Doubly Hybrid Functionals Close to Chemical Accuracy for Both Finite and Extended Systems: Implementation and Test of XYG3 and XYGJ-OS

Overview

Journal JACS Au

Publisher American Chemical Society

Specialty Chemistry

Date 2021 Sep 1

PMID 34467317

Citations 6

Authors

Yizhen Wang

Yajing Li

Jun Chen

Igor Ying Zhang

Xin Xu

Affiliations

Soon will be listed here.

Abstract

While being widely used to understand the chemical reactions in heterogeneous catalysis or other multidisciplinary systems, a great challenge that semilocal and hybrid density functional approximations (DFAs) are facing is to deliver a uniformly accurate description for both finite and extended systems. Herein, we perform reliable and well-converged periodic calculations of two doubly hybrid approximations (DHAs), XYG3 and XYGJ-OS, and demonstrate that the good accuracy of DHAs achieved for molecules is transferable to the semiconductors and insulators. Such an accuracy is not only for energetic properties but also for the first- and second-order response properties, which is general for different kinds of chemical environments, including simple cubic bulks, perovskite-type transition metal oxides like TiO, and heterogeneous systems like CO adsorption on the NaCl(100) surface. The present finding has strengthened the predictive power of DFT, which not only will inspire the future development of the top-rung DFAs but also will boost their applications in multidisciplinary studies with high accuracy and efficiency.

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References

Paier J, Marsman M, Kresse G . Why does the B3LYP hybrid functional fail for metals?. J Chem Phys. 2007; 127(2):024103. DOI: 10.1063/1.2747249. View

Marsman M, Gruneis A, Paier J, Kresse G . Second-order Møller-Plesset perturbation theory applied to extended systems. I. Within the projector-augmented-wave formalism using a plane wave basis set. J Chem Phys. 2009; 130(18):184103. DOI: 10.1063/1.3126249. View

Sun J, Xiao B, Fang Y, Haunschild R, Hao P, Ruzsinszky A . Density functionals that recognize covalent, metallic, and weak bonds. Phys Rev Lett. 2014; 111(10):106401. DOI: 10.1103/PhysRevLett.111.106401. View

Gruneis A, Booth G, Marsman M, Spencer J, Alavi A, Kresse G . Natural Orbitals for Wave Function Based Correlated Calculations Using a Plane Wave Basis Set. J Chem Theory Comput. 2015; 7(9):2780-5. DOI: 10.1021/ct200263g. View

Chen B, Xu X . XO-PBC: An Accurate and Efficient Method for Molecular Crystals. J Chem Theory Comput. 2020; 16(7):4271-4285. DOI: 10.1021/acs.jctc.0c00232. View

Santra G, Sylvetsky N, Martin J . Minimally Empirical Double-Hybrid Functionals Trained against the GMTKN55 Database: revDSD-PBEP86-D4, revDOD-PBE-D4, and DOD-SCAN-D4. J Phys Chem A. 2019; 123(24):5129-5143. PMC: 9479158. DOI: 10.1021/acs.jpca.9b03157. View

Gorling , Levy . Exact Kohn-Sham scheme based on perturbation theory. Phys Rev A. 1994; 50(1):196-204. DOI: 10.1103/physreva.50.196. View

Barca G, McKenzie S, Bloomfield N, Gilbert A, Gill P . Q-MP2-OS: Møller-Plesset Correlation Energy by Quadrature. J Chem Theory Comput. 2020; 16(3):1568-1577. DOI: 10.1021/acs.jctc.9b01142. View

Bremond E, Adamo C . Seeking for parameter-free double-hybrid functionals: the PBE0-DH model. J Chem Phys. 2011; 135(2):024106. DOI: 10.1063/1.3604569. View

10.

Sharkas K, Toulouse J, Maschio L, Civalleri B . Double-hybrid density-functional theory applied to molecular crystals. J Chem Phys. 2014; 141(4):044105. DOI: 10.1063/1.4890439. View

11.

Perdew , Burke , Ernzerhof . Generalized Gradient Approximation Made Simple. Phys Rev Lett. 1996; 77(18):3865-3868. DOI: 10.1103/PhysRevLett.77.3865. View

12.

Zhang I, Xu X . Exploring the Limits of the XYG3-Type Doubly Hybrid Approximations for the Main-Group Chemistry: The xDH@B3LYP Model. J Phys Chem Lett. 2021; 12(10):2638-2644. DOI: 10.1021/acs.jpclett.1c00360. View

13.

Benighaus T, DiStasio Jr R, Lochan R, Chai J, Head-Gordon M . Semiempirical double-hybrid density functional with improved description of long-range correlation. J Phys Chem A. 2008; 112(12):2702-12. DOI: 10.1021/jp710439w. View

14.

Vogt J, Vogt B . The structure of carbon monoxide adsorbed on the NaCl(100) surface—a combined LEED and DFT-D/vdW-DF study. J Chem Phys. 2014; 141(21):214708. DOI: 10.1063/1.4903192. View

15.

Chai J, Head-Gordon M . Long-range corrected double-hybrid density functionals. J Chem Phys. 2009; 131(17):174105. DOI: 10.1063/1.3244209. View

16.

Marsman M, Paier J, Stroppa A, Kresse G . Hybrid functionals applied to extended systems. J Phys Condens Matter. 2011; 20(6):064201. DOI: 10.1088/0953-8984/20/6/064201. View

17.

Grimme S . Semiempirical hybrid density functional with perturbative second-order correlation. J Chem Phys. 2006; 124(3):034108. DOI: 10.1063/1.2148954. View

18.

Zhao Y, Truhlar D . A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions. J Chem Phys. 2006; 125(19):194101. DOI: 10.1063/1.2370993. View

19.

Mardirossian N, Head-Gordon M . Survival of the most transferable at the top of Jacob's ladder: Defining and testing the ωB97M(2) double hybrid density functional. J Chem Phys. 2018; 148(24):241736. PMC: 5991970. DOI: 10.1063/1.5025226. View

20.

Lee , Yang , PARR . Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B Condens Matter. 1988; 37(2):785-789. DOI: 10.1103/physrevb.37.785. View