skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Perspective: Explicitly correlated electronic structure theory for complex systems

Authors:
 [1]; ORCiD logo [2];  [3];  [4]
  1. Max Planck Institute for Solid State Research, Heisenbergstrasse 1, 70569 Stuttgart, Germany, Department Chemie, Technische Universität München (TUM), Lichtenbergstrasse 4, D-85747 Garching, Germany, Graduate School of Science, Technology, and Innovation, Kobe University, Nada-ku, Kobe 657-8501, Japan
  2. Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA
  3. Graduate School of System Informatics, Kobe University, Nada-ku, Kobe 657-8501, Japan
  4. Graduate School of Science, Technology, and Innovation, Kobe University, Nada-ku, Kobe 657-8501, Japan, Graduate School of System Informatics, Kobe University, Nada-ku, Kobe 657-8501, Japan
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1349358
Grant/Contract Number:
FG02-11ER16211
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 8; Related Information: CHORUS Timestamp: 2018-02-14 19:35:19; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Grüneis, Andreas, Hirata, So, Ohnishi, Yu-ya, and Ten-no, Seiichiro. Perspective: Explicitly correlated electronic structure theory for complex systems. United States: N. p., 2017. Web. doi:10.1063/1.4976974.
Grüneis, Andreas, Hirata, So, Ohnishi, Yu-ya, & Ten-no, Seiichiro. Perspective: Explicitly correlated electronic structure theory for complex systems. United States. doi:10.1063/1.4976974.
Grüneis, Andreas, Hirata, So, Ohnishi, Yu-ya, and Ten-no, Seiichiro. Tue . "Perspective: Explicitly correlated electronic structure theory for complex systems". United States. doi:10.1063/1.4976974.
@article{osti_1349358,
title = {Perspective: Explicitly correlated electronic structure theory for complex systems},
author = {Grüneis, Andreas and Hirata, So and Ohnishi, Yu-ya and Ten-no, Seiichiro},
abstractNote = {},
doi = {10.1063/1.4976974},
journal = {Journal of Chemical Physics},
number = 8,
volume = 146,
place = {United States},
year = {Tue Feb 28 00:00:00 EST 2017},
month = {Tue Feb 28 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1063/1.4976974

Citation Metrics:
Cited by: 5works
Citation information provided by
Web of Science

Save / Share:
  • The principal challenge in using explicitly correlated wavefunctions for molecules is the evaluation of nonfactorizable integrals over the coordinates of three or more electrons. Immense progress was made in tackling this problem through the introduction of a single-particle resolution of the identity. Decompositions of sufficient accuracy can be achieved, but only with large auxiliary basis sets. Density fitting is an alternative integral approximation scheme, which has proven to be very reliable for two-electron integrals. Here, we extend density fitting to the treatment of all three-electron integrals that appear at the MP2-F12/3*A level of theory. We demonstrate that the convergence ofmore » energies with respect to auxiliary basis size is much more rapid with density fitting than with the traditional resolution-of-the-identity approach.« less
  • The nuclear electronic orbital (NEO) reduced explicitly correlated Hartree-Fock (RXCHF) approach couples select electronic orbitals to the nuclear orbital via Gaussian-type geminal functions. This approach is extended to enable the use of a restricted basis set for the explicitly correlated electronic orbitals and an open-shell treatment for the other electronic orbitals. The working equations are derived and the implementation is discussed for both extensions. The RXCHF method with a restricted basis set is applied to HCN and FHF{sup −} and is shown to agree quantitatively with results from RXCHF calculations with a full basis set. The number of many-particle integralsmore » that must be calculated for these two molecules is reduced by over an order of magnitude with essentially no loss in accuracy, and the reduction factor will increase substantially for larger systems. Typically, the computational cost of RXCHF calculations with restricted basis sets will scale in terms of the number of basis functions centered on the quantum nucleus and the covalently bonded neighbor(s). In addition, the RXCHF method with an odd number of electrons that are not explicitly correlated to the nuclear orbital is implemented using a restricted open-shell formalism for these electrons. This method is applied to HCN{sup +}, and the nuclear densities are in qualitative agreement with grid-based calculations. Future work will focus on the significance of nonadiabatic effects in molecular systems and the further enhancement of the NEO-RXCHF approach to accurately describe such effects.« less
  • A discretization for an explicitly correlated formulation of the electronic Schroedinger equation based on hyperbolic wavelets and exponential sum approximations of potentials is described, covering mathematical results as well as algorithmic realization, and discussing in particular the potential of methods of this type for parallel computing.
  • Monte Carlo (MC) simulations and an analytical theory are presented to describe electronic excitation transport (EET) among static chromophores constrained to lie on the surfaces of spherical micelles. Both donor--trap (DT) and donor--donor (DD) EET are examined for two types of systems: probe molecules on the surfaces of isolated (low concentration) micelles, and probes on the surfaces of interacting (concentrated) micelles. The EET dynamics are described by the function, [l angle][ital G][sup [ital s]]([ital t])[r angle], the probability of finding the excitation on the originally excited chromophore. For the isolated micelle calculations, the excitation dynamics depend on the distribution ofmore » probes on a single hard sphere surface. For the interacting micelle calculations, the hard sphere structure is accounted for by using the radial pair distribution function, g([ital r]). Both single micelle and many micelle DT calculations do not involve approximations. Consequently, the DT expressions agree exactly with the MC calculations. For the DD calculations, a first order cumulant approximation is used to obtain analytically tractable solutions to [l angle][ital G][sup [ital s]]([ital t])[r angle]. Pade approximants of the cumulant solution, accurate over a broad range of chromophore number and Foerster interaction strengths, are used to describe DD EET on isolated micelles. For DD EET in many micelle systems, the first order cumulant approach is shown to be a suitable method for intermicelle structural studies. Both the cumulant and MC calculations are simultaneously compared to time resolved flourescence depolarization measurements performed on octadecylrhodamine B(ODRB)/triton X-100/water systems made in previous investigations.« less
  • Abstract is currently not available for viewing at this time.