skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Polishing the Gold Standard: The Role of Orbital Choice in CCSD(T) Vibrational Frequency Prediction

Journal Article · · Journal of Chemical Theory and Computation
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Columbia Univ., New York, NY (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
+ Show Author Affiliations

While CCSD(T) with spin-restricted Hartree-Fock (RHF) orbitals has long been lauded for its ability to accurately describe closed-shell interactions, the performance of CCSD(T) on open-shell species is much more erratic, especially when using a spin-unrestricted HF (UHF) reference. Previous studies have shown improved treatment of open-shell systems when a non-HF set of molecular orbitals, like Brueckner or Kohn-Sham density functional theory (DFT) orbitals, is used as a reference. Inspired by the success of regularized orbital-optimized second-order Møller-Plesset perturbation theory (κ-OOMP2) orbitals as reference orbitals for MP3, we investigate the use of κ-OOMP2 orbitals and various DFT orbitals as reference orbitals for CCSD(T) calculations of the corrected ground-state harmonic vibrational frequencies of a set of 36 closed-shell (29 neutrals, 6 cations, 1 anion) and 59 open-shell diatomic species (38 neutrals, 15 cations, 6 anions). The aug-cc-pwCVTZ basis set is used for all calculations. The use of κ-OOMP2 orbitals in this context alleviates difficult cases observed for both UHF orbitals and OOMP2 orbitals. Removing two multireference systems and 12 systems with ambiguous experimental data leaves a pruned data set. Overall performance on the pruned data set highlights CCSD(T) with a B97 orbital reference (CCSD(T):B97), CCSD(T) with a κ-OOMP2 orbital reference (CCSD(T):κ-OOMP2), and CCSD(T) with a B97M-rV orbital reference (CCSD(T):B97M-rV) with RMSDs of 8.48 cm-1, and 8.50 cm-1, and 8.75 cm-1 respectively, outperforming CCSD(T):UHF by nearly a factor of 5. Moreover, the performance on the closed- and open-shell subsets shows these methods are able to treat open-shell and closed-shell systems with comparable accuracy and robustness. CCSD(T) with RHF orbitals is seen to improve upon UHF for the closed-shell species, while spatial symmetry breaking in a number of restricted open-shell HF (ROHF) references leads CCSD(T) with ROHF reference orbitals to exhibit the poorest statistical performance of all methods surveyed for open-shell species. The use of κ-OOMP2 orbitals has also proven useful in diagnosing multireference character that can hinder the reliability of CCSD(T).

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1779272
Journal Information:
Journal of Chemical Theory and Computation, Vol. 17, Issue 2; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (96)

