ABSTRACT
Following our recent work on the benzene molecule [P.-F. Loos, Y. Damour, and A. Scemama, J. Chem. Phys. 153, 176101 (2020)], motivated by the blind challenge of Eriksen et al. [J. Phys. Chem. Lett. 11, 8922 (2020)] on the same system, we report accurate full configuration interaction (FCI) frozen-core correlation energy estimates for 12 five- and six-membered ring molecules (cyclopentadiene, furan, imidazole, pyrrole, thiophene, benzene, pyrazine, pyridazine, pyridine, pyrimidine, s-tetrazine, and s-triazine) in the standard correlation-consistent double-ζ Dunning basis set (cc-pVDZ). Our FCI correlation energy estimates, with an estimated error smaller than 1 millihartree, are based on energetically optimized-orbital selected configuration interaction calculations performed with the configuration interaction using a perturbative selection made iteratively algorithm. Having at our disposal these accurate reference energies, the respective performance and convergence properties of several popular and widely used families of single-reference quantum chemistry methods are investigated. In particular, we study the convergence properties of (i) the Møller-Plesset perturbation series up to fifth-order (MP2, MP3, MP4, and MP5), (ii) the iterative approximate coupled-cluster series CC2, CC3, and CC4, and (iii) the coupled-cluster series CCSD, CCSDT, and CCSDTQ. The performance of the ground-state gold standard CCSD(T) as well as the completely renormalized CC model, CR-CC(2,3), is also investigated. We show that MP4 provides an interesting accuracy/cost ratio, while MP5 systematically worsens the correlation energy estimates. In addition, CC3 outperforms CCSD(T) and CR-CC(2,3), as well as its more expensive parent CCSDT. A similar trend is observed for the methods including quadruple excitations, where the CC4 model is shown to be slightly more accurate than CCSDTQ, both methods providing correlation energies within 2 millihartree of the FCI limit.
ABSTRACT
Quantum chemistry is a discipline which relies heavily on very expensive numerical computations. The scaling of correlated wave function methods lies, in their standard implementation, between O(N5) and O(eN) , where N is proportional to the system size. Therefore, performing accurate calculations on chemically meaningful systems requires (i) approximations that can lower the computational scaling and (ii) efficient implementations that take advantage of modern massively parallel architectures. Quantum Package is an open-source programming environment for quantum chemistry specially designed for wave function methods. Its main goal is the development of determinant-driven selected configuration interaction (sCI) methods and multireference second-order perturbation theory (PT2). The determinant-driven framework allows the programmer to include any arbitrary set of determinants in the reference space, hence providing greater methodological freedom. The sCI method implemented in Quantum Package is based on the CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively) algorithm which complements the variational sCI energy with a PT2 correction. Additional external plugins have been recently added to perform calculations with multireference coupled cluster theory and range-separated density-functional theory. All the programs are developed with the IRPF90 code generator, which simplifies collaborative work and the development of new features. Quantum Package strives to allow easy implementation and experimentation of new methods, while making parallel computation as simple and efficient as possible on modern supercomputer architectures. Currently, the code enables, routinely, to realize runs on roughly 2 000 CPU cores, with tens of millions of determinants in the reference space. Moreover, we have been able to push up to 12 288 cores in order to test its parallel efficiency. In the present manuscript, we also introduce some key new developments: (i) a renormalized second-order perturbative correction for efficient extrapolation to the full CI limit and (ii) a stochastic version of the CIPSI selection performed simultaneously to the PT2 calculation at no extra cost.
ABSTRACT
We report unphysical irregularities and discontinuities in some key experimentally measurable quantities computed within the GW approximation of many-body perturbation theory applied to molecular systems. In particular, we show that the solution obtained with partially self-consistent GW schemes depends on the algorithm one uses to self-consistently solve the quasiparticle (QP) equation. The main observation of the present study is that each branch of the self-energy is associated with a distinct QP solution and that each switch between solutions implies a significant discontinuity in the quasiparticle energy as a function of the internuclear distance. Moreover, we clearly observe "ripple" effects, i.e., when a discontinuity in one of the QP energies induces (smaller) discontinuities in the other QP energies. Going from one branch to another implies a transfer of weight between two solutions of the QP equation. The cases of occupied, virtual, and frontier orbitals are separately discussed on distinct diatomics. In particular, we show that multisolution behavior in frontier orbitals is more likely if the HOMO-LUMO gap is small.
