Efficient Estimation of Formation Enthalpies for Closed-Shell Organic Compounds with Local Coupled-Cluster Methods

Paulechka, Eugene; Kazakov, Andrei F.

doi:10.1021/acs.jctc.8b00593

Cited by 42 publications

(102 citation statements)

References 57 publications

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“…The strong pair selection and ED construction controlled by ε w = 10 –5 E h were found to be similarly accurate previously for a number of alternative systems containing up to 260 atoms and for various reaction and interaction energies involving closed-shell systems. 38 , 89 , 90 , 134 , 135 …”

Section: Accuracy Of the Local Approximationsmentioning

confidence: 99%

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

Szabó

Csóka

Kállay

et al. 2021

J. Chem. Theory Comput.

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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.

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Section: Accuracy Of the Local Approximationsmentioning

confidence: 99%

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

Szabó

Csóka

Kállay

et al. 2021

J. Chem. Theory Comput.

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“…To obtain a deeper insight into the antiradical properties, the thermodynamics of these processes for C 10 (DAPANO) 2 and C 10 PDA was evaluated using the DFT approach (B3LYP, B2PLYP, and M06-2X) and the ab initio coupled cluster-type method [DLPNO-CCSD(T)]). The DLPNO-CCSD(T) method has been reported to reproduce results of the “golden standard” canonical CCSD(T) while remaining computationally feasible for real chemical systems [ 32 , 33 , 34 , 35 , 36 , 37 ]. Moreover, the excellent performance of the DLPNO-CCSD(T) method has been confirmed for the determination of the energetics of the hydrogen atom transfer reaction [ 38 ].…”

Section: Resultsmentioning

confidence: 99%

Antiradical Properties of N-Oxide Surfactants—Two in One

Lewińska

Kulbacka

Domżał-Kędzia

et al. 2021

IJMS

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Surfactants are molecules that lower surface or interfacial tension, and thus they are broadly used as detergents, wetting agents, emulsifiers, foaming agents, or dispersants. However, for modern applications, substances that can perform more than one function are desired. In this study we evaluated antioxidant properties of two homological series of N-oxide surfactants: monocephalic 3-(alkanoylamino)propyldimethylamine-N-oxides and dicephalic N,N-bis[3 ,3′-(dimethylamino)propyl]alkylamide di-N-oxides. Their antiradical properties were tested against stable radicals using electron paramagnetic resonance (EPR) and UV-vis spectroscopy. The experimental investigation was supported by theoretical density functional theory (DFT) and ab initio modeling of the X–H bonds dissociation enthalpies, ionization potentials, and Gibbs free energies for radical scavenging reactions. The evaluation was supplemented with a study of biological activity. We found that the mono- and di-N-oxides are capable of scavenging reactive radicals; however, the dicephalic surfactants are more efficient than their linear analogues.

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“…Despite excellent performance of the DLPNO-CCSD(T) approach in reproducing coinage metals-noncovalently bonded ligands dissociation enthalpies, 39 reaction energies, 20,24,40,76,77 gas phase heats of formation of inorganic 36 and organic substances, 38,78,79 a few recent works revealed some limitations as well. Chen and coworkers found that DLPNO-CCSD(T) method significantly overestimated gas phase bond dissociation energies in proton bound organic dimers.…”

Section: A Accuracy Of the Dlpno−ccsd(t) Methodsmentioning

confidence: 99%

Evaluation of experimental alkali metal ion–ligand noncovalent bond strengths with DLPNO-CCSD(T) method

Maity

Minenkov

Cavallo

2019

The Journal of Chemical Physics

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We applied the domain based local pair natural orbital coupled cluster approach with single, double, and perturbative triple excitations, DLPNO-CCSD(T), to rationalize more than 130 experimental bond dissociation enthalpies collected in the work of Rodgers and Armentrout [Chem. Rev. 116, 5642-5687 (2016)] and involving alkali metal cations and versatile neutral organic and inorganic ligands ranging from common solvents to amino acids. In general, a remarkable agreement has been obtained between predicted and experimental alkali metal ionligand noncovalent bond strengths, highlighting a high degree of reliability of data assembled by Rodgers and Armentrout. In the case of some inconsistent experimental data given for some species, we pointed to a number for which best agreement with DLPNO-CCSD(T) calculations has been achieved. In addition, we refined a couple of ∆H 0 for which DLPNO-CCSD(T) values turned out to be significantly different from their experimental counterparts. We suggest an application of the DLPNO-CCSD(T) to derive the reference values to train/validate force field and neural network methods to be further applied in molecular dynamic simulations to unravel the mechanisms in biological systems and alkali metal ion batteries.

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Efficient Estimation of Formation Enthalpies for Closed-Shell Organic Compounds with Local Coupled-Cluster Methods

Cited by 42 publications

References 57 publications

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

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

Antiradical Properties of N-Oxide Surfactants—Two in One

Evaluation of experimental alkali metal ion–ligand noncovalent bond strengths with DLPNO-CCSD(T) method

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