Binding in Radical-Solvent Binary Complexes: Benchmark Energies and Performance of Approximate Methods journal February 2013
Laser photoelectron spectrometry of PO − , PH − , and PH − 2 journal August 1976
Velocity modulation laser spectroscopy of molecular ions: The hyperfine-resolved rovibrational spectrum of HF + journal October 1989
Threshold photoelectron spectroscopy of HF and DF in the outer valence ionization region journal January 1999
Semiempirical hybrid density functional with perturbative second-order correlation journal January 2006
THE EMISSION SPECTRUM OF THE PH + MOLECULE journal August 1957
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples journal February 1982
W4-11: A high-confidence benchmark dataset for computational thermochemistry derived from first-principles W4 data journal July 2011
Thermochemical and Theoretical Investigations of the Sodium‐Oxygen System. II. Properties of NaO and Its Ions from Hartree‐Fock Molecular Orbital Studies journal May 1972
Size-consistent Brueckner theory limited to double substitutions journal December 1989
The accurate determination of molecular equilibrium structures journal April 2001
Is the oxywater radical cation more stable than neutral oxywater? journal May 1996
The Electronic Spectrum of HF + journal June 1975
Coupled‐cluster calculations on the C 2 molecule and the C + 2 and C − 2 molecular ions journal April 1992
Orthogonally spin-adapted coupled-cluster equations involving singly and doubly excited clusters. Comparison of different procedures for spin-adaptation journal October 1989
Orbital-optimized opposite-spin scaled second-order correlation: An economical method to improve the description of open-shell molecules journal April 2007
Gaussian basis sets for use in correlated molecular calculations. III. The atoms aluminum through argon journal January 1993
Distinguishing artificial and essential symmetry breaking in a single determinant: approach and application to the C 60 , C 36 , and C 20 fullerenes journal January 2019
Self‐consistent molecular orbital methods. XVIII. Constraints and stability in Hartree–Fock theory journal April 1977
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
Photoelectron spectra of halides: V. Experimental and theoretical study of the electronic structures of ClF, ClF 3 , BrF and BrF 3 journal November 1972
Geometries and Vibrational Frequencies of Small Radicals: Performance of Coupled Cluster and More Approximate Methods journal May 2012
Efficient use of the correlation consistent basis sets in resolution of the identity MP2 calculations journal February 2002
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals journal April 2017
Experimental Vibrational Zero-Point Energies: Diatomic Molecules journal June 2007
Vibrational Frequency and Dissociation Energy of the Superoxide Ion journal March 1964
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Gaussian basis sets for use in correlated molecular calculations. VII. Valence, core-valence, and scalar relativistic basis sets for Li, Be, Na, and Mg journal May 2010
Structure of O 2 journal December 1970
The Theoretical Prediction of Molecular Radical Species:  a Systematic Study of Equilibrium Geometries and Harmonic Vibrational Frequencies journal October 2001
Brueckner orbitals and density-functional theory journal January 2002
Large-scale correlated electronic structure calculations: the RI-MP2 method on parallel computers journal March 1996
Vibrational structure in electron scattering by O2 journal February 1972
The Energy Levels of a Rotating Vibrator journal September 1932
The electronic ground states of alkali monoxides journal April 1975
Regularized orbital-optimized second-order perturbation theory journal December 2013
On the connections between Brueckner-coupled-cluster, density-dependent Hartree-Fock, and density functional theory journal July 1995
The quadratic coupled cluster doubles model journal November 2000
Regularized Orbital-Optimized Second-Order Møller–Plesset Perturbation Theory: A Reliable Fifth-Order-Scaling Electron Correlation Model with Orbital Energy Dependent Regularizers journal August 2018
Approaching closed-shell accuracy for radicals using coupled cluster theory with perturbative triple substitutions journal January 2003
Spin‐adapted multireference coupled‐cluster approach: Linear approximation for two closed‐shell‐type reference configurations journal May 1988
Brueckner's Theory and the Method of Superposition of Configurations journal March 1958
Dissociation energies of PH and PH+ journal December 1995
Assessment of Orbital-Optimized, Spin-Component Scaled Second-Order Many-Body Perturbation Theory for Thermochemistry and Kinetics journal October 2009
The balance between theoretical method and basis set quality: A systematic study of equilibrium geometries, dipole moments, harmonic vibrational frequencies, and infrared intensities journal July 1993
Triplet instability in doublet systems journal January 2004
The C̃ 2A2 excited state of NO 2 : Evidence for a Cs equilibrium structure and a failure of some spin-restricted reference wavefunctions journal August 1997
Quadratically convergent algorithm for orbital optimization in the orbital-optimized coupled-cluster doubles method and in orbital-optimized second-order Møller-Plesset perturbation theory journal September 2011
The optimization of molecular orbitals for coupled cluster wavefunctions journal December 1987
Wavefunction stability analysis without analytical electronic Hessians: application to orbital-optimised second-order Møller–Plesset theory and VV10-containing density functionals journal March 2015
The full CCSDT model for molecular electronic structure journal June 1987
On the choice of orbitals for symmetry breaking problems with application to NO 3 journal October 1992
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
A comparison of the efficiency and accuracy of the quadratic configuration interaction (QCISD), coupled cluster (CCSD), and Brueckner coupled cluster (BCCD) methods journal February 1992
