Development of Linear-Scaling Methods for Calculating Energy Gradients and NMR Chemical Shifts at the Second-Order Møller-Plesset Perturbation Level

• Applicant: Professor Dr. Christian Ochsenfeld
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
• Term: from 2013 to 2017
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 244944579

• Final Report Year: 2018

Final Report Abstract

Overall the present project funded by the DFG has lead to a pletora of new approaches useful for calculating first- and second-order properties at the MP2 and also at the double-hybrid DFT level. We were able to acquire a solid basis for further developments regarding molecular properties: Our new RI-CDD MP2 energy gradients allow for further studies, especially in regard of EPR spectroscopic parameters. With investigations of second-order properties both at DFT as well as the newly parametrized SCS-/SOS-MP2 methods for calculating NMR chemical shifts new applications for extending the links between theory and experiment open up. Despite the success, many challenges remain for the efficient calculation of MP2 NMR shieldings for large systems and we are continuing our work in this direction, while the accuracies of MP2 shieldings are most promising.

Publications

• (2018) Gauge-origin dependence in electronic g-tensor calculations. The Journal of chemical physics 148 (21) 214101
  Glasbrenner, Michael; Vogler, Sigurd; Ochsenfeld, Christian
  (See online at https://doi.org/10.1063/1.5028454)
• (2018) Selected-Nuclei Method for the Computation of Hyperfine Coupling Constants within Second-Order Møller-Plesset Perturbation Theory. Journal of chemical theory and computation 14 (6) 3014–3024
  Vogler, Sigurd; Savasci, Gökcen; Ludwig, Martin; Ochsenfeld, Christian
  (See online at https://dx.doi.org/10.1021/acs.jctc.8b00116)
• A linear- and sublinear-scaling method for calculating NMR shieldings in atomic orbital-based second-order Møller-Plesset perturbation theory, J. Chem. Phys. 2013, 138, 174104
  M. Maurer, C. Ochsenfeld
  (See online at https://doi.org/10.1063/1.4801084)
• Benchmarking Hydrogen and Carbon NMR Chemical Shifts at HF, DFT, and MP2 Levels, J. Chem. Theory Comput. 2014, 10, 572–578
  D. Flaig, M. Maurer, M. Hanni, K. Braunger, L. Kick, M. Thubauville, C. Ochsenfeld
  (See online at https://doi.org/10.1021/ct400780f)
• Cholesky-decomposed density MP2 with density fitting: accurate MP2 and double-hybrid DFT energies for large systems, J. Chem. Phys. 2014, 140, 224112
  S. A. Maurer, L. Clin, C. Ochsenfeld
  (See online at https://doi.org/10.1063/1.4881144)
• Communication: A reduced scaling J-engine based refomulation of SOS-MP2 using graphics processing units, J. Chem. Phys. 2014, 141, 051106
  S. Maurer, J. Kussmann, C. Ochsenfeld
  (See online at https://doi.org/10.1063/1.4891797)
• A reduced-scaling density matrixbased method for the computation of vibrational Hessian matrix at the selfconsistent field level, J. Chem. Phys. 2015, 142, 094101
  J. Kussmann, A. Luenser, C. Ochsenfeld
  (See online at https://doi.org/10.1063/1.4908131)
• Preselective Screening for Linear-Scaling Exact Exchange-Gradient Calculations for Graphics Processing Units and General Strong-Scaling Massively Parallel Calculations, J. Chem. Theory Comput. 2015, 11, 918–922
  J. Kussmann, C. Ochsenfeld
  (See online at https://doi.org/10.1021/ct501189u)
• Spin Component-Scaled Second-Order Møller- Plesset Perturbation Theory for Calculating NMR Shieldings, J. Chem. Theory Comput. 2015, 11, 37–44
  M. Maurer, C. Ochsenfeld
  (See online at https://doi.org/10.1021/ct5007295)
• Computation of indirect nuclear spin–spin couplings with reduced complexity in pure and hybrid density functional approximations, J. Chem. Phys. 2016, 145, 124103
  A. Luenser, J. Kussmann, C. Ochsenfeld
  (See online at https://doi.org/10.1063/1.4962260)
• Intermolecular 119 Sn,31 P Through-Space Spin-Spin Coupling in a Solid Bivalent Tin Phosphido Complex, Inorg. Chem. 2016, 55, 4669–4675
  J. Arras, K. Eichele, B. Maryasin, H. Schubert, C. Ochsenfeld, K. Wesemann
  (See online at https://doi.org/10.1021/acs.inorgchem.6b00573)
• Communication: Almost errorfree resolution-of-the-identity correlation methods by null space removal of the particle-hole interactions, J. Chem. Phys. 2017, 146, 211106
  H. F. Schurkus, A. Luenser, C. Ochsenfeld
  (See online at https://doi.org/10.1063/1.4985085)
• Distance-including rigorous upper bounds and tight estimates for two-electron integrals over long- and short-range operators, J. Chem. Phys. 2017, 147, 144101
  T. H. Thompson, C. Ochsenfeld
  (See online at https://doi.org/10.1063/1.4994190)
• Low-scaling first-order properties within second-order Møller-Plesset perturbation theory using Cholesky decomposed density matrices, J. Chem. Phys. 2017, 147, 024101
  S. Vogler, M. Ludwig, M. Maurer, C. Ochsenfeld
  (See online at https://doi.org/10.1063/1.4990413)
• Nuclear Magnetic Shieldings of Stacked Aromatic and Antiaromatic Molecules, J. Chem. Theory Comput. 2017, 13, 1952–1962
  D. Sundholm, M. Rauhalahti, N. Özcan, R. Mera-Adasme, J. Kussmann, C. Ochsenfeld
  (See online at https://doi.org/10.1021/acs.jctc.6b01250)
• Vanishing-Overhead Linear- Scaling Random Phase Approximation by Cholesky Decomposition and an Attenuated Coulomb-Metric, J. Chem. Theory Comput. 2017, 13, 1647–1655
  A. Luenser, H. F. Schurkus, C. Ochsenfeld
  (See online at https://doi.org/10.1021/acs.jctc.6b01235)