Is it worthwhile to go beyond the local-density approximation in subsystem density functional theory?

Autor(es)

Grimmel, Stephanie A. ; Teodoro, Tiago Q. ; Visscher, Lucas

• Tipo de documento: Artigo Científico
• Fonte: International Journal of Quantum Chemistry; v. 120, n. 21, p. 11-pg., 2019-12-11.

Resumo

Frozen density embedding (FDE) theory is one of the major techniques aiming to bring modeling of extended chemical systems into the realm of high accuracy calculations. To improve its accuracy it is of interest to develop kinetic energy density functional approximations specifically for FDE applications. In the study reported here we focused on optimizing parameters of a generalized gradient approximation-like kinetic energy functional with the purpose of better describing electron excitation energies. We found that our optimized parametrizations, named excPBE and excPBE-3 (as these are derived from a Perdew-Burke-Ernzerhof-like parametrization), could not yield improvements over available functionals when applied on a test set of systems designed to probe solvatochromic shifts. Moreover, as several different functionals yielded very similar errors to the simple local-density approximation (LDA), it is questionable whether it is worthwhile to go beyond the LDA in this context. (AU)

• Processo FAPESP: 16/07787-4 - Desenvolvimento de um código computacional para a análise de moléculas quirais através do dicroísmo circular vibracional
• Beneficiário: Tiago Quevedo Teodoro
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado
• Processo FAPESP: 16/23165-3 - Implementação de uma técnica de Hessiana combinada para obtenção de espectros VCD
• Beneficiário: Tiago Quevedo Teodoro
• Modalidade de apoio: Bolsas no Exterior - Estágio de Pesquisa - Pós-Doutorado