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Earth Mover’s Distance as a Metric to Evaluate the Extent of Charge Transfer in Excitations Using Discretized Real-Space Densities

Journal Article · · Journal of Chemical Theory and Computation
 [1];  [1];  [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
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This paper presents a novel theoretical measure, μEMD, based on the earth mover's distance (EMD), for quantifying the density shift caused by electronic excitations in molecules. As input, the EMD metric uses only the discretized ground- and excited-state electron densities in real space, rendering it compatible with almost all electronic structure methods used to calculate excited states. The EMD metric is compared against other popular theoretical metrics for describing the extent of electron-hole separation in a wide range of excited states (valence, Rydberg, charge transfer, etc.). Further, the results showcase the EMD metric's effectiveness across all excitation types and suggest that it is useful as an additional tool to characterize electronic excitations. The study also reveals that μEMD can function as a promising diagnostic tool for predicting the failure of pure exchange-correlation functionals. Specifically, we show statistical relationships among the functional-driven errors, the exact exchange content within the functional, and the magnitude of μEMD values.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
2473031
Journal Information:
Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 21 Vol. 19; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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