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Density Functional Theory Embedding for Correlated Wavefunctions


Goodpaster, Jason Daniel (2014) Density Functional Theory Embedding for Correlated Wavefunctions. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/RX3S-GH65.


Methods that exploit the intrinsic locality of molecular interactions show significant promise in making tractable the electronic structure calculation of large-scale systems. In particular, embedded density functional theory (e-DFT) offers a formally exact approach to electronic structure calculations in which the interactions between subsystems are evaluated in terms of their electronic density. In the following dissertation, methodological advances of embedded density functional theory are described, numerically tested, and applied to real chemical systems.

First, we describe an e-DFT protocol in which the non-additive kinetic energy component of the embedding potential is treated exactly. Then, we present a general implementation of the exact calculation of the non-additive kinetic potential (NAKP) and apply it to molecular systems. We demonstrate that the implementation using the exact NAKP is in excellent agreement with reference Kohn-Sham calculations, whereas the approximate functionals lead to qualitative failures in the calculated energies and equilibrium structures.

Next, we introduce density-embedding techniques to enable the accurate and stable calculation of correlated wavefunction (CW) in complex environments. Embedding potentials calculated using e-DFT introduce the effect of the environment on a subsystem for CW calculations (WFT-in-DFT). We demonstrate that WFT-in-DFT calculations are in good agreement with CW calculations performed on the full complex.

We significantly improve the numerics of the algorithm by enforcing orthogonality between subsystems by introduction of a projection operator. Utilizing the projection-based embedding scheme, we rigorously analyze the sources of error in quantum embedding calculations in which an active subsystem is treated using CWs, and the remainder using density functional theory. We show that the embedding potential felt by the electrons in the active subsystem makes only a small contribution to the error of the method, whereas the error in the nonadditive exchange-correlation energy dominates. We develop an algorithm which corrects this term and demonstrate the accuracy of this corrected embedding scheme.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Density Functional Theory Quantum Embedding Wavefunction Theory Nonadditive Kinetic Energy
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemical Engineering
Minor Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Miller, Thomas F.
Thesis Committee:
  • Miller, Thomas F. (chair)
  • Goddard, William A., III
  • Davis, Mark E.
  • Wang, Zhen-Gang
Defense Date:15 May 2014
Non-Caltech Author Email:jgoodpa2 (AT)
Funding AgencyGrant Number
Department of EnergyDE-SC0006598
U. S. Army Research Lab- oratory and the U. S. Army Research OfficeW911NF-10-1-0202
Air Force Office of Scientific ResearchFA9550-11-1-0288
Record Number:CaltechTHESIS:05302014-220000101
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8451
Deposited By: Jason Goodpaster
Deposited On:03 Jun 2014 19:01
Last Modified:04 Oct 2019 00:05

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