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Absolutely Localized Projection-Based Embedding for Excited States
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posted on 2019-12-11, 21:46 authored by Xuelan Wen, Daniel S. Graham, Dhabih V. Chulhai, Jason D. GoodpasterWe 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.
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subsystemlocalization methodProjection-based quantum embedding methodologiesLocalized Projection-Based Embeddingcomputationally efficiencychemical moietiesembedding resultsWF-in-DFT calculationsWF calculationenvironment responsedensitybasis functionsprojection-based quantum embeddingWF methodsexcitation energiesexcited-state energyquantum embedding methodcharge-transfer statescanonical EOM-CCSDTDDFT-in-DFTTDDFT resultsExcited Statescanonical TDDFTsystem resultswave function
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