Density Functional and Ab Initio Study of Molecular Response

• Main Author: Peng, Degao
• Other Authors: Yang, Weitao
• Published: 2014
• Subjects: Chemistry; Physical chemistry; ab initio theory; density functional theory; response theory
• Online Access: http://hdl.handle.net/10161/8681

<p>Quantum chemistry methods nowadays reach its maturity with various robust ground state correlation methods. However, many problems related to response do not have satisfactory solutions. Chemical reactivity indexes are some static response to external fields and number of particle change. These chemical reactivity indexes have important chemical significance, while not all of them had analytical expressions for direct evaluations. By solving coupled perturbed self-consistent field equations, analytical expressions were obtained and verified numerically. In the particle-particle (pp) channel, the response to the pairing field can describe <italic>N&plusmn;2</italic> excitations, i.e. double ionization potentials and double electron affinities. The linear response time-dependent density-functional theory (DFT) with pairing fields is the response theory in the density-functional theory (DFT) framework to describe $N\pm 2$ excitations. Both adiabatic and dynamic kernels can be included in this response theory. The correlation energy based on this response, the correlation energy of the particle-particle random phase approximation (pp-RPA), can also be proved equivalent to the ladder approximation of the well-established coupled-cluster doubles. These connections between the response theory, <italic>ab initio</italic> methods, and Green's function theory would be beneficial for further development. Based on RPA and pp-RPA, the theory of second RPA and the second pp-RPA with restrictions can be used to capture single and double excitations efficiently. We also present a novel methods, variational fractional spin DFT, to calculate singlet-triplet energy gaps for diradicals, which are usually calculated through spin-flip response theories.</p> === Dissertation