High-resolution studies of the A2Π-X2Π system of rotationally cooled SO+ journal July 1988
Assessment of Orbital-Optimized MP2.5 for Thermochemistry and Kinetics: Dramatic Failures of Standard Perturbation Theory Approaches for Aromatic Bond Dissociation Energies and Barrier Heights of Radical Reactions journal March 2015
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
�ber das Bandenspektrum des ionisierten Aluminiumhydrides journal January 1934
Quantum Monte Carlo calculations for ground and excited states journal November 2001
Use of Improved Orbitals for CCSD(T) Calculations for Predicting Heats of Formation of Group IV and Group VI Metal Oxide Monomers and Dimers and UCl 6 journal July 2016
Utilizing Essential Symmetry Breaking in Auxiliary-Field Quantum Monte Carlo: Application to the Spin Gaps of the C 36 Fullerene and an Iron Porphyrin Model Complex journal April 2020
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Third-Order Møller–Plesset Theory Made More Useful? The Role of Density Functional Theory Orbitals journal November 2020
Nuclear Saturation and Two-Body Forces. II. Tensor Forces journal October 1954
Use of the rVV10 Nonlocal Correlation Functional in the B97M-V Density Functional: Defining B97M-rV and Related Functionals journal December 2016
High resolution photodetachment study of OH − and OD − in the threshold region 7000–6450 Å journal March 1974
Frozen natural orbital coupled-cluster theory: Forces and application to decomposition of nitroethane journal April 2008
Third-Order Møller–Plesset Perturbation Theory Made Useful? Choice of Orbitals and Scaling Greatly Improves Accuracy for Thermochemistry, Kinetics, and Intermolecular Interactions journal July 2019
Prediction of Bond Dissociation Energies/Heats of Formation for Diatomic Transition Metal Compounds: CCSD(T) Works journal January 2017
Size-consistent wave functions for nondynamical correlation energy: The valence active space optimized orbital coupled-cluster doubles model journal December 1998
Use of approximate integrals in ab initio theory. An application in MP2 energy calculations journal June 1993
Two single-reference approaches to singlet biradicaloid problems: Complex, restricted orbitals and approximate spin-projection combined with regularized orbital-optimized Møller-Plesset perturbation theory journal June 2019
Symmetry breaking in O+4: an application of the Brueckner coupled-cluster method journal June 1994
ωB97X-V: A 10-parameter, range-separated hybrid, generalized gradient approximation density functional with nonlocal correlation, designed by a survival-of-the-fittest strategy journal January 2014
Eliminating spin contamination in auxiliary-field quantum Monte Carlo: Realistic potential energy curve of F2 journal March 2008
The Only Stable State of O 2 - Is the X 2 Π g Ground State and It (Still!) Has an Adiabatic Electron Detachment Energy of 0.45 eV journal October 2003
A combined zero electronic kinetic energy spectroscopy and ion-pair dissociation imaging study of the F2+(XΠg2) structure journal April 2005
On the performance of density functional theory for symmetry-breaking problems journal March 1999
The elusive dynamics of aqueous permanganate photochemistry journal January 2020
The prediction of molecular equilibrium structures by the standard electronic wave functions journal April 1997
Experimental Study of Low Energy e-O2 Collision Processes journal October 1971
An examination of the Brueckner condition for the selection of molecular orbitals in correlated wavefunctions journal February 1977
Accurate correlation consistent basis sets for molecular core–valence correlation effects: The second row atoms Al–Ar, and the first row atoms B–Ne revisited journal December 2002
Correlation consistent basis sets for explicitly correlated wavefunctions: valence and core–valence basis sets for Li, Be, Na, and Mg journal January 2010
ω B97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlation journal June 2016
XXXIV. Notes on the molecular orbital treatment of the hydrogen molecule journal April 1949
High-resolution threshold photoelectron spectroscopy of molecular fluorine journal December 1996
High-Resolution Photoelectron Spectroscopy with Angular Selectivity - A Tool To Probe Valence-Rydberg States and Couplings in HCl + journal June 2014
Binding of an electron by the field of a molecular dipole — LiCl− journal January 1976
Configuration interaction with Kohn–Sham orbitals and their relation to excited electronic states journal September 2001
Single‐Configuration Wavefunctions and Potential Curves for Low‐Lying States of He2+, Ne2+, Ar2+, F2−, Cl2− and the Ground State of Cl 2 journal December 1971
Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionals journal November 1997
Optimization of auxiliary basis sets for RI-MP2 and RI-CC2 calculations: Core–valence and quintuple-ζ basis sets for H to Ar and QZVPP basis sets for Li to Kr journal January 2005
Photoelectron spectrum of chlorine monofluoride journal December 1971
First-order intermolecular interaction energies from Kohn–Sham orbitals journal May 2002
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals [Supplemental Data] fileset June 2017

Similar Records

Assessment of the accuracy of coupled cluster perturbation theory for open-shell systems. I. Triples expansions
Journal Article · Sat May 21 00:00:00 EDT 2016 · Journal of Chemical Physics · OSTI ID:1779272
Utilizing Essential Symmetry Breaking in Auxiliary-Field Quantum Monte Carlo: Application to the Spin Gaps of the C36 Fullerene and an Iron Porphyrin Model Complex
Journal Article · Mon Apr 13 00:00:00 EDT 2020 · Journal of Chemical Theory and Computation · OSTI ID:1779272
Components of the Bond Energy in Polar Diatomic Molecules, Radicals, and Ions Formed by Group-1 and Group-2 Metal Atoms
Journal Article · Tue May 26 00:00:00 EDT 2015 · Journal of Chemical Theory and Computation · OSTI ID:1779272

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Energy
Quantum mechanics
Chemical calculations
Density functional theory
Fourier transforms