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Title: Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms

Abstract

While many transition metal complexes are known to have high multireference character, the multireference character of main-group closed-shell singlet diatomic molecules like BeF, CaO, and MgO has been less studied. Yet, many group-1 and group-2 diatomic molecules do have multireference character, and they provide informative systems for studying multireference character because they are simpler than transition metal compounds. The goal of the present work is to understand these multireference systems better so that, ultimately, we can apply what we learn to more complicated multireference systems and to the design of new exchange-correlation functionals for treating multireference systems more adequately. Fourteen main-group diatomic molecules and one triatomic molecule (including radicals, cations, and anions, as well as neutral closed-shell species) have been studied for this article. Eight of these molecules contain a group-1 element, and six contain a group-2 element. Seven of these molecules are multireference systems, and eight of them are single-reference systems. Fifty-three exchange-correlation functionals of 11 types [local spin-density approximation (LSDA), generalized gradient approximation (GGA), nonseparable gradient approximation (NGA), global-hybrid GGA, meta-GGA, meta-NGA, global-hybrid meta GGA, range-separated hybrid GGA, range-separated hybrid meta-GGA, range-separated hybrid meta-NGA, and DFT augmented with molecular mechanics damped dispersion (DFT-D)] and the Hartree–Fock method havemore » been applied to calculate the bond distance, bond dissociation energy (BDE), and dipole moment of these molecules. All of the calculations are converged to a stable solution by allowing the symmetry of the Slater determinant to be broken. A reliable functional should not only predict an accurate BDE but also predict accurate components of the BDE, so each bond dissociation energy has been decomposed into ionization potential (IP) of the electropositive element, electron affinity of the electronegative bonding partner (EA), atomic excitation energy (EE) to prepare the valence states of the interacting partners, and interaction energy (IE) of the valence-prepared states. Adding Hartree–Fock exchange helps to obtain better results for atomic excitation energy, and this leads to improvements in getting the right answer for the right reason. The following functionals are singled out for reasonably good performance on all three of bond distance, BDE, and dipole moment: B97-1, B97-3, MPW1B95, M05, M06, M06-2X, M08-SO, N12-SX, O3LYP, TPSS, τ-HCTHhyb, and GAM; all but two (TPSS and GAM) of these functionals are hybrid functionals.« less

Authors:
 [1];  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1388610
Grant/Contract Number:  
SC0012702
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 11; Journal Issue: 7; Related Information: ICDC partners with University of Minnesota(lead); Argonne National Laboratory; Clemson University; Dow Chemical Company; Northwestern University; Pacific Northwest National Laboratory; University of California Davis; University of Washington; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); materials and chemistry by design; synthesis (novel materials)

Citation Formats

Yu, Haoyu, and Truhlar, Donald G. Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms. United States: N. p., 2015. Web. doi:10.1021/acs.jctc.5b00083.
Yu, Haoyu, & Truhlar, Donald G. Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms. United States. https://doi.org/10.1021/acs.jctc.5b00083
Yu, Haoyu, and Truhlar, Donald G. 2015. "Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms". United States. https://doi.org/10.1021/acs.jctc.5b00083. https://www.osti.gov/servlets/purl/1388610.
@article{osti_1388610,
title = {Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms},
author = {Yu, Haoyu and Truhlar, Donald G.},
abstractNote = {While many transition metal complexes are known to have high multireference character, the multireference character of main-group closed-shell singlet diatomic molecules like BeF, CaO, and MgO has been less studied. Yet, many group-1 and group-2 diatomic molecules do have multireference character, and they provide informative systems for studying multireference character because they are simpler than transition metal compounds. The goal of the present work is to understand these multireference systems better so that, ultimately, we can apply what we learn to more complicated multireference systems and to the design of new exchange-correlation functionals for treating multireference systems more adequately. Fourteen main-group diatomic molecules and one triatomic molecule (including radicals, cations, and anions, as well as neutral closed-shell species) have been studied for this article. Eight of these molecules contain a group-1 element, and six contain a group-2 element. Seven of these molecules are multireference systems, and eight of them are single-reference systems. Fifty-three exchange-correlation functionals of 11 types [local spin-density approximation (LSDA), generalized gradient approximation (GGA), nonseparable gradient approximation (NGA), global-hybrid GGA, meta-GGA, meta-NGA, global-hybrid meta GGA, range-separated hybrid GGA, range-separated hybrid meta-GGA, range-separated hybrid meta-NGA, and DFT augmented with molecular mechanics damped dispersion (DFT-D)] and the Hartree–Fock method have been applied to calculate the bond distance, bond dissociation energy (BDE), and dipole moment of these molecules. All of the calculations are converged to a stable solution by allowing the symmetry of the Slater determinant to be broken. A reliable functional should not only predict an accurate BDE but also predict accurate components of the BDE, so each bond dissociation energy has been decomposed into ionization potential (IP) of the electropositive element, electron affinity of the electronegative bonding partner (EA), atomic excitation energy (EE) to prepare the valence states of the interacting partners, and interaction energy (IE) of the valence-prepared states. Adding Hartree–Fock exchange helps to obtain better results for atomic excitation energy, and this leads to improvements in getting the right answer for the right reason. The following functionals are singled out for reasonably good performance on all three of bond distance, BDE, and dipole moment: B97-1, B97-3, MPW1B95, M05, M06, M06-2X, M08-SO, N12-SX, O3LYP, TPSS, τ-HCTHhyb, and GAM; all but two (TPSS and GAM) of these functionals are hybrid functionals.},
doi = {10.1021/acs.jctc.5b00083},
url = {https://www.osti.gov/biblio/1388610}, journal = {Journal of Chemical Theory and Computation},
issn = {1549-9618},
number = 7,
volume = 11,
place = {United States},
year = {2015},
month = {5}
}

