Complexity Reduction in Large Quantum Systems: Fragment Identification and Population Analysis via a Local Optimized Minimal Basis

doi:https://doi.org/10.1021/acs.jctc.7b00291

Title: Complexity Reduction in Large Quantum Systems: Fragment Identification and Population Analysis via a Local Optimized Minimal Basis

Full Record
Other Related Research

Abstract

We present, within Kohn-Sham Density Functional Theory calculations, a quantitative method to identify and assess the partitioning of a large quantum mechanical system into fragments. We then introduce a simple and efficient formalism (which can be written as generalization of other well-known population analyses) to extract, from first principles, electrostatic multipoles for these fragments. The corresponding fragment multipoles can in this way be seen as reliable (pseudo-) observables. By applying our formalism within the code BigDFT, we show that the usage of a minimal set of in-situ optimized basis functions is of utmost importance for having at the same time a proper fragment definition and an accurate description of the electronic structure. With this approach it becomes possible to simplify the modeling of environmental fragments by a set of multipoles, without notable loss of precision in the description of the active quantum mechanical region. Furthermore, this leads to a considerable reduction of the degrees of freedom by an effective coarsegraining approach, eventually also paving the way towards efficient QM/QM and QM/MM methods coupling together different levels of accuracy.

Authors:

^[1]; Masella, Michel ^[2]; Ratcliff, Laura E. ^[3]; Genovese, Luigi ^[4]

Barcelona Supercomputing Center (BSC), Barcelona (Spain)
Institut de Biologie et de Technologie de Saclay, Gif-sur-Yvette Cedex (France)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. Grenoble Alpes, Grenoble (France); CEA, Grenoble (France)

Publication Date:: 2017-07-21

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: European Commission, Community Research and Development Information Service (CORDIS), EXTended Model of Organic Semiconductors (ExtMOS); Energy Oriented Centre of Excellence (EoCoE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Argonne National Laboratory, Argonne Leadership Computing Facility; MaX Centre of Excellence

OSTI Identifier:: 1400406

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of Chemical Theory and Computation

Additional Journal Information:: Journal Volume: 13; Journal Issue: 9; Journal ID: ISSN 1549-9618

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Mohr, Stephan, Masella, Michel, Ratcliff, Laura E., and Genovese, Luigi. Complexity Reduction in Large Quantum Systems: Fragment Identification and Population Analysis via a Local Optimized Minimal Basis.  United States: N. p., 2017. 
        Web.  doi:10.1021/acs.jctc.7b00291.

Copy to clipboard


                    Mohr, Stephan, Masella, Michel, Ratcliff, Laura E., & Genovese, Luigi. Complexity Reduction in Large Quantum Systems: Fragment Identification and Population Analysis via a Local Optimized Minimal Basis.  United States.  https://doi.org/10.1021/acs.jctc.7b00291

Copy to clipboard


                    Mohr, Stephan, Masella, Michel, Ratcliff, Laura E., and Genovese, Luigi. Fri .  
        "Complexity Reduction in Large Quantum Systems: Fragment Identification and Population Analysis via a Local Optimized Minimal Basis".  United States.  https://doi.org/10.1021/acs.jctc.7b00291.  https://www.osti.gov/servlets/purl/1400406.

Copy to clipboard


                    
@article{osti_1400406,

  title        = {Complexity Reduction in Large Quantum Systems: Fragment Identification and Population Analysis via a Local Optimized Minimal Basis},

  author       = {Mohr, Stephan and Masella, Michel and Ratcliff, Laura E. and Genovese, Luigi},

  abstractNote = {We present, within Kohn-Sham Density Functional Theory calculations, a quantitative method to identify and assess the partitioning of a large quantum mechanical system into fragments. We then introduce a simple and efficient formalism (which can be written as generalization of other well-known population analyses) to extract, from first principles, electrostatic multipoles for these fragments. The corresponding fragment multipoles can in this way be seen as reliable (pseudo-) observables. By applying our formalism within the code BigDFT, we show that the usage of a minimal set of in-situ optimized basis functions is of utmost importance for having at the same time a proper fragment definition and an accurate description of the electronic structure. With this approach it becomes possible to simplify the modeling of environmental fragments by a set of multipoles, without notable loss of precision in the description of the active quantum mechanical region. Furthermore, this leads to a considerable reduction of the degrees of freedom by an effective coarsegraining approach, eventually also paving the way towards efficient QM/QM and QM/MM methods coupling together different levels of accuracy.},

