An efficient, fragment-based electronic structure method for molecular systems: Self-consistent polarization with perturbative two-body exchange and dispersion

Jacobson, Leif D.; Herbert, John M.

doi:10.1063/1.3560026

Cited by 95 publications

(197 citation statements)

References 107 publications

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“…Second-order SAPT works well for non-covalent clusters whose interactions are dominated by polarisation (induction) and electrostatics, but inherits MP2's problems with overestimating dispersion energies in the basis-set limit. For dispersion-bound systems, good results are only obtained by carefully choosing a small basis set to exploit error cancellation [319,320].…”

Section: Qm/mm and Fragment Methodsmentioning

confidence: 99%

“…A fragment-based method for non-covalent interactions that is currently unique to Q-CHEM is an extended (cluster) version of symmetry-adapted perturbation theory [264,303,304,319,320]. This so-called XSAPT method generalises the traditional SAPT methodology [321] to clusters of arbitrary size, treating many-body polarisation effects in a self-consistent way but approximating other non-covalent interactions (exchange and dispersion) in a pairwise-additive but ab initio fashion.…”

Section: Qm/mm and Fragment Methodsmentioning

confidence: 99%

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Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Shao¹,

Gan²,

Epifanovsky³

et al. 2014

Molecular Physics

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2,746

2,077

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A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and openshell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly correlated Cr 2 dimer, exploring zeolitecatalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.Keywords quantum chemistry, software, electronic structure theory, density functional theory, electron correlation, computational modelling, Q-Chem Disciplines Chemistry CommentsThis article is from Molecular Physics: An International Journal at the Interface Between Chemistry and Physics 113 (2015): 184, doi:10.1080/00268976.2014. RightsWorks produced by employees of the U.S. Government as part of their official duties are not copyrighted within the U.S. The content of this document is not copyrighted. Authors 185A summary of the technical advances that are incorporated in the fourth major release of the Q-CHEM quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Some specific chemical examples include calculations on the strongly corre...

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Section: Qm/mm and Fragment Methodsmentioning

confidence: 99%

Section: Qm/mm and Fragment Methodsmentioning

confidence: 99%

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Shao¹,

Gan²,

Epifanovsky³

et al. 2014

Molecular Physics

Self Cite

2,746

2,077

View full text Add to dashboard Cite

show abstract

“…As an example, today the importance of both cooperativity [109][110][111] and intramolecular dispersion [112][113][114][115] in various aspects of chemistry is becoming increasingly clear. To date, no SAPT variant which is able to treat systems consisting of more than three fragments has been proposed and other perturbation based many-fragment approaches are also scarce (the efficient, but approximate XSAPT, 116 the Chemical Hamiltonian approach of Halász et al 117 and expensive, highly basis-set dependent supermolecular Møller-Plesset PT methods 118 are noteworthy, but scarcely applied, examples). For standard SAPT, the treatment of many-fragment systems is both expensive and complicated, as it necessitates imposing the antisymmetry condition multiple times.…”

Section: B Beyond and Beneath Dimersmentioning

confidence: 99%

“…145 Still, SAPT generally remains more costly than variational EDAs and visualization tools (vide infra). The work to improve efficiency has produced the aforementioned XSAPT 116,146 as well as linear-scaling SAPT, 147 but these approaches use modified or semiempirical dispersion expressions. Nevertheless, there are reasons tobelieve that the computational cost is becoming of diminishing importance.…”

