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Linear-Scaling Open-Shell MP2 Approach: Algorithm, Benchmarks, and Large-Scale Applications.

ABSTRACT: A linear-scaling local second-order Møller-Plesset (MP2) method is presented for high-spin open-shell molecules based on restricted open-shell (RO) reference functions. The open-shell local MP2 (LMP2) approach inherits the iteration- and redundancy-free formulation and the completely integral-direct, OpenMP-parallel, and memory and disk use economic algorithms of our closed-shell LMP2 implementation. By utilizing restricted local molecular orbitals for the demanding integral transformation step and by introducing a novel long-range spin-polarization approximation, the computational cost of RO-LMP2 approaches that of closed-shell LMP2. Extensive benchmarks were performed for reactions of radicals, ionization potentials, as well as spin-state splittings of carbenes and transition-metal complexes. Compared to the conventional MP2 reference for systems of up to 175 atoms, local errors of at most 0.1 kcal/mol were found, which are well below the intrinsic accuracy of MP2. RO-LMP2 computations are presented for challenging protein models of up to 601 atoms and 11 000 basis functions, which involve either spin states of a complexed iron ion or a highly delocalized singly occupied orbital. The corresponding runtimes of 9-15 h obtained with a single, many-core CPU demonstrate that MP2, as well as spin-scaled MP2 and double-hybrid density functional methods, become widely accessible for open-shell systems of unprecedented size and complexity.

SUBMITTER: Szabo PB

PROVIDER: S-EPMC8154337 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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Linear-Scaling Open-Shell MP2 Approach: Algorithm, Benchmarks, and Large-Scale Applications.

Szabó P Bernát PB Csóka József J Kállay Mihály M Nagy Péter R PR

Journal of chemical theory and computation 20210405 5

A linear-scaling local second-order Møller-Plesset (MP2) method is presented for high-spin open-shell molecules based on restricted open-shell (RO) reference functions. The open-shell local MP2 (LMP2) approach inherits the iteration- and redundancy-free formulation and the completely integral-direct, OpenMP-parallel, and memory and disk use economic algorithms of our closed-shell LMP2 implementation. By utilizing restricted local molecular orbitals for the demanding integral transformation step ...[more]

PMID: 33819030

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Project description:The extension of the highly optimized local natural orbital (LNO) coupled cluster (CC) with single-, double-, and perturbative triple excitations [LNO-CCSD(T)] method is presented for high-spin open-shell molecules based on restricted open-shell references. The techniques enabling the outstanding efficiency of the closed-shell LNO-CCSD(T) variant are adopted, including the iteration- and redundancy-free second-order Møller-Plesset and (T) formulations as well as the integral-direct, memory- and disk use-economic, and OpenMP-parallel algorithms. For large molecules, the efficiency of our open-shell LNO-CCSD(T) method approaches that of its closed-shell parent method due to the application of restricted orbital sets for demanding integral transformations and a novel approximation for higher-order long-range spin-polarization effects. The accuracy of open-shell LNO-CCSD(T) is extensively tested for radicals and reactions thereof, ionization processes, as well as spin-state splittings, and transition-metal compounds. At the size range where the canonical CCSD(T) reference is accessible (up to 20-30 atoms), the average open-shell LNO-CCSD(T) correlation energies are found to be 99.9 to 99.95% accurate, which translates into average absolute deviations of a few tenths of kcal/mol in the investigated energy differences already with the default settings. For more extensive molecules, the local errors may grow, but they can be estimated and decreased via affordable systematic convergence studies. This enables the accurate modeling of large systems with complex electronic structures, as illustrated on open-shell organic radicals and transition-metal complexes of up to 179 atoms as well as on challenging biochemical systems, including up to 601 atoms and 11,000 basis functions. While the protein models involve difficulties for local approximations, such as the spin states of a bounded iron ion or an extremely delocalized singly occupied orbital, the corresponding single-node LNO-CCSD(T) computations were feasible in a matter of days with 10s to 100 GB of memory use. Therefore, the new LNO-CCSD(T) implementation enables highly accurate computations for open-shell systems of unprecedented size and complexity with widely accessible hardware.

Project description:Recent advances in local electron correlation approaches have enabled the relatively routine access to CCSD(T) [that is, coupled cluster (CC) with single, double, and perturbative triple excitations] computations for molecules of a hundred or more atoms. Here, approaching their complete basis set (CBS) limit becomes more challenging due to extensive basis set superposition errors, often necessitating the use of large atomic orbital (AO) basis sets with diffuse functions. Here, we study a potential remedy in the form of non-atom-centered or floating orbitals (FOs). FOs are still rarely employed even for small molecules due to the practical complication of defining their position, number, exponents, etc. The most frequently used FO method thus simply places a single FO center with a large number of FOs toward the middle of noncovalent dimers; however, a single FO center for larger complexes can soon become insufficient. A recent alternative uses a grid of FO centers around the monomers with a single s function per center, which is currently applicable only for H, C, N, and O atoms. Here, we build on the above advantages and mitigate some drawbacks of previous FO approaches by using a layer of FO centers and 4-9 FOs/center for each monomer. Thus, a double layer of FOs is placed between the interacting subsystems. When extending the double-ζ AO basis with this double layer of FOs, the quality of conventional augmented double-ζ or conventional triple-ζ AO bases can be reached or surpassed with less orbitals, leading to few tenths of a kcal/mol basis set errors for medium-sized dimers. This good performance extends to larger molecules (shown here up to 72 atoms), as efficient local natural orbital (LNO) CCSD(T) computations with only double-ζ AO and 4 FOs/center FO bases match our LNO-CCSD(T)/CBS reference within ca. 0.1 kcal/mol. These developments introduce FO methods to the accurate modeling of large molecular complexes without limitations to atom types by further accelerating efficient correlation calculations, like LNO-CCSD(T).

Dataset Information

Linear-Scaling Open-Shell MP2 Approach: Algorithm, Benchmarks, and Large-Scale Applications.

Publications

Linear-Scaling Open-Shell MP2 Approach: Algorithm, Benchmarks, and Large-Scale Applications.

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