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Title: Size-dependent error of the density functional theory ionization potential in vacuum and solution

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4937417· OSTI ID:1233558
 [1];  [1]
  1. Univ. of California, Merced, CA (United States)
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Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potential for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. As a result, in vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.

Research Organization:
Univ. of California, Merced, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0014437
OSTI ID:
1233558
Alternate ID(s):
OSTI ID: 1234092
Journal Information:
Journal of Chemical Physics, Vol. 143, Issue 24; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

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Cited By (8)

Dielectric Screening Meets Optimally Tuned Density Functionals journal April 2018
Modeling absorption spectra of molecules in solution journal September 2018
Noncentrosymmetric organic crystals of barbiturates as potential nonlinear optical phores: experimental and theoretical analyses journal June 2019
Density functional approximations for orbital energies and total energies of molecules and solids journal August 2018
On combining the conductor-like screening model and optimally tuned range-separated hybrid density functionals journal May 2019
Prediction of electronic couplings for molecular charge transfer using optimally tuned range-separated hybrid functionals journal March 2018
Prediction of electronic couplings for molecular charge transfer using optimally tuned range-separated hybrid functionals text January 2020
Prediction of electronic couplings for molecular charge transfer using optimally tuned range-separated hybrid functionals text January 2018

Figures / Tables (8)

FIG. 1(p. 4)figure FIG. 1
FIG. 2(p. 5)figure FIG. 2
FIG. 3(p. 5)figure FIG. 3
FIG. 4(p. 6)figure FIG. 4
FIG. 5(p. 6)figure FIG. 5
FIG. 6(p. 7)figure FIG. 6
FIG. 7(p. 8)figure FIG. 7
FIG. 8(p. 8)figure FIG. 8

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Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
density functional theory
solvents
ionization
exact exchange
size-dependent error
polarization
single molecule techniques