Improved Accuracy and Efficiency in Quantum Embedding through Absolute Localization

Chulhai, Dhabih V.; Goodpaster, Jason D.

doi:10.1021/acs.jctc.7b00034

Cited by 70 publications

(138 citation statements)

References 45 publications

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“…Numerous studies have utilized each of these localization approaches to success as an aid to reduce computational cost. Examples include the use of PM localization to improve the accuracy and efficiency of quantum embedding, the use of FB localization for quantum treatment of protons with the reduced explicitly correlated HF approach, and the use of both localization approaches for the development of a linear scaling implementation of the direct random‐phase approximation …”

Section: Introductionmentioning

confidence: 99%

Domain‐based local pair natural orbital methods within the correlation consistent composite approach

Patel

Wilson

2019

J Comput Chem

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Ab initio composite approaches have been utilized to model and predict main group thermochemistry within 1 kcal mol −1 , on average, from well-established reliable experiments, primarily for molecules with less than 30 atoms. For molecules of increasing size and complexity, such as biomolecular complexes, composite methodologies have been limited in their application. Therefore, the domain-based local pair natural orbital (DLPNO) methods have been implemented within the correlation consistent composite approach (ccCA) framework, namely DLPNO-ccCA, to reduce the computational cost (disk space, CPU (central processing unit) time, memory) and predict energetic properties such as enthalpies of formation, noncovalent interactions, and conformation energies for organic biomolecular complexes including one of the largest molecules examined via composite strategies, within 1 kcal mol −1 , after calibration with 119 molecules and a set of linear alkanes.

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Section: Introductionmentioning

confidence: 99%

Domain‐based local pair natural orbital methods within the correlation consistent composite approach

Patel

Wilson

2019

J Comput Chem

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“…In a previous paper, however, our group demonstrated higher accuracy for absolutely localized WF-in-DFT reaction energies than for supersystem basis WF-in-DFT reaction energies. 64 We attribute this improved accuracy to systematic error cancellation.…”

Section: Complex Subsystem Divisionsmentioning

confidence: 98%

“…Our group generalized the Huzinaga level-shift projection operator with a freeze-and-thaw localization scheme and demonstrated significant success using absolute localization on molecular and periodic systems. 64,77 In order to make WF-in-DFT embedding feasible for large systems, the number of valence orbitals in the WF region must be managed. Including the basis functions of the full system in the embedded WF subsystem simply moves orbitals not occupied in the WF subsystem to the virtual space, which for CC calculations actually increases the computational cost upon embedding due to the higher scaling of CC methods with respect to virtual orbitals compared to occupied orbitals.…”

Section: Introductionmentioning

confidence: 99%

Robust, Accurate, and Efficient: Quantum Embedding Using the Huzinaga Level-Shift Projection Operator for Complex Systems

Graham

Wen

Chulhai

et al. 2020

J. Chem. Theory Comput.

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Wave function (WF) in density functional theory (DFT) embedding methods provide a framework for performing localized, high accuracy WF calculations on a system, while not incurring the full computational cost of the WF calculation on the full system. In order to effectively partition a system into localized WF and DFT subsystems, we utilize the Huzinaga level-shift projection operator within an absolutely localized basis. In this work, we study the ability of the absolutely localized Huzinaga level-shift projection operator method to study complex WF and DFT partitions, including partitions between multiple covalent bonds, a double bond, and transition metal-ligand bonds. We find that our methodology can accurately describe all of these complex partitions. Additionally, we study the robustness of this method with respect to the 1 arXiv:1911.12449v1 [physics.chem-ph] 27 Nov 2019 WF method, specifically where the embedded systems were described using a multiconfigurational WF method. We found that the method is systematically improvable with respect to both the number of atoms in the WF region and the size of the basis set used, with energy errors less than 1 kcal/mol. Additionally, we calculated the adsorption energy of H 2 to a model of an iron metal organic framework to within 1 kcal/mol compared to CASPT2 calculations performed on the full model while incurring only a small fraction of the full computational cost. This work demonstrates that the absolutely localized Huzinaga level-shift projection operator method is applicable to very complex systems with difficult electronic structures.

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“…The simplest and most popular option still consists in the implementation of TDDFT within the QM/MM [22][23][24][25] (quantum mechanics / molecular mechanics) scheme. However, more interestingly, TDDFT has been also interfaced with fully quantum mechanical embedding methods, such as the density matrix [26][27][28][29] and density functional embedding approaches [30][31][32][33][34][35][36][37][38][39][40][41][42] . In the former case, TDDFT has been coupled with the Embedded Mean Field Theory (EMFT) 28 , as suggested by Manby and Miller, who proposed the so-called Linear-Response Time-Dependent EMFT (LR-TD-EMFT) 43 , or by Parkhill and coworkers, who actually exploited the blockorthogonalized version of EMFT and extended it to Real-Time Time-Dependent Density Functional Theory (RT-TDDFT) 44 .…”

Section: Introductionmentioning

confidence: 99%

Quantum Mechanics / Extremely Localized Molecular Orbital Embedding Strategy for Excited-States. 1. Coupling to Time-Dependent Density Functional Theory

Macetti¹,

Genoni²

2020

Preprint

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The QM/ELMO (quantum mechanics / extremely localized molecular orbital) method is a recently developed embedding technique in which the most important region of the system under exam is treated at fully quantum mechanical level, while the rest is described by means of transferred and frozen extremely localized molecular orbitals. In this paper, we propose the first application of the QM/ELMO approach to the investigation of excited-states and, in particular, we present the coupling of the QM/ELMO philosophy with Time-Dependent Density Functional Theory (TDDFT). The proposed TDDFT/ELMO strategy has been subjected to a series of preliminary tests that were already considered for the validations of other embedding TDDFT methods. The obtained results show that the novel technique allows the accurate description of local excitations in large systems by only including a relatively small group of atoms in the region treated at fully quantum chemical level. Furthermore, it was observed that, even using functionals that do not take into account long-range corrections, the method enables to avoid the presence of artificial low-lying charge-transfer states that may affect traditional TDDFT calculations. Finally, through the application to a reduced model of the Green Fluorescent Protein, it was proved that the TDDFT/ELMO approach can be also successfully exploited to investigate local electronic transitions in large systems and that the accuracy of the results can be improved by including a sufficient number of fragments/residues that are chemically crucial in the quantum mechanical region. This work paves the way to further extensions of the QM/ELMO philosophy for the study of local excitations in extended systems, suggesting the coupling of the QM/ELMO approach with other quantum chemical methods for excited-states, from the simplest ΔSCF techniques to the most advanced and computationally expensive multi-references methods.

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Improved Accuracy and Efficiency in Quantum Embedding through Absolute Localization

Cited by 70 publications

References 45 publications

Domain‐based local pair natural orbital methods within the correlation consistent composite approach

Domain‐based local pair natural orbital methods within the correlation consistent composite approach

Robust, Accurate, and Efficient: Quantum Embedding Using the Huzinaga Level-Shift Projection Operator for Complex Systems

Quantum Mechanics / Extremely Localized Molecular Orbital Embedding Strategy for Excited-States. 1. Coupling to Time-Dependent Density Functional Theory

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