Accession Number : ADA617256


Title :   Density Functional Theory Embedding for Correlated Wavefunctions


Descriptive Note : Doctoral thesis


Corporate Author : CALIFORNIA INST OF TECH PASADENA


Personal Author(s) : Goodpaster, Jason D


Full Text : https://apps.dtic.mil/dtic/tr/fulltext/u2/a617256.pdf


Report Date : Jan 2014


Pagination or Media Count : 149


Abstract : 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 e ect 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.


Descriptors :   *DENSITY FUNCTIONAL THEORY , ELECTRON DENSITY , EMBEDDING , KINETICS , METHODOLOGY , MOLECULAR STRUCTURE , MOLECULE MOLECULE INTERACTIONS , THESES , WAVE FUNCTIONS


Subject Categories : Physical Chemistry


Distribution Statement : APPROVED FOR PUBLIC RELEASE