Kállay, Mihály and Nagy, Péter and Ladóczki, Bence and Mester, Dávid (2026) A Linear-Scaling Integral-Direct Explicitly Correlated Second-Order Møller-Plesset Approach. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 22 (6). pp. 2946-2958. ISSN 1549-9618
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Abstract
We present an integral-direct, iteration-free, linear-scaling, local explicitly correlated second-order M & oslash;ller-Plesset (MP2-F12) approach, extending our previous local MP2 method [J. Chem. Theory Comput. 2016, 12, 4897]. The correlation contributions for individual electron pairs are computed within domains defined by the corresponding localized orbitals, while the correlation energies of spatially distant electron pairs are determined via multipole expansions. All the various types of integrals are computed and transformed directly, thereby precluding the need for integral storage and yielding asymptotically constant memory as well as negligible disk I/O demand. Another competitive advantage is the implementation of the 2B MP2-F12 ansatz, the most complete one so far with local approximations, enabling excellent basis set convergence even with double-zeta basis sets. Our validation studies indicate that the approach recovers at least 99.9% of the canonical MP2-F12 correlation energy and yields reaction energies with a mean error of less than 1 kJ/mol. With respect to the complete basis set limit of MP2, the error of our local approach is just slightly larger than that of canonical MP2-F12. With the new local MP2-F12 approach, we were able to compute the correlation energy for a small protein containing 644 atoms, which is the largest system ever considered in an explicitly correlated calculation.
| Item Type: | Article |
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| Additional Information: | Funding Agency and Grant Number: European Research Council [101076972]; Magyar Tudom?nyos Akad?mia [NA]; Nemzeti Kutat?si Fejleszt?si ?s Innov?ci?s Hivatal [FK142489] Funding text: The work is supported by the National Research, Development, and Innovation Office (NKFIH, grant nos. PD142372 and FK142489), the Janos Bolyai Research Scholarship of the Hungarian Academy of Sciences, and the ERC Starting Grant No. 101076972, "aCCuracy". The research reported in this paper is part of project BME-EGA-02, implemented with the support provided by the Ministry of Innovation and Technology of Hungary from the National Research, Development, and Innovation Fund, financed under the TKP2021 funding scheme. The Hungarian Governmental Information-Technology Development Agency is acknowledged for awarding access to the Komondor and the LEONARDO supercomputer, owned by the EuroHPC Joint Undertaking, hosted by CINECA (Italy) and the LEONARDO consortium. |
| Uncontrolled Keywords: | Chemistry, Physical; WAVE-FUNCTIONS; MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; PLESSET PERTURBATION-THEORY; ELECTRON CORRELATION METHODS; CONSISTENT BASIS-SETS; AUXILIARY BASIS-SETS; LOCAL CORRELATION APPROACH; CCSD(T) ENERGIES; |
| Subjects: | Q Science / természettudomány > QD Chemistry / kémia |
| SWORD Depositor: | MTMT SWORD |
| Depositing User: | MTMT SWORD |
| Date Deposited: | 10 Sep 2026 08:06 |
| Last Modified: | 10 Sep 2026 08:06 |
| URI: | https://real.mtak.hu/id/eprint/246005 |
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