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Title: How Accurate Are the Minnesota Density Functionals for Noncovalent Interactions, Isomerization Energies, Thermochemistry, and Barrier Heights Involving Molecules Composed of Main-Group Elements?

Abstract

The 14 Minnesota density functionals published between the years 2005 and early 2016 are benchmarked on a comprehensive database of 4986 data points (84 data sets) involving molecules composed of main-group elements. The database includes noncovalent interactions, isomerization energies, thermochemistry, and barrier heights, as well as equilibrium bond lengths and equilibrium binding energies of noncovalent dimers. Additionally, the sensitivity of the Minnesota density functionals to the choice of basis set and integration grid is explored for both noncovalent interactions and thermochemistry. By and large, the main strength of the hybrid Minnesota density functionals is that the best ones provide very good performance for thermochemistry (e.g., M06-2X), barrier heights (e.g., M08-HX, M08-SO, MN15), and systems heavily characterized by self-interaction error (e.g., M06-2X, M08-HX, M08-SO, MN15), while the main weakness is that none of them are state-of-the-art for the full spectrum of noncovalent interactions and isomerization energies (although M06-2X is recommended from the 10 hybrid Minnesota functionals). Similarly, the main strength of the local Minnesota density functionals is that the best ones provide very good performance for thermochemistry (e.g., MN15-L), barrier heights (e.g., MN12-L), and systems heavily characterized by self-interaction error (e.g., MN12-L and MN15-L), while the main weakness is that nonemore » of them are state-of-the-art for the full spectrum of noncovalent interactions and isomerization energies (although M06-L is clearly the best from the four local Minnesota functionals). Finally, as an overall guide, M06-2X and MN15 are perhaps the most broadly useful hybrid Minnesota functionals, while M06-L and MN15-L are perhaps the most broadly useful local Minnesota functionals, although each has different strengths and weaknesses.« less

Authors:
 [1];  [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Center for Theoretical Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)
OSTI Identifier:
1377487
Grant/Contract Number:  
AC02-05CH11231; AC03-76SF00098
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 12; 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

Mardirossian, Narbe, and Head-Gordon, Martin. How Accurate Are the Minnesota Density Functionals for Noncovalent Interactions, Isomerization Energies, Thermochemistry, and Barrier Heights Involving Molecules Composed of Main-Group Elements?. United States: N. p., 2016. Web. doi:10.1021/acs.jctc.6b00637.
Mardirossian, Narbe, & Head-Gordon, Martin. How Accurate Are the Minnesota Density Functionals for Noncovalent Interactions, Isomerization Energies, Thermochemistry, and Barrier Heights Involving Molecules Composed of Main-Group Elements?. United States. https://doi.org/10.1021/acs.jctc.6b00637
Mardirossian, Narbe, and Head-Gordon, Martin. 2016. "How Accurate Are the Minnesota Density Functionals for Noncovalent Interactions, Isomerization Energies, Thermochemistry, and Barrier Heights Involving Molecules Composed of Main-Group Elements?". United States. https://doi.org/10.1021/acs.jctc.6b00637. https://www.osti.gov/servlets/purl/1377487.
@article{osti_1377487,
title = {How Accurate Are the Minnesota Density Functionals for Noncovalent Interactions, Isomerization Energies, Thermochemistry, and Barrier Heights Involving Molecules Composed of Main-Group Elements?},
author = {Mardirossian, Narbe and Head-Gordon, Martin},
abstractNote = {The 14 Minnesota density functionals published between the years 2005 and early 2016 are benchmarked on a comprehensive database of 4986 data points (84 data sets) involving molecules composed of main-group elements. The database includes noncovalent interactions, isomerization energies, thermochemistry, and barrier heights, as well as equilibrium bond lengths and equilibrium binding energies of noncovalent dimers. Additionally, the sensitivity of the Minnesota density functionals to the choice of basis set and integration grid is explored for both noncovalent interactions and thermochemistry. By and large, the main strength of the hybrid Minnesota density functionals is that the best ones provide very good performance for thermochemistry (e.g., M06-2X), barrier heights (e.g., M08-HX, M08-SO, MN15), and systems heavily characterized by self-interaction error (e.g., M06-2X, M08-HX, M08-SO, MN15), while the main weakness is that none of them are state-of-the-art for the full spectrum of noncovalent interactions and isomerization energies (although M06-2X is recommended from the 10 hybrid Minnesota functionals). Similarly, the main strength of the local Minnesota density functionals is that the best ones provide very good performance for thermochemistry (e.g., MN15-L), barrier heights (e.g., MN12-L), and systems heavily characterized by self-interaction error (e.g., MN12-L and MN15-L), while the main weakness is that none of them are state-of-the-art for the full spectrum of noncovalent interactions and isomerization energies (although M06-L is clearly the best from the four local Minnesota functionals). Finally, as an overall guide, M06-2X and MN15 are perhaps the most broadly useful hybrid Minnesota functionals, while M06-L and MN15-L are perhaps the most broadly useful local Minnesota functionals, although each has different strengths and weaknesses.},
doi = {10.1021/acs.jctc.6b00637},
url = {https://www.osti.gov/biblio/1377487}, journal = {Journal of Chemical Theory and Computation},
issn = {1549-9618},
number = 9,
volume = 12,
place = {United States},
year = {2016},
month = {8}
}

