat
  
• “Linear-scaling explicitly correlated treatment of solids: Periodic local MP2-F12 method”. In: J. Chem. Phys. 139 (2013), p. 194101
  D. Usvyat
  
• “Approaching an exact treatment of electronic correlations at solid surfaces: The binding energy of the lowest bound state of helium adsorbed on MgO (100)”. In: Phys. Rev. B 89 (2014), p. 205138
  R. Martinez-Casado, D. Usvyat, L. Maschio, G. Mallia, S. Casassa, J. Ellis, M. Schütz, and N. M. Harrison
  
• “Efficient and accurate treatment of weak pairs in local CCSD (T) calculations. II. Beyond the ring approximation”. In: J. Chem. Phys. 140 (2014), p. 244107
  M. Schütz, O. Masur, and D. Usvyat
  
• “High precision quantum-chemical treatment of adsorption: Benchmarking physisorption of molecular hydrogen on graphane”. In: J. Chem. Phys. 143 (2015), p. 104704
  D. Usvyat
  
• “Periodic local MP2 method employing orbital specific virtuals”. In: J. Chem. Phys. 143 (2015), p. 102805
  D. Usvyat, L. Maschio, and M. Schütz
  
• “Fragment-Based Direct-Local-Ring-Coupled-Cluster Doubles Treatment Embedded in the Periodic Hartree–Fock Solution”. In: J. Chem. Theory Comput. 12 (2016), p. 5145
  O. Masur, M. Schütz, L. Maschio, and D. Usvyat
  
• “A comparison between quantum chemistry and quantum Monte Carlo techniques for the adsorption of water on the (001) LiH surface”. In: J. Chem. Phys. 146 (2017), p. 204108
  T. Tsatsoulis, F. Hummel, D. Usvyat, M. Schütz, G. H. Booth, S. S. Binnie, M. J. Gillan, D. Alfe, A. Michaelides, and A. Gruneis
  
• “Exfoliation Energy of Black Phosphorus Revisited: A Coupled Cluster Benchmark”. In: J. Phys. Chem. Lett. 8 (2017), p. 1290
  M. Schütz, L. Maschio, A. J. Karttunen, and D. Usvyat
  
• “Periodic and fragment models based on the local correlation approach”. In: WIREs: Comput. Mol. Sci. 8 (2018), e1357
  D. Usvyat, L. Maschio, and M. Schütz
  
• “Fragment-based restricted active space configuration interaction with second-order corrections embedded in periodic Hartree–Fock wave function”. In: J. Chem. Theory Comput. 16 (2020), p. 7100
  H. H. Lin, L. Maschio, D. Kats, D. Usvyat, and T. Heine
  
• “Full Configuration Interaction Quantum Monte Carlo treatment of fragments embedded in periodic mean field”. In: J. Chem. Phys. 156 (2022), p. 154107
  E. Christlmaier, D. Kats, A. Alavi, and D. Usvyat
  
• “Reaction barriers on non-conducting surfaces beyond periodic local MP2: diffusion of hydrogen on α-Al2O3(0001) as a test case”. In: J. Chem. Phys. 156 (2022), p. 074109
  T. Mullan, L. Maschio, P. Saalfrank, and D. Usvyat