Section: Applying Pt-based Edasmentioning

confidence: 99%

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

Pastorczak¹,

Corminbœuf²

2017

The Journal of Chemical Physics

110

102

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Today's quantum chemistry methods are extremely powerful but rely upon complex quantities such as the massively multidimensional wavefunction or even the simpler electron density. Consequently, chemical insight and a chemist's intuition are often lost in this complexity leaving the results obtained difficult to rationalize. To handle this overabundance of information, computational chemists have developed tools and methodologies that assist in composing a more intuitive picture that permits better understanding of the intricacies of chemical behavior. In particular, the fundamental comprehension of phenomena governed by non-covalent interactions is not easily achieved in terms of either the total wavefunction or the total electron density, but can be accomplished using more informative quantities. This perspective provides an overview of these tools and methods that have been specifically developed or used to analyze, identify, quantify, and visualize non-covalent interactions. These include the quantitative energy decomposition analysis schemes and the more qualitative class of approaches such as the Non-covalent Interaction index, the Density Overlap Region Indicator, or quantum theory of atoms in molecules. Aside from the enhanced knowledge gained from these schemes, their strengths, limitations, as well as a roadmap for expanding their capabilities are emphasized. ©2017Author(s

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“…[31][32][33] In addition, Turbomole [34] has its own implementation by the Della Sala group. [35][36][37][38][39] We also mention here that other embedding methods, which can be categorized as exact density embedding, exact orbital embedding, or electrostatic embedding, are now found in ADF, [40] MOLPRO, [41][42][43][44][45] Q-Chem, [46,47] CP2K, [48] NWChem, [49] and GAMESS. [50] In this work, we present a novel implementation of the FDE approach that aims at filling the following gap that has persisted over the years, namely, the absence of a code that: (1) has a proven strong parallel efficiency that consistently outperforms semilocal KS-DFT, (2) has the ability to Figure 1 [12] The k-point grids and simulation cells (basis sets) are subsystem-specific, achieving the best performance.…”

mentioning

confidence: 99%

eQE: An open‐source density functional embedding theory code for the condensed phase

Genova

Ceresoli

Krishtal

et al. 2017

Int J of Quantum Chemistry

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In this work, we present the main features and algorithmic details of a novel implementation of the frozen density embedding (FDE) formulation of subsystem density functional theory (DFT) that is specifically designed to enable ab initio molecular dynamics (AIMD) simulations of largescale condensed-phase systems containing 1000s of atoms. This code (available at http://eqe. rutgers.edu) has been given the moniker of embedded Quantum ESPRESSO (eQE) as it is a generalization of the open-source Quantum ESPRESSO (QE) suite of programs. The strengths of eQE reside in a hierarchical parallelization scheme that allows for an efficient and fully self-consistent treatment of the electronic structure (via the addition of an additional DIIS extrapolation layer) while simultaneously exploiting the inherent symmetries and periodicities in the system (via sampling of subsystem-specific first Brillouin zones and utilization of subsystem-specific basis sets).While bulk liquids and molecular crystals are two classes of systems that exemplify the utility of the FDE approach (as these systems can be partitioned into weakly interacting subunits), we show that eQE has significantly extended this regime of applicability by outperforming standard semilocal Kohn-Sham DFT (KS-DFT) for large-scale heterogeneous catalysts with quite different layerspecific electronic structure and intrinsic periodicities. eQE features very favorable strong parallel scaling for a model system of bulk liquid water composed of 256 water molecules, which allows for a significant decrease in the overall time to solution when compared to KS-DFT. We show that eQE achieves speedups greater than one order of magnitude (>103) when performing AIMD simulations of such large-scale condensed-phase systems as: (1) | I N T R O D U C T I O NThe Kohn-Sham (KS) formulation of density functional theory (DFT) [1] is currently the most widely employed electronic structure method in the fields of chemistry, physics, and materials science. This is largely due to the fact that KS-DFT employing semilocal exchange-correlation (xc) functionals produces models of remarkable accuracy and predictive capability [2] with a relatively low associated computational cost (that in general Int J Quantum Chem. 2017;117:e25401.

show abstract

An efficient, fragment-based electronic structure method for molecular systems: Self-consistent polarization with perturbative two-body exchange and dispersion

Cited by 95 publications

References 107 publications

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

Perspective: Found in translation: Quantum chemical tools for grasping non-covalent interactions

eQE: An open‐source density functional embedding theory code for the condensed phase

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