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Works referenced in this record:

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Twelve outstanding problems in ground-state density functional theory: A bouquet of puzzles
journal, January 2011


Challenges for Density Functional Theory
journal, December 2011


Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993


Generalized Gradient Approximation Made Simple
journal, October 1996


Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999


A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006


M11-L: A Local Density Functional That Provides Improved Accuracy for Electronic Structure Calculations in Chemistry and Physics
journal, December 2011


MN15-L: A New Local Exchange-Correlation Functional for Kohn–Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids
journal, February 2016


Exchange-correlation functional with broad accuracy for metallic and nonmetallic compounds, kinetics, and noncovalent interactions
journal, October 2005


Improving the Accuracy of Hybrid Meta-GGA Density Functionals by Range Separation
journal, October 2011


Screened-exchange density functionals with broad accuracy for chemistry and solid-state physics
journal, January 2012


Density Functionals for Inorganometallic and Organometallic Chemistry
journal, December 2005


Delocalization errors in density functionals and implications for main-group thermochemistry
journal, November 2008


Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionals
journal, November 1997


Quest for a universal density functional: the accuracy of density functionals across a broad spectrum of databases in chemistry and physics
journal, March 2014

  • Peverati, Roberto; Truhlar, Donald G.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 372, Issue 2011
  • https://doi.org/10.1098/rsta.2012.0476

Simulation of delocalized exchange by local density functionals
journal, March 2000


Correlation energy of an inhomogeneous electron gas: A coordinate‐space model
journal, January 1988


A novel form for the exchange-correlation energy functional
journal, July 1998


Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999


Correlation energies in the spin-density functional formalism: II. Applications and empirical corrections
journal, January 1980


Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992


Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006


A standard grid for density functional calculations
journal, July 1993


Nonlocal van der Waals density functional: The simpler the better
journal, December 2010


Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992


Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon
journal, January 1993


Polarization consistent basis sets: Principles
journal, November 2001


Polarization consistent basis sets. II. Estimating the Kohn–Sham basis set limit
journal, May 2002


Polarization consistent basis sets. III. The importance of diffuse functions
journal, November 2002


Fully optimized contracted Gaussian basis sets for atoms Li to Kr
journal, August 1992


Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr
journal, April 1994


Gaussian basis sets of quadruple zeta valence quality for atoms H–Kr
journal, December 2003


Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005


Property-optimized Gaussian basis sets for molecular response calculations
journal, October 2010


Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014


Benchmark Interaction Energies for Biologically Relevant Noncovalent Complexes Containing Divalent Sulfur
journal, January 2012


Advanced Corrections of Hydrogen Bonding and Dispersion for Semiempirical Quantum Mechanical Methods
journal, December 2011


