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Title: A remarkable case of basis set dependence: the false convergence patterns of the methyl anion

Abstract

Here, the gas phase methyl anion, CH 3¯, has been difficult to study experimentally, and the extreme basis set dependence of its molecular properties has presented a comparable challenge to theoreticians. Reliable predictions for the electronic structure of CH 3¯ require the use of basis sets capable of describing both the diffuse and valence characteristics of the system. The present study examines the basis set dependence of the equilibrium geometry and harmonic vibrational frequencies of CH 3¯. Both Hartree–Fock and CCSD(T) levels of theories are used with cc-pVXZ (, T, Q, 5, 6) basis sets with up to triple augmentation to describe the diffuse nature of the electron distribution. We find that non-augmented basis sets systematically yield vibrational frequencies that are too high for the umbrella mode and too low for the C–H symmetric and antisymmetric stretch even when extrapolated to the complete basis set limit, displaying false convergence patterns. The inclusion of one set of augmented functions significantly improves the convergence of these properties, but again yields false convergence patterns. Only with the doubly augmented basis set do we approach the basis set limit for the CH 3¯ vibrational frequencies.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]
  1. Univ. of Georgia, Athens, GA (United States)
Publication Date:
Research Org.:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1468298
Grant/Contract Number:  
SC0018412
Resource Type:
Accepted Manuscript
Journal Name:
Molecular Physics
Additional Journal Information:
Journal Name: Molecular Physics; Journal ID: ISSN 0026-8976
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; methyl anion; methide; CH; basis set dependence; false convergence

Citation Formats

Bowman, Michael C., Zhang, Boyi, James Morgan, W., and Schaefer, III, Henry F. A remarkable case of basis set dependence: the false convergence patterns of the methyl anion. United States: N. p., 2018. Web. doi:10.1080/00268976.2018.1478139.
Bowman, Michael C., Zhang, Boyi, James Morgan, W., & Schaefer, III, Henry F. A remarkable case of basis set dependence: the false convergence patterns of the methyl anion. United States. doi:10.1080/00268976.2018.1478139.
Bowman, Michael C., Zhang, Boyi, James Morgan, W., and Schaefer, III, Henry F. Sun . "A remarkable case of basis set dependence: the false convergence patterns of the methyl anion". United States. doi:10.1080/00268976.2018.1478139. https://www.osti.gov/servlets/purl/1468298.
@article{osti_1468298,
title = {A remarkable case of basis set dependence: the false convergence patterns of the methyl anion},
author = {Bowman, Michael C. and Zhang, Boyi and James Morgan, W. and Schaefer, III, Henry F.},
abstractNote = {Here, the gas phase methyl anion, CH3¯, has been difficult to study experimentally, and the extreme basis set dependence of its molecular properties has presented a comparable challenge to theoreticians. Reliable predictions for the electronic structure of CH3¯ require the use of basis sets capable of describing both the diffuse and valence characteristics of the system. The present study examines the basis set dependence of the equilibrium geometry and harmonic vibrational frequencies of CH3¯. Both Hartree–Fock and CCSD(T) levels of theories are used with cc-pVXZ (, T, Q, 5, 6) basis sets with up to triple augmentation to describe the diffuse nature of the electron distribution. We find that non-augmented basis sets systematically yield vibrational frequencies that are too high for the umbrella mode and too low for the C–H symmetric and antisymmetric stretch even when extrapolated to the complete basis set limit, displaying false convergence patterns. The inclusion of one set of augmented functions significantly improves the convergence of these properties, but again yields false convergence patterns. Only with the doubly augmented basis set do we approach the basis set limit for the CH3¯ vibrational frequencies.},
doi = {10.1080/00268976.2018.1478139},
journal = {Molecular Physics},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {5}
}

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Works referenced in this record:

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Predicting electron affinities with density functional theory: Some positive results for negative ions
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    Works referencing / citing this record:

    Mind the correct basis set: A case study for predicting gas phase acidities of small compounds using calculations from first principles
    journal, September 2014

    • Tymińska, Nina; Włoch, Marta; Royappa, A. Timothy
    • International Journal of Quantum Chemistry, Vol. 115, Issue 1
    • DOI: 10.1002/qua.24792

    The lower ionosphere of Titan
    journal, July 1976


    Theoretical studies of CH3, CH+3 and CH−3 using correlated wavefunctions
    journal, July 1977


    Negative ion chemistry in Titan's upper atmosphere
    journal, November 2009


    Gas-phase carbanion chemistry
    journal, October 1992


    The gas-phase acidities of the alkanes
    journal, March 1989

    • DePuy, Charles H.; Gronert, Scott; Barlow, Stephan E.
    • Journal of the American Chemical Society, Vol. 111, Issue 6
    • DOI: 10.1021/ja00188a003

    An experimental determination of the geometry and electron affinity of methyl radical
    journal, April 1978

