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Title: On the accuracy of density functional theory and wave function methods for calculating vertical ionization energies

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4921037· OSTI ID:1391934
 [1];  [2];  [3];  [4]
  1. Univ. of Cambridge (United Kingdom). Cavendish Lab.
  2. King’s College London, (United Kingdom). Theory and Simulation of Condensed Matter
  3. Univ. of Cambridge (United Kingdom)
  4. Univ. of Cambridge (United Kingdom). Cavendish Lab.; Argonne National Lab. (ANL), Argonne, IL (United States)
+ Show Author Affiliations

In this work, the best practice in computational methods for determining vertical ionization energies (VIEs) is assessed, via reference to experimentally determined VIEs that are corroborated by highly accurate coupled-cluster calculations. These reference values are used to benchmark the performance of density-functional theory (DFT) and wave function methods: Hartree-Fock theory (HF), second-order Møller-Plesset perturbation theory (MP2) and Electron Propagator Theory (EPT). The core test set consists of 147 small molecules. An extended set of six larger molecules, from benzene to hexacene, is also considered to investigate the dependence of the results on molecule size. The closest agreement with experiment is found for ionization energies obtained from total energy diff calculations. In particular, DFT calculations using exchange-correlation functionals with either a large amount of exact exchange or long-range correction perform best. The results from these functionals are also the least sensitive to an increase in molecule size. In general, ionization energies calculated directly from the orbital energies of the neutral species are less accurate and more sensitive to an increase in molecule size. For the single-calculation approach, the EPT calculations are in closest agreement for both sets of molecules. For the orbital energies from DFT functionals, only those with long-range correction give quantitative agreement with dramatic failing for all other functionals considered. The results offer a practical hierarchy of approximations for the calculation of vertical ionization energies. In addition, the experimental and computational reference values can be used as a standardized set of benchmarks, against which other approximate methods can be compared.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; Engineering and Physical Sciences Research Council (EPSRC)
Grant/Contract Number:
AC02-06CH11357; EP/P505445/1
OSTI ID:
1391934
Alternate ID(s):
OSTI ID: 1228252
Journal Information:
Journal of Chemical Physics, Vol. 142, Issue 19; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 41 works
Citation information provided by
Web of Science

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Cited By (6)

Assignment of photoelectron spectra of intramolecular silicon complexes: 1-vinyl- and 1-phenylsilatranes journal January 2018
Polypyrrole derivatives for optoelectronic applications: a DFT study on the influence of side groups journal January 2019
Accurate density functional prediction of molecular electron affinity with the scaling corrected Kohn–Sham frontier orbital energies journal October 2017
A density functional theory study on the superacidity of sulfuric, fluorosulfuric, and triflic acid derivatives with two cyclopentadiene rings: ion pairs formation in the gas phase journal June 2019
Micropollutant Oxidation Studied by Quantum Chemical Computations: Methodology and Applications to Thermodynamics, Kinetics, and Reaction Mechanisms journal March 2019
The LDA-1/2 method applied to atoms and molecules text January 2018

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