Formal Estimation of Errors in Computed Absolute Interaction Energies of Protein−Ligand Complexes
journal, February 2011


Effects of Heteroatoms on Aromatic π−π Interactions: Benzene−Pyridine and Pyridine Dimer
journal, February 2009


Performance of spin-component-scaled Møller–Plesset theory (SCS-MP2) for potential energy curves of noncovalent interactions
journal, January 2007


Benchmark database of accurate (MP2 and CCSD(T) complete basis set limit) interaction energies of small model complexes, DNA base pairs, and amino acid pairs
journal, January 2006


Benchmark Calculations of Noncovalent Interactions of Halogenated Molecules
journal, September 2012


Beyond Energies: Geometries of Nonbonded Molecular Complexes as Metrics for Assessing Electronic Structure Approaches
journal, March 2015


Hydrocarbon/Water Interactions: Encouraging Energetics and Structures from DFT but Disconcerting Discrepancies for Hessian Indices
journal, April 2012


Basis Set Convergence of the Post-CCSD(T) Contribution to Noncovalent Interaction Energies
journal, June 2014


S66: A Well-balanced Database of Benchmark Interaction Energies Relevant to Biomolecular Structures
journal, July 2011


Extensions of the S66 Data Set: More Accurate Interaction Energies and Angular-Displaced Nonequilibrium Geometries
journal, October 2011


Benchmark Calculations of Three-Body Intermolecular Interactions and the Performance of Low-Cost Electronic Structure Methods
journal, June 2015


Accuracy of Several Wave Function and Density Functional Theory Methods for Description of Noncovalent Interaction of Saturated and Unsaturated Hydrocarbon Dimers
journal, June 2012


An accurate benchmark description of the interactions between carbon dioxide and polyheterocyclic aromatic compounds containing nitrogen
journal, January 2015


Assessment of Coupled Cluster Theory and more Approximate Methods for Hydrogen Bonded Systems
journal, September 2013


Basis set limit coupled-cluster studies of hydrogen-bonded systems
journal, February 2015


Density Functional Theory and Hydrogen Bonds: Are We There Yet?
journal, February 2015


Accurate Description of Intermolecular Interactions Involving Ions Using Symmetry-Adapted Perturbation Theory
journal, May 2015


Accurate and Efficient Quantum Chemistry Calculations for Noncovalent Interactions in Many-Body Systems: The XSAPT Family of Methods
journal, December 2014


Benchmark Structures and Binding Energies of Small Water Clusters with Anharmonicity Corrections
journal, November 2011


The Performance of Density Functionals for Sulfate–Water Clusters
journal, February 2013


Evaluation of B3LYP, X3LYP, and M06-Class Density Functionals for Predicting the Binding Energies of Neutral, Protonated, and Deprotonated Water Clusters
journal, March 2009


Performance of Density Functional Theory Procedures for the Calculation of Proton-Exchange Barriers: Unusual Behavior of M06-Type Functionals
journal, July 2014


New accurate benchmark energies for large water clusters: DFT is better than expected
journal, January 2014


Binding in Radical-Solvent Binary Complexes: Benchmark Energies and Performance of Approximate Methods
journal, February 2013


Halogen Bonds: Benchmarks and Theoretical Analysis
journal, March 2013


On the Reliability of Pure and Hybrid DFT Methods for the Evaluation of Halogen, Chalcogen, and Pnicogen Bonds Involving Anionic and Neutral Electron Donors
journal, October 2013


Halogen Bonding from Dispersion-Corrected Density-Functional Theory: The Role of Delocalization Error
journal, November 2014


Why are the Interaction Energies of Charge-Transfer Complexes Challenging for DFT?
journal, April 2012


Conformational Equilibria in Butane-1,4-diol: A Benchmark of a Prototypical System with Strong Intramolecular H-bonds
journal, December 2013


Performance of Ab Initio and Density Functional Methods for Conformational Equilibria of C n H 2 n +2 Alkane Isomers ( n = 4−8)
journal, October 2009


