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Title: Intensive Atomization Energy: Re-Thinking a Metric for Electronic Structure Theory Methods


Abstract The errors in atomization energies (

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Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for the Computational Design of Functional Layered Materials (CCDM)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Zeitschrift fuer Physikalische Chemie; Journal Volume: 230; Journal Issue: 5-7; Related Information: CCDM partners with Temple University (lead); Brookhaven National Laboratory; Drexel University; Duke University; North Carolina State University; Northeastern University; Princeton University; Rice University; University of Pennsylvania
Country of Publication:
United States
catalysis (heterogeneous), solar (photovoltaic), energy storage (including batteries and capacitors), hydrogen and fuel cells, defects, mechanical behavior, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Perdew, John P., Sun, Jianwei, Garza, Alejandro J., and Scuseria, Gustavo E. Intensive Atomization Energy: Re-Thinking a Metric for Electronic Structure Theory Methods. United States: N. p., 2016. Web. doi:10.1515/zpch-2015-0713.
Perdew, John P., Sun, Jianwei, Garza, Alejandro J., & Scuseria, Gustavo E. Intensive Atomization Energy: Re-Thinking a Metric for Electronic Structure Theory Methods. United States. doi:10.1515/zpch-2015-0713.
Perdew, John P., Sun, Jianwei, Garza, Alejandro J., and Scuseria, Gustavo E. 2016. "Intensive Atomization Energy: Re-Thinking a Metric for Electronic Structure Theory Methods". United States. doi:10.1515/zpch-2015-0713.
title = {Intensive Atomization Energy: Re-Thinking a Metric for Electronic Structure Theory Methods},
author = {Perdew, John P. and Sun, Jianwei and Garza, Alejandro J. and Scuseria, Gustavo E.},
abstractNote = {Abstract The errors in atomization energies (},
doi = {10.1515/zpch-2015-0713},
journal = {Zeitschrift fuer Physikalische Chemie},
number = 5-7,
volume = 230,
place = {United States},
year = 2016,
month = 1
  • Abstract The errors in atomization energies (
  • No abstract prepared.
  • While the formalism of multiresolution analysis (MRA), based on wavelets and adaptive integral representations of operators, is actively progressing in electronic structure theory (mostly on the independent-particle level and, recently, second-order perturbation theory), the concepts of multiresolution and adaptivity can also be utilized within the traditional formulation of correlated (many-particle) theory which is based on second quantization and the corresponding (generally nonorthogonal) tensor algebra. In this paper, we present a formalism called scale-adaptive tensor algebra (SATA) which exploits an adaptive representation of tensors of many-body operators via the local adjustment of the basis set quality. Given a series of locallymore » supported fragment bases of a progressively lower quality, we formulate the explicit rules for tensor algebra operations dealing with adaptively resolved tensor operands. The formalism suggested is expected to enhance the applicability and reliability of local correlated many-body methods of electronic structure theory, especially those directly based on atomic orbitals (or any other localized basis functions).« less
  • In many cases, variational transition states for a chemical reaction are significantly displaced from a saddle point because of zero-point and entropic effects that depend on the reaction coordinate. Such displacements are often controlled by the competition between the potential energy along the minimum-energy reaction path and the energy requirements of one or more vibrational modes whose frequencies show a large variation along the reaction path. In calculating reaction rates from potential-energy functions we need to take account of these factors and---especially at lower temperatures---to include tunneling contributions, which also depend on the variation of vibrational frequencies along a reactionmore » path. To include these effects requires more information about the activated complex region of the potential-energy surface than is required for conventional transition-state theory. In the present article we show how the vibrational and entropic effects of variational transition-state theory and the effective potentials and effective masses needed to calculate tunneling probabilities can be estimated with a minimum of electronic structure information, thereby allowing their computation at a higher level of theory than would otherwise be possible. As examples, we consider the reactions OH+H{sub 2}, CH{sub 3}+H{sub 2}, and Cl+CH{sub 4} and some of their isotopic analogs. We find for Cl+CH{sub 4}{r arrow}HCl+CH{sub 3} that the reaction rate is greatly enhanced by tunneling under conditions of interest for atmospheric chemistry.« less
  • Domain based local pair natural orbital coupled cluster theory with single-, double-, and perturbative triple excitations (DLPNO-CCSD(T)) is a highly efficient local correlation method. It is known to be accurate and robust and can be used in a black box fashion in order to obtain coupled cluster quality total energies for large molecules with several hundred atoms. While previous implementations showed near linear scaling up to a few hundred atoms, several nonlinear scaling steps limited the applicability of the method for very large systems. In this work, these limitations are overcome and a linear scaling DLPNO-CCSD(T) method for closed shellmore » systems is reported. The new implementation is based on the concept of sparse maps that was introduced in Part I of this series [P. Pinski, C. Riplinger, E. F. Valeev, and F. Neese, J. Chem. Phys. 143, 034108 (2015)]. Using the sparse map infrastructure, all essential computational steps (integral transformation and storage, initial guess, pair natural orbital construction, amplitude iterations, triples correction) are achieved in a linear scaling fashion. In addition, a number of additional algorithmic improvements are reported that lead to significant speedups of the method. The new, linear-scaling DLPNO-CCSD(T) implementation typically is 7 times faster than the previous implementation and consumes 4 times less disk space for large three-dimensional systems. For linear systems, the performance gains and memory savings are substantially larger. Calculations with more than 20 000 basis functions and 1000 atoms are reported in this work. In all cases, the time required for the coupled cluster step is comparable to or lower than for the preceding Hartree-Fock calculation, even if this is carried out with the efficient resolution-of-the-identity and chain-of-spheres approximations. The new implementation even reduces the error in absolute correlation energies by about a factor of two, compared to the already accurate previous implementation.« less