English

Unitary coupled-cluster based self-consistent polarization propagator theory: a quadratic unitary coupled-cluster singles and doubles scheme

Chemical Physics 2024-06-19 v2

Abstract

The development of a quadratic unitary coupled-cluster singles and doubles (qUCCSD) based self-consistent polarization propagator method is reported. We present a simple strategy for truncating the commutator expansion of the UCC transformed Hamiltonian Hˉ\bar{H}. The qUCCSD method for the electronic ground-state includes up to double commutators for the amplitude equations and up to cubic commutators for the energy expression. The qUCCSD excited-state eigenvalue equations include up to double commutators for the singles-singles block of Hˉ\bar{H}, single commutators for the singles-doubles and doubles-singles blocks, and the bare Hamiltonian for the doubles-doubles block. Benchmark qUCCSD calculations of the ground-state properties and excitation energies for representative molecules demonstrate significant improvement of the accuracy and robustness over the previous UCC3 scheme derived using M{\o}ller-Plesset perturbation theory.

Keywords

Cite

@article{arxiv.2107.01099,
  title  = {Unitary coupled-cluster based self-consistent polarization propagator theory: a quadratic unitary coupled-cluster singles and doubles scheme},
  author = {Junzi Liu and Lan Cheng},
  journal= {arXiv preprint arXiv:2107.01099},
  year   = {2024}
}