Optimization of the linear-scaling local natural orbital CCSD(T) method: Redundancy-free triples correction using Laplace transform.

@article{Nagy2017OptimizationOT,
  title={Optimization of the linear-scaling local natural orbital CCSD(T) method: Redundancy-free triples correction using Laplace transform.},
  author={P{\'e}ter R. Nagy and Mih{\'a}ly K{\'a}llay},
  journal={The Journal of chemical physics},
  year={2017},
  volume={146 21},
  pages={
          214106
        }
}
An improved algorithm is presented for the evaluation of the (T) correction as a part of our local natural orbital (LNO) coupled-cluster singles and doubles with perturbative triples [LNO-CCSD(T)] scheme [Z. Rolik et al., J. Chem. Phys. 139, 094105 (2013)]. The new algorithm is an order of magnitude faster than our previous one and removes the bottleneck related to the calculation of the (T) contribution. First, a numerical Laplace transformed expression for the (T) fragment energy is… 

Figures and Tables from this paper

Optimization of the Linear-Scaling Local Natural Orbital CCSD(T) Method: Improved Algorithm and Benchmark Applications.
TLDR
The integral-direct, in-core, highly efficient domain construction technique of the local second-order Møller-Plesset (LMP2) scheme is extended to the CC level and the memory demand, the domain and LNO construction, the auxiliary basis compression, and the previously rate-determining two-external integral transformation have been significantly improved.
Communication: An improved linear scaling perturbative triples correction for the domain based local pair-natural orbital based singles and doubles coupled cluster method [DLPNO-CCSD(T)].
TLDR
An improved perturbative triples correction (T) algorithm for domain based local pair-natural orbital singles and doubles coupled cluster (DLPNO-CCSD) theory is reported, using triples natural orbitals to represent the virtual spaces for triples amplitudes, storage bottlenecks are avoided.
Basis set truncation corrections for improved frozen natural orbital CCSD(T) energies
A number of approaches are proposed and assessed to reduce the frozen natural orbital (FNO) truncation error of coupled-cluster singles and doubles with perturbative triples [CCSD(T)] energies. The
Approaching the basis set limit of CCSD(T) energies for large molecules with local natural orbital coupled-cluster methods.
TLDR
It is demonstrated that the complete basis set limit (CBS) of LNO-CCSD(T) energies can be reliably approached via basis set extrapolation using large basis sets including diffuse functions.
Accurate spin-densities based on the domain-based local pair-natural orbital coupled-cluster theory.
TLDR
This paper extends the DLPNO-based Lagrangian scheme to the high-spin open-shell reference cases, thus enabling the accurate computation of the electron- and spin-densities for large open- shell species and applies this newly developed approach to various first-order electronic and magnetic properties such as isotropic and anisotropic components in the hyperfine coupling interactions and the electric field gradient.
Integral-direct and parallel implementation of the CCSD(T) method: algorithmic developments and large-scale applications.
TLDR
The efficiency of this implementation allowed us to perform some of the largest CCSD(T) calculations ever presented for systems of 31-43 atoms and 1037-1569 orbitals using only 4-8 many-core CPUs and 1-3 days of wall time.
Reduced-scaling correlation methods for the excited states of large molecules: implementation and benchmarks for the second-order algebraic-diagrammatic construction approach.
TLDR
The presented reduced-scaling algorithm allows us to carry out correlated excited-state calculations using triple-zeta basis sets with diffuse functions for systems of up to 400 atoms or 13000 atomic orbitals in a matter of days using an 8-core processor.
Analytical gradient for the domain-based local pair natural orbital second order Møller-Plesset perturbation theory method (DLPNO-MP2).
TLDR
The formally complete analytical gradient is derived for the domain-based local pair natural orbital second order Møller-Plesset (MP2) perturbation theory method and a procedure is introduced to circumvent instabilities of the gradient caused by singular coupled-perturbed localization equations.
Accurate Reduced-Cost CCSD(T) Energies: Parallel Implementation, Benchmarks, and Large-Scale Applications
TLDR
The accurate and systematically improvable frozen natural orbital (FNO) and natural auxiliary function (NAF) cost-reducing approaches are combined with recent coupled-cluster singles, doubles, and perturbative triples implementations to create the practically “gold standard” quality FNO-CCSD(T) method.
A Quadratic Pair Atomic Resolution of the Identity Based SOS-AO-MP2 Algorithm Using Slater Type Orbitals
We report a production level implementation of pair atomic resolution of the identity (PARI) based second-order Møller–Plesset perturbation theory (MP2) in the Slater type orbital (STO) based
...
...

References

SHOWING 1-10 OF 144 REFERENCES
An efficient linear-scaling CCSD(T) method based on local natural orbitals.
TLDR
Test calculations demonstrate that currently the improved version of the general-order local coupled-cluster (CC) approach is one of the most efficient local CCSD(T) approaches and can be routinely applied to molecules of up to 100 atoms with reasonable basis sets.
Perturbative triples correction for local pair natural orbital based explicitly correlated CCSD(F12*) using Laplace transformation techniques.
We present an implementation of pair natural orbital coupled cluster singles and doubles with perturbative triples, PNO-CCSD(T), which avoids the quasi-canonical triples approximation (T0) where
The orbital-specific virtual local triples correction: OSV-L(T).
TLDR
The interaction energies of the guanine-cytosine dimers in the Watson-Crick and stacked arrangements are investigated at the level of local coupled cluster theory with singles and doubles and perturbative triples and new complete-basis-set-limit estimates are proposed.
Linear-Scaling Coupled Cluster with Perturbative Triple Excitations: The Divide-Expand-Consolidate CCSD(T) Model.
We propose a reformulation of the traditional (T) triples correction to the coupled cluster singles and doubles (CCSD) energy in terms of local Hartree-Fock (HF) orbitals such that its structural
The CCSD(T) Model With Cholesky Decomposition of Orbital Energy Denominators
TLDR
The Cholesky algorithm is better suited for studying large systems and shows a speed-up factor larger than O-2/V, and in general at most 5 vectors are needed to get a precision of mu E-h.
Low-order scaling local electron correlation methods. V. Connected triples beyond (T): Linear scaling local CCSDT-1b
A new O(N ) method for the iterative treatment of connected triple substitutions in the framework of local coupled cluster theory is introduced here, which is the local equivalent of the canonical
An efficient and near linear scaling pair natural orbital based local coupled cluster method.
TLDR
This work redesigns the LPNO-CCSD method with a new method based on the combination of the concepts of PNOs and projected atomic orbitals (PAOs), which is as accurate as the original method while leading to computational savings exceeding one order of magnitude for larger systems.
Cost reduction of high-order coupled-cluster methods via active-space and orbital transformation techniques.
TLDR
It is demonstrated that high-order CC calculations are possible for considerably larger systems than before using the implemented techniques, and the orbital transformation techniques outperform the active-space approaches.
Linear-scaling implementation of the direct random-phase approximation.
TLDR
The linear-scaling implementation of the direct random-phase approximation (dRPA) for closed-shell molecular systems is reported and it is demonstrated that the new method enables dRPA calculations for molecules with more than 1000 atoms and 10,000 basis functions on a single processor.
Efficient Parallel Implementation of the CCSD External Exchange Operator and the Perturbative Triples (T) Energy Calculation.
TLDR
An efficient parallel implementation of the perturbative triples correction to CCSD and related methods is described, using the Array Files tool for distributed filesystems, which allows the simultaneous use of two normally conflicting techniques for speeding up the C CSD procedure.
...
...