Self-Consistent Field Response Theory and Coupled-Cluster Theory

Aleksandra Tucholska

Haifeng Lang, Takeshi Sato

Five time-dependent orbital optimized coupled-cluster methods, of which four can converge to the time-dependent complete active space self-consistent-field method, are presented for fermion-mixtures with arbitrary fermion kinds and numbers. Truncation schemes maintaining the intragroup orbital rotation invariance, as well as equations of motion of coupled-cluster (CC) amplitudes and orbitals, are derived. Present methods are compact CC-parameterization alternatives to the time-dependent multiconfiguration self-consistent-field method for systems consisting of arbitrarily different kinds and numbers of interacting fermions. Theoretical analysis of applications of present methods to various chemical systems is reported.

Isaiah Shavitt, Rodney J. Bartlett

David J. Dean

Daniel G. A. Smith, Lori A. Burns, Dominic A. Sirianni +24 more

Psi4NumPy demonstrates the use of efficient computational kernels from the open-source Psi4 program through the popular NumPy library for linear algebra in Python to facilitate the rapid development of clear, understandable Python computer code for new quantum chemical methods, while maintaining a relatively low execution time. Using these tools, reference implementations have been created for a number of methods, including self-consistent field (SCF), SCF response, many-body perturbation theory, coupled-cluster theory, configuration interaction, and symmetry-adapted perturbation theory. Furthermore, several reference codes have been integrated into Jupyter notebooks, allowing background, underlying theory, and formula information to be associated with the implementation. Psi4NumPy tools and associated reference implementations can lower the barrier for future development of quantum chemistry methods. These implementations also demonstrate the power of the hybrid C++/Python programming approach employed by the Psi4 program.

Werner Kutzelnigg