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Works referenced in this record:

What Dominates the Error in the CaO Diatomic Bond Energy Predicted by Various Approximate Exchange–Correlation Functionals?
journal, May 2014


W4 theory for computational thermochemistry: In pursuit of confident sub-kJ/mol predictions
journal, October 2006


Basis set convergence of post-CCSD contributions to molecular atomization energies
journal, August 2007


A fifth-order perturbation comparison of electron correlation theories
journal, May 1989


Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994


Note on an Approximation Treatment for Many-Electron Systems
journal, October 1934


MP2 energy evaluation by direct methods
journal, December 1988


Performance of W4 theory for spectroscopic constants and electrical properties of small molecules
journal, October 2010


The electronic structure of Be and BeO: benchmark EMS measurements and LCAO calculations
journal, March 2003


Valence States of BeO Feynman's Way
journal, January 2000


Ab initio studies of the low-lying states of BeO
journal, January 1992


An atomic charge study of highly ionic diatomic molecular systems: Highly Ionic Diatomic Molecular Systems
journal, October 2009


Minimally augmented Karlsruhe basis sets
journal, December 2010


Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon
journal, September 1995


Self‐consistent molecular orbital methods. XVIII. Constraints and stability in Hartree–Fock theory
journal, April 1977


Stability analysis for solutions of the closed shell Kohn–Sham equation
journal, June 1996


A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980


Multireference Model Chemistries for Thermochemical Kinetics
journal, July 2008


Molecular Electronic-Structure Theory
book, August 2000


NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010


Density Functionals for Inorganometallic and Organometallic Chemistry
journal, December 2005


Thermochemical Kinetics for Multireference Systems: Addition Reactions of Ozone
journal, May 2009


A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples
journal, February 1982


An efficient reformulation of the closed‐shell coupled cluster single and double excitation (CCSD) equations
journal, December 1988


Is coupled cluster singles and doubles (CCSD) more computationally intensive than quadratic configuration interaction (QCISD)?
journal, April 1989


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


Toward reliable adiabatic connection models free from adjustable parameters
journal, August 1997


Charge Model 5: An Extension of Hirshfeld Population Analysis for the Accurate Description of Molecular Interactions in Gaseous and Condensed Phases
journal, February 2012

  • Marenich, Aleksandr V.; Jerome, Steven V.; Cramer, Christopher J.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 2, p. 527-541
  • https://doi.org/10.1021/ct200866d

A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions
journal, January 2011


Nonseparable exchange–correlation functional for molecules, including homogeneous catalysis involving transition metals
journal, January 2015


An improved B3LYP method in the calculation of organic thermochemistry and reactivity
journal, July 2013


Quantum electrodynamical corrections to the fine structure of helium
journal, January 1974


The dissociation energy of MgO
journal, October 1982


Spectroscopy and metastability of BeO +
journal, October 2008


Computed Ground State properties of BeO, MgO, CaO and SrO in Molecular Orbital Approximation
journal, October 1968


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


Über eine Approximation des Hartree-Fockschen Potentials Durch eine Universelle Potentialfunktion
journal, April 1954


Statistical exchange for electron in shell and theXα method
journal, March 1974


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


Left-right correlation energy
journal, March 2001


Toward improved density functionals for the correlation energy
journal, October 2009


Generalized Gradient Approximation Made Simple
journal, October 1996


Generalized Gradient Approximation That Recovers the Second-Order Density-Gradient Expansion with Optimized Across-the-Board Performance
journal, July 2011


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


Workhorse Semilocal Density Functional for Condensed Matter Physics and Quantum Chemistry
journal, July 2009


Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids
journal, September 2003


Reparameterization of hybrid functionals based on energy differences of states of different multiplicity
journal, December 2001

  • Reiher, Markus; Salomon, Oliver; Artur Hess, Bernd
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 107, Issue 1
  • https://doi.org/10.1007/s00214-001-0300-3

Development and assessment of new exchange-correlation functionals
journal, October 1998


Semiempirical hybrid functional with improved performance in an extensive chemical assessment
journal, September 2005


Bonding of NO to NiO(100) and NixMg1−xO(100) surfaces: A challenge for theory
journal, August 2002


Adiabatic Connection for Kinetics
journal, June 2000


Assessment of a new local exchange functional OPTX
journal, June 2001


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


Development and Assessment of a New Hybrid Density Functional Model for Thermochemical Kinetics
journal, April 2004


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


Design of Density Functionals That Are Broadly Accurate for Thermochemistry, Thermochemical Kinetics, and Nonbonded Interactions
journal, June 2005


Global Hybrid Functionals: A Look at the Engine under the Hood
journal, November 2010


Comparative assessment of a new nonempirical density functional: Molecules and hydrogen-bonded complexes
journal, December 2003


New exchange-correlation density functionals: The role of the kinetic-energy density
journal, June 2002


A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004


Hybrid functionals based on a screened Coulomb potential
journal, May 2003


Can short-range hybrids describe long-range-dependent properties?
journal, July 2009


Systematic optimization of long-range corrected hybrid density functionals
journal, February 2008


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


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


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


A density-functional model of the dispersion interaction
journal, October 2005


A post-Hartree–Fock model of intermolecular interactions
journal, July 2005


A post-Hartree-Fock model of intermolecular interactions: Inclusion of higher-order corrections
journal, May 2006


Works referencing / citing this record:

‘Diet GMTKN55’ offers accelerated benchmarking through a representative subset approach
journal, January 2018


Semi-empirical or non-empirical double-hybrid density functionals: which are more robust?
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