Conformers of Gaseous Cysteine
journal, May 2009


What Can We Learn about Dispersion from the Conformer Surface of n -Pentane?
journal, March 2013


High-Level Ab Initio Electronic Structure Calculations of Water Clusters (H 2 O) 16 and (H 2 O) 17 : A New Global Minimum for (H 2 O) 16
journal, October 2010


The Melatonin Conformer Space: Benchmark and Assessment of Wave Function and DFT Methods for a Paradigmatic Biological and Pharmacological Molecule
journal, March 2013


Benchmark ab Initio Conformational Energies for the Proteinogenic Amino Acids through Explicitly Correlated Methods. Assessment of Density Functional Methods
journal, December 2015


An assessment of theoretical procedures for π -conjugation stabilisation energies in enones
journal, December 2014


W4-11: A high-confidence benchmark dataset for computational thermochemistry derived from first-principles W4 data
journal, July 2011


What Are the Ground State Structures of C 20 and C 24 ? An Explicitly Correlated Ab Initio Approach
journal, December 2015


Gaussian‐2 theory for molecular energies of first‐ and second‐row compounds
journal, June 1991


Benchmark Database of Barrier Heights for Heavy Atom Transfer, Nucleophilic Substitution, Association, and Unimolecular Reactions and Its Use to Test Theoretical Methods
journal, March 2005


Multi-coefficient extrapolated density functional theory for thermochemistry and thermochemical kinetics
journal, January 2005


Effectiveness of Diffuse Basis Functions for Calculating Relative Energies by Density Functional Theory
journal, March 2003


The Mechanism of Dihydrogen Activation by Frustrated Lewis Pairs Revisited
journal, January 2010


A dataset of highly accurate homolytic NBr bond dissociation energies obtained by Means of W2 theory
journal, October 2015


Assessment of Theoretical Procedures for Calculating Barrier Heights for a Diverse Set of Water-Catalyzed Proton-Transfer Reactions
journal, April 2012


Heats of formation of platonic hydrocarbon cages by means of high-level thermochemical procedures
journal, June 2015


Representative Benchmark Suites for Barrier Heights of Diverse Reaction Types and Assessment of Electronic Structure Methods for Thermochemical Kinetics
journal, December 2006


Can DFT and ab initio methods describe all aspects of the potential energy surface of cycloreversion reactions?
journal, September 2015


Ground-state correlation energies for atomic ions with 3 to 18 electrons
journal, May 1993


The van der Waals potentials between all the rare gas atoms from He to Rn
journal, March 2003


Kinetics of hydrogen-transfer isomerizations of butoxyl radicals
journal, January 2010


Kinetics of the Hydrogen Atom Abstraction Reactions from 1-Butanol by Hydroxyl Radical: Theory Matches Experiment and More
journal, January 2013


Avoiding singularity problems associated with meta-GGA (generalized gradient approximation) exchange and correlation functionals containing the kinetic energy density
journal, December 2007


Oscillations in meta-generalized-gradient approximation potential energy surfaces for dispersion-bound complexes
journal, July 2009


Integration Grid Errors for Meta-GGA-Predicted Reaction Energies: Origin of Grid Errors for the M06 Suite of Functionals
journal, January 2010


Mapping the genome of meta-generalized gradient approximation density functionals: The search for B97M-V
journal, February 2015


Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory
journal, May 2016


ω B97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlation
journal, June 2016


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010


Effect of the damping function in dispersion corrected density functional theory
journal, March 2011


Reformulation of the D3(Becke–Johnson) Dispersion Correction without Resorting to Higher than C 6 Dispersion Coefficients
journal, June 2015


Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008


Semilocal and hybrid meta-generalized gradient approximations based on the understanding of the kinetic-energy-density dependence
journal, January 2013


Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections
journal, November 2012


Strongly Constrained and Appropriately Normed Semilocal Density Functional
journal, July 2015


Comment on “Generalized Gradient Approximation Made Simple”
journal, January 1998


Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980


Works referencing / citing this record:

Strategic Design and Utilization of Molecular Flexibility for Straddling the Application of Organic Superbases: A DFT Study
journal, January 2018


A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions
journal, January 2017


The S66 Non-Covalent Interactions Benchmark Reconsidered Using Explicitly Correlated Methods Near the Basis Set Limit
journal, January 2018


Interaction between water and carbon nanostructures: How good are current density functional approximations?
journal, October 2019


Statistical analysis of activation and reaction energies with quasi-variational coupled-cluster theory
journal, November 2017


The halogen bond with isocyano carbon reduces isocyanide odor
journal, June 2020


Silver(I) complexes with long-chain diamines in non-aqueous solvents: Thermodynamic and modeling studies
journal, August 2019


Computational prediction of chiroptical properties in structure elucidation of natural products
journal, January 2019


A Benchmark of Density Functional Approximations For Thermochemistry and Kinetics of Hydride Reductions of Cyclohexanones
journal, June 2019


para -Aminosalicylic acid in the treatment of manganese toxicity. Complexation of Mn 2+ with 4-amino-2-hydroxybenzoic acid and its N -acetylated metabolite
journal, January 2018


Kinetically controlled asymmetric synthesis of silicon-stereogenic methoxy silanes using a planar chiral ferrocene backbone
journal, January 2019


Vibrational Signatures of Chirality Recognition Between α‐Pinene and Alcohols for Theory Benchmarking
journal, June 2019


Conformational preferences of N -acetyl- N ′-methylprolineamide in different media: a 1 H NMR and theoretical investigation
journal, January 2019


Machine learning prediction of coordination energies for alkali group elements in battery electrolyte solvents
journal, January 2019


Amyloid fibrils from organic solutions of an amphiphilic dipeptide
journal, January 2019


Fantasy versus reality in fragment-based quantum chemistry
journal, November 2019


Atlas of putative minima and low-lying energy networks of water clusters n = 3–25
journal, December 2019


Reactivity of Gold(I) Monocarbene Complexes with Protein Targets: A Theoretical Study
journal, February 2019


Stretching of cis -formic acid: warm-up and cool-down as molecular work-out
journal, January 2019


A GAP‐GTPase‐GDP‐P i Intermediate Crystal Structure Analyzed by DFT Shows GTP Hydrolysis Involves Serial Proton Transfers
journal, May 2019


Highly Selective Halide Receptors Based on Chalcogen, Pnicogen, and Tetrel Bonds
journal, November 2016


Computational investigation of the α 2 β 1 integrin–collagen triple helix complex interaction
journal, January 2018


Ionic liquid containing electron-rich, porous polyphosphazene nanoreactors catalyze the transformation of CO 2 to carbonates
journal, January 2018


Structured water chains in external electric fields
journal, September 2019


Errors in DFT integration grids and their potential impact on chemical shift calculations
journal, December 2019


Thermochemical Conversion of Guaiacol in Aqueous Phase by Density Functional Theory
journal, May 2019


Ligand dynamics and protonation preferences of Rh and Ir complexes bearing an almost, but not quite, pendent base
journal, January 2018


Delayed catalyst function enables direct enantioselective conversion of nitriles to NH 2 -amines
journal, April 2019


Computational Insights into Mg‐Cl Complex Electrolytes for Rechargeable Magnesium Batteries
journal, June 2019


Unraveling the regioselectivity of odd electron halogen bond formation using electrophilicity index and chemical hardness parameters
journal, January 2019


DFT simulation of Watson–Crick-like guanine–thymine mismatch in quaternary systems involving DNA bases
journal, December 2019


Mechanistic investigation in the [1,4] and [1,2] Wittig rearrangement reactions: a DFT study
journal, January 2018


Density functional theory and ab initio studies on hyperfine coupling constants of phosphinyl radicals
journal, October 2018


Vibrational Signatures of Chirality Recognition Between α‐Pinene and Alcohols for Theory Benchmarking
journal, May 2019