Constrained Density-Functional Theory--Configuration Interaction
Name
809542537-MIT.pdf
Description
Full printable version
Size
2.88 MB
Format
Adobe PDF
Checksum (MD5)
5fbe24c5cd597be4a8b678a9194c8b91
Author(s)
Kaduk, Benjamin James
Advisor(s)
Troy Van Voorhis.
Alternative Title
Constrained DFT--Configuration Interaction
CDFT-CI
Date Issued
2012
Publisher
Massachusetts Institute of Technology
Abstract
In this thesis, I implemented a method for performing electronic structure calculations, "Constrained Density Functional Theory-- Configuration Interaction" (CDFT-CI), which builds upon the computational strengths of Density Functional Theory and improves upon it by including higher level treatments of electronic correlation which are not readily available in Density-Functional Theory but are a keystone of wavefunction-based electronic structure methods. The method involves using CDFT to construct a small basis of hand-picked states which suffice to reasonably describe the static correlation present in a particular system, and efficiently computing electronic coupling elements between them. Analytical gradients were also implemented, involving computational effort roughly equivalent to the evaluation of an analytical Hessian for an ordinary DFT calculation. The routines were implemented within Q-Chem in a fashion accessible to end users; calculations were performed to assess how CDFT-CI improves reaction transition state energies, and to assess its ability to produce conical intersections, as compared to ordinary DFT. The analytical gradients enabled optimization of reaction transition-state structures, as well as geometry optimization on electronic excited states, with good results.
Description
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2012.
This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.
Cataloged from student-submitted PDF version of thesis.
Includes bibliographical references (p. 117-136).
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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