  doi          = {10.1021/acs.jctc.7b00291},

  url          = {https://www.osti.gov/biblio/1400406},
  journal      = {Journal of Chemical Theory and Computation},

  issn         = {1549-9618},

  number       = 9,

  volume       = 13,

  place        = {United States},

  year         = {2017},

  month        = {7}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.jctc.7b00291

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 4 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Computation of the free energy due to electron density fluctuation of a solute in solution: A QM/MM method with perturbation approach combined with a theory of solutions

Journal Article Suzuoka, Daiki ; Takahashi, Hideaki ; Morita, Akihiro - Journal of Chemical Physics

We developed a perturbation approach to compute solvation free energy Δμ within the framework of QM (quantum mechanical)/MM (molecular mechanical) method combined with a theory of energy representation (QM/MM-ER). The energy shift η of the whole system due to the electronic polarization of the solute is evaluated using the second-order perturbation theory (PT2), where the electric field formed by surrounding solvent molecules is treated as the perturbation to the electronic Hamiltonian of the isolated solute. The point of our approach is that the energy shift η, thus obtained, is to be adopted for a novel energy coordinate of the distributionmore »« less
https://doi.org/10.1063/1.4870037
Fragment approach to constrained density functional theory calculations using Daubechies wavelets

Journal Article Ratcliff, Laura E., E-mail: lratcliff@anl.gov ; Université de Grenoble Alpes, CEA, INAC-SP2M, L-Sim, F-38000 Grenoble ; Genovese, Luigi ; ... - Journal of Chemical Physics

In a recent paper, we presented a linear scaling Kohn-Sham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix ofmore »« less
https://doi.org/10.1063/1.4922378
Fragment approach to constrained density functional theory calculations using Daubechies wavelets

Journal Article Ratcliff, Laura E. ; Genovese, Luigi ; Mohr, Stephan ; ... - Journal of Chemical Physics

In a recent paper, we presented a linear scaling Kohn-Sham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix ofmore »« less
Cited by 6
https://doi.org/10.1063/1.4922378

Full Text Available
A Wigner Monte Carlo approach to density functional theory

Journal Article Sellier, J.M., E-mail: jeanmichel.sellier@gmail.com ; Dimov, I. - Journal of Computational Physics

In order to simulate quantum N-body systems, stationary and time-dependent density functional theories rely on the capacity of calculating the single-electron wave-functions of a system from which one obtains the total electron density (Kohn–Sham systems). In this paper, we introduce the use of the Wigner Monte Carlo method in ab-initio calculations. This approach allows time-dependent simulations of chemical systems in the presence of reflective and absorbing boundary conditions. It also enables an intuitive comprehension of chemical systems in terms of the Wigner formalism based on the concept of phase-space. Finally, being based on a Monte Carlo method, it scales verymore »« less
https://doi.org/10.1016/J.JCP.2014.03.065
Electron dynamics in complex environments with real-time time dependent density functional theory in a QM-MM framework

Journal Article Morzan, Uriel N. ; Ramírez, Francisco F. ; Scherlis, Damián A., E-mail: damian@qi.fcen.uba.ar, E-mail: mcgl@qb.ffyb.uba.ar ; ... - Journal of Chemical Physics

This article presents a time dependent density functional theory (TDDFT) implementation to propagate the Kohn-Sham equations in real time, including the effects of a molecular environment through a Quantum-Mechanics Molecular-Mechanics (QM-MM) hamiltonian. The code delivers an all-electron description employing Gaussian basis functions, and incorporates the Amber force-field in the QM-MM treatment. The most expensive parts of the computation, comprising the commutators between the hamiltonian and the density matrix—required to propagate the electron dynamics—, and the evaluation of the exchange-correlation energy, were migrated to the CUDA platform to run on graphics processing units, which remarkably accelerates the performance of the code.more »« less
https://doi.org/10.1063/1.4871688

Similar Records