    • Ellison, G. Barney; Engelking, P. C.; Lineberger, W. C.
    • Journal of the American Chemical Society, Vol. 100, Issue 8
    • DOI: 10.1021/ja00476a054

    Structure of the 7-phenylnorbornyl carbanion. A pyramidal organolithium and planar organopotassium
    journal, July 1980

    • Peoples, P. Robert; Grutzner, John B.
    • Journal of the American Chemical Society, Vol. 102, Issue 14
    • DOI: 10.1021/ja00534a025

    Photoelectron Spectroscopy of the Methide Anion: Electron Affinities of CH 3 and CD 3 and Inversion Splittings of CH 3 and CD 3
    journal, September 2015

    • Oliveira, Allan M.; Lu, Yu-Ju; Lehman, Julia H.
    • Journal of the American Chemical Society, Vol. 137, Issue 40
    • DOI: 10.1021/jacs.5b07013

    Accurate Calculations of the Electron Affinity and Ionization Potential of the Methyl Radical
    journal, December 1997

    • Dixon, David A.; Feller, David; Peterson, Kirk A.
    • The Journal of Physical Chemistry A, Vol. 101, Issue 49
    • DOI: 10.1021/jp970964l

    First observation of autodetachment lifetimes of methide, CH3−
    journal, June 2003

    • Mitchell, Stephen E.; Conklin, Philip M.; Farley, John W.
    • The Journal of Chemical Physics, Vol. 118, Issue 24
    • DOI: 10.1063/1.1574017

    Six-dimensional ab initio potential energy surfaces for H3O+ and NH3: Approaching the subwave number accuracy for the inversion splittings
    journal, June 2003

    • Rajamäki, Timo; Miani, Andrea; Halonen, Lauri
    • The Journal of Chemical Physics, Vol. 118, Issue 24
    • DOI: 10.1063/1.1574784

    Potential‐Energy Surfaces of CH 3 + and CH 3
    journal, February 1969

    • Kari, R. E.; Csizmadia, I. G.
    • The Journal of Chemical Physics, Vol. 50, Issue 3
    • DOI: 10.1063/1.1671209

    Near‐Molecular Hartree—Fock Wavefunction for CH 3
    journal, June 1967

    • Kari, R. E.; Csizmadia, I. G.
    • The Journal of Chemical Physics, Vol. 46, Issue 12
    • DOI: 10.1063/1.1840605

    Systematic study of molecular anions within the self‐consistent‐field approximation: OH , CN , C 2 H , NH 2 , and CH 3
    journal, August 1985

    • Lee, Timothy J.; Schaefer, Henry F.
    • The Journal of Chemical Physics, Vol. 83, Issue 4
    • DOI: 10.1063/1.449367

    Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
    journal, January 1989

    • Dunning, Thom H.
    • The Journal of Chemical Physics, Vol. 90, Issue 2
    • DOI: 10.1063/1.456153

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

    • Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
    • The Journal of Chemical Physics, Vol. 96, Issue 9
    • DOI: 10.1063/1.462569

    Application of systematic sequences of wave functions to the water dimer
    journal, April 1992

    • Feller, David
    • The Journal of Chemical Physics, Vol. 96, Issue 8
    • DOI: 10.1063/1.462652

    Gaussian basis sets for use in correlated molecular calculations. IV. Calculation of static electrical response properties
    journal, February 1994

    • Woon, David E.; Dunning, Thom H.
    • The Journal of Chemical Physics, Vol. 100, Issue 4
    • DOI: 10.1063/1.466439

    Basis-set convergence of correlated calculations on water
    journal, June 1997

    • Helgaker, Trygve; Klopper, Wim; Koch, Henrik
    • The Journal of Chemical Physics, Vol. 106, Issue 23
    • DOI: 10.1063/1.473863

    Predicting electron affinities with density functional theory: Some positive results for negative ions
    journal, August 1997

    • Tschumper, Gregory S.; Schaefer, Henry F.
    • The Journal of Chemical Physics, Vol. 107, Issue 7
    • DOI: 10.1063/1.474593

    Lithium monoxide anion: A ground-state triplet with the strongest base to date
    journal, May 2008

    • Tian, Z.; Chan, B.; Sullivan, M. B.
    • Proceedings of the National Academy of Sciences, Vol. 105, Issue 22
    • DOI: 10.1073/pnas.0801393105

    Electron affinity of the methyl radical: Structures of CH3 and CH3-
    journal, February 1977

    • Marynick, D. S.; Dixon, D. A.
    • Proceedings of the National Academy of Sciences, Vol. 74, Issue 2
    • DOI: 10.1073/pnas.74.2.410

    Umbrella motion of the methyl cation, radical, and anion molecules: I. Potentials, energy levels and partition functions
    journal, March 2016

    • Ragni, Mirco; Bitencourt, Ana Carla P.; Prudente, Frederico V.
    • The European Physical Journal D, Vol. 70, Issue 3
    • DOI: 10.1140/epjd/e2016-60530-2