2000 character limit reached
Combining complex conjugation, time-reversal, and spin symmetry projection of coupled cluster wave functions
Published 10 May 2024 in cond-mat.str-el and physics.chem-ph | (2405.06776v2)
Abstract: Complex conjugation symmetry breaking and restoration generate two non-orthogonal configurations at the Hartree-Fock level that can capture static correlation naturally. In conjunction with broken spin-symmetry coupled cluster theory, the symmetry-projected wave function shows good agreement with full configuration interaction in beryllium hydride insertion, lithium fluoride dissociation, and symmetric stretching of tetrahedral H$_4$. By adding spin flip projection, we can also recover time reversal symmetry in the same coupled cluster framework.
- R. Seeger and J. A. Pople, Self‐consistent molecular orbital methods. XVIII. Constraints and stability in Hartree–Fock theory, J. Chem. Phys. 66, 3045 (1977).
- H. Fukutome, Unrestricted Hartree-Fock theory and its applications to molecules and chemical reactions, Int. J. Quantum Chem. 20, 955 (1981).
- J. L. Stuber and J. Paldus, Fundamental World of Quantum Chemistry: A Tribute Volume to the Memory of Per-Olov Löwdin (Kluwer, New York, 2003).
- D. W. Small, E. J. Sundstrom, and M. Head-Gordon, Restricted Hartree Fock using complex-valued orbitals: A long-known but neglected tool in electronic structure theory, J. Chem. Phys. 142, 024104 (2015).
- L. C. Jake, T. M. Henderson, and G. E. Scuseria, Hartree-Fock symmetry breaking around conical intersections, J. Chem. Phys. 148, 024109 (2018).
- H. G. A. Burton, M. Gross, and A. J. W. Thom, Holomorphic Hartree–Fock Theory: The Nature of Two-Electron Problems, J. Chem. Theory Comput. 14, 607 (2018).
- T. M. Henderson, C. A. Jiménez-Hoyos, and G. E. Scuseria, Magnetic structure of density matrices, J. Chem. Theory Comput. 14, 649 (2018).
- J. Hendekoviá, Method of complex molecular orbitals, Int. J. Quantum Chem. 8, 799 (1974).
- T. Tsuchimochi and S. Ten-no, Communication: Configuration interaction combined with spin-projection for strongly correlated molecular electronic structures, J. Chem. Phys. 144, 011101 (2016).
- R. Song, T. M. Henderson, and G. E. Scuseria, A power series approximation in symmetry projected coupled cluster theory, J. Chem. Phys. 156, 104105 (2022).
- T. Tsuchimochi and S. L. Ten-no, Orbital-invariant spin-extended approximate coupled-cluster for multi-reference systems, J. Chem. Phys. 149, 044109 (2018).
- T. Tsuchimochi and S. L. Ten-no, Second-Order Perturbation Theory with Spin-Symmetry-Projected Hartree–Fock, J. Chem. Theory Comput. 15, 6688 (2019).
- K. Schmid, On the use of general symmetry-projected Hartree–Fock–Bogoliubov configurations in variational approaches to the nuclear many-body problem, Prog. Part. Nucl. Phys. 52, 565 (2004).
- E. P. Wigner, Normal Form of Antiunitary Operators, J. Math. Phys. 1, 409 (1960).
- Y. Smeyers, Etude d’une fonction unrestricted—Hartree-Fock ameliorée, An. Fis. Madrid 67, 17 (1971).
- Y. G. Smeyers, The half projected Hartree-Fock model for determining singlet excited states. (Academic Press, 2000) pp. 253–270.
- D. J. Thouless, Stability conditions and nuclear rotations in the Hartree-Fock theory, Nucl. Phys. 21, 225 (1960).
- H. G. A. Burton and A. J. W. Thom, Reaching Full Correlation through Nonorthogonal Configuration Interaction: A Second-Order Perturbative Approach, J. Chem. Theory Comput. 16, 5586 (2020).
- J. Nite and C. A. Jiménez-Hoyos, Efficient Multi-Configurational Wavefunction Method with Dynamical Correlation Using Non-Orthogonal Configuration Interaction Singles and Doubles (NOCISD), ChemRxiv (2019).
- C. A. Jiménez-Hoyos, T. M. Henderson, and G. E. Scuseria, Generalized Hartree–Fock description of molecular dissociation, J. Chem. Theory Comput. 7, 2667 (2011).
- C. A. Jiménez-Hoyos, R. Rodríguez-Guzmán, and G. E. Scuseria, Excited electronic states from a variational approach based on symmetry-projected Hartree-Fock configurations, J. Chem. Phys. 139, 224110 (2013).
Paper Prompts
Sign up for free to create and run prompts on this paper using GPT-5.
Top Community Prompts
Collections
Sign up for free to add this paper to one or more collections.