Title: Assessment of two hybrid van der Waals density functionals for covalent and non-covalent binding of molecules

Abstract

Two hybrid van der Waals density functionals (vdW-DFs) are developed using 25% Fock exchange with (i) the consistent-exchange vdW-DF-cx functional [K. Berland and P. Hyldgaard, Phys. Rev. B 89, 035412 (2014)] and (ii) with the vdW-DF2 functional [K. Lee et al., Phys. Rev. B 82, 081101 (2010)]. The ability to describe covalent and non-covalent binding properties of molecules is assessed. For properties related to covalent binding, atomization energies (G2-1 set), molecular reaction energies (G2RC set), and ionization energies (G21IP set) are benchmarked against experimental reference values. We find that hybrid-vdW-DF-cx yields results that are rather similar to those of the standard non-empirical hybrid PBE0 [C. Adamo and V. Barone, J. Chem. Phys. 110, 6158 (1999)], with mean average deviations (MADs) of 4.9 and 5.0 kcal/mol for the G2-1 set, respectively. In this comparison, experimental reference values are used, back corrected by wavefunction-based quantum-chemistry calculations of zero-point energies. Hybrid vdW-DF2 follows somewhat different trends, showing on average significantly larger deviations from the reference energies, with a MAD of 14.5 kcal/mol for the G2-1 set. Non-covalent binding properties of molecules are assessed using the S22 benchmark set of non-covalently bonded dimers and the X40 set of dimers of small halogenated molecules, usingmore » wavefunction-based quantum chemistry results as references. For the S22 set, hybrid-vdW-DF-cx performs better than standard vdW-DF-cx for the mostly hydrogen-bonded systems, with MAD dropping from 0.6 to 0.3 kcal/mol, but worse for purely dispersion-bonded systems, with MAD increasing from 0.2 to 0.6 kcal/mol. Hybrid-vdW-DF2 offers a slight improvement over standard vdW-DF2. Similar trends are found for the X40 set, with hybrid-vdW-DF-cx performing particularly well for binding energies involving the strongly polar hydrogen halides, but poorly for systems with tiny binding energies. Our study of the X40 set reveals the potential of mixing Fock exchange with vdW-DF, but also highlights shortcomings of the hybrids constructed here. In conclusion, the solid performance of hybrid-vdW-DF-cx for covalent-bonded systems, as well as the strengths and issues uncovered for non-covalently bonded systems, makes this study a good starting point for developing even more accurate hybrid vdW-DFs.« less

Authors:

Berland, Kristian ^[1]; Jiao, Yang  ^[2];

• Search DOE PAGES for author "Jiao, Yang"
• Search DOE PAGES for ORCID "0000-0003-4771-0088"

Lee, Jung-Hoon ^[3]; Rangel, Tonatiuh ^[3]; Neaton, Jeffrey B. ^[4]; Hyldgaard, Per  ^[2]

• Search DOE PAGES for author "Hyldgaard, Per"
• Search DOE PAGES for ORCID "0000-0001-5810-8119"

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+ Show Author Affiliations

1. Univ. of Oslo, Oslo (Norway). Centre for Materials Science and Nanotechnology (SMN), Dept. of Physics
2. Chalmers Univ. of Technology, Gothenburg (Sweden). Microtechnology and Nanoscience–MC2
3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics
4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Kavli Energy NanoScience Inst. at Berkeley, Berkeley, CA (United States)

Publication Date:

Wed Jun 21 00:00:00 EDT 2017

Research Org.:

Univ. of California, Berkeley, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); Swedish Research Council (SRC); Research Council of Norway; Swedish National Infrastructure for Computing (SNIC)

OSTI Identifier:

1388990

Alternate Identifier(s):

OSTI ID: 1364666

Grant/Contract Number:  

SC0001015; AC02-05CH11231; 2016-10-12

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Chemical Physics

Additional Journal Information:

Journal Volume: 146; Journal Issue: 23; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 0021-9606

Publisher:

American Institute of Physics (AIP)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)