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Title: Influence of pseudopotentials on excitation energies from selected configuration interaction and diffusion Monte Carlo

Journal Article · · Results in Chemistry
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Due to their diverse nature, the faithful description of excited states within electronic structure theory methods remains one of the grand challenges of modern theoretical chemistry. Quantum Monte Carlo (QMC) methods have been applied very successfully to ground state properties but still remain generally less effective than other non-stochastic methods for electronically excited states. Nonetheless, we have recently reported accurate excitation energies for small organic molecules at the fixed-node diffusion Monte Carlo (FN-DMC) within a Jastrow-free QMC protocol relying on a deterministic and systematic construction of nodal surfaces using the selected configuration interaction (sCI) algorithm known as CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively). Albeit highly accurate, these all-electron calculations are computationally expensive due to the presence of core electrons. One very popular approach to remove these chemically-inert electrons from the QMC simulation is to introduce pseudopotentials (also known as effective core potentials). Taking the water molecule as an example, we investigate the influence of Burkatzki-Filippi-Dolg (BFD) pseudopotentials and their associated basis sets on vertical excitation energies obtained with sCI and FN-DMC methods. Although these pseudopotentials are known to be relatively safe for ground state properties, we evidence that special care may be required if one strives for highly accurate vertical transition energies. Indeed, comparing all-electron and valence-only calculations, we show that using pseudopotentials with the associated basis sets can induce differences of the order of 0.05 eV on the excitation energies. Fortunately, a reasonable estimate of this shift can be estimated at the sCI level.

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
Grant/Contract Number:
AC02-06CH11357; 2018-A0040801738
OSTI ID:
1529010
Alternate ID(s):
OSTI ID: 1595775
Journal Information:
Results in Chemistry, Journal Name: Results in Chemistry Vol. 1 Journal Issue: C; ISSN 2211-7156
Publisher:
ElsevierCopyright Statement
Country of Publication:
Netherlands
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Quantum Monte Carlo
Fixed-node error
Excited states
PseudopotentialEffective core potential