Absolutely Localized Projection-Based Embedding for Excited States

Xuelan Wen, Daniel S. Graham, Dhabih V. Chulhai, Jason D. Goodpaster

Research output: Contribution to journalArticle

Abstract

We present a quantum embedding method that allows for calculation of local excited states embedded in a Kohn-Sham density functional theory (DFT) environment. Projection-based quantum embedding methodologies provide a rigorous framework for performing DFT-in-DFT and wave function in DFT (WF-in-DFT) calculations. The use of absolute localization, where the density of each subsystem is expanded in only the basis functions associated with the atoms of that subsystem, provide improved computationally efficiency for WF-in-DFT calculations by reducing the number of orbitals in the WF calculation. In this work, we extend absolutely localized projection-based quantum embedding to study localized excited states using EOM-CCSD-in-DFT and TDDFT-in-DFT. The embedding results are highly accurate compared to the corresponding canonical EOM-CCSD and TDDFT results on the full system, with TDDFT-in-DFT frequently more accurate than canonical TDDFT. The absolute localization method is shown to eliminate the spurious low-lying excitation energies for charge-transfer states and prevent overdelocalization of excited states. Additionally, we attempt to recover the environment response caused by the electronic excitations in the high-level subsystem using different schemes and compare their accuracy. Finally, we apply this method to the calculation of the excited-state energy of green fluorescent protein and show that we systematically converge to the full system results. Here we demonstrate how this method can be useful in understanding excited states, specifically which chemical moieties polarize to the excitation. This work shows absolutely localized projection-based quantum embedding can treat local electronic excitations accurately and make computationally expensive WF methods applicable to systems beyond current computational limits.

Original languageEnglish (US)
Pages (from-to)385-398
Number of pages14
JournalJournal of Chemical Theory and Computation
Volume16
Issue number1
DOIs
StatePublished - Jan 14 2020

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Excited states
embedding
Density functional theory
projection
density functional theory
excitation
Wave functions
Excitation energy
wave functions
Green Fluorescent Proteins
Discrete Fourier transforms
Charge transfer
electronics
Proteins
Atoms
charge transfer
methodology
proteins
orbitals
energy

PubMed: MeSH publication types

  • Journal Article

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Absolutely Localized Projection-Based Embedding for Excited States. / Wen, Xuelan; Graham, Daniel S.; Chulhai, Dhabih V.; Goodpaster, Jason D.

In: Journal of Chemical Theory and Computation, Vol. 16, No. 1, 14.01.2020, p. 385-398.

Research output: Contribution to journalArticle

Wen, Xuelan ; Graham, Daniel S. ; Chulhai, Dhabih V. ; Goodpaster, Jason D. / Absolutely Localized Projection-Based Embedding for Excited States. In: Journal of Chemical Theory and Computation. 2020 ; Vol. 16, No. 1. pp. 385-398.
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