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Analytical gradients for excitation energies from frozen-density embedding.
Kovyrshin, Arseny; Neugebauer, Johannes.
Afiliação
  • Kovyrshin A; Laboratorium für Physikalische Chemie, ETH Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland. j.neugebauer@uni-muenster.de.
Phys Chem Chem Phys ; 18(31): 20955-75, 2016 Aug 21.
Article em En | MEDLINE | ID: mdl-26996970
The formulation of analytical excitation-energy gradients from time-dependent density functional theory within the frozen-density embedding framework is presented. In addition to a comprehensive mathematical derivation, we discuss details of the numerical implementation in the Slater-function based Amsterdam Density Functional (ADF) program. Particular emphasis is put on the consistency in the use of approximations for the evaluation of second- and third-order non-additive kinetic-energy and exchange-correlation functional derivatives appearing in the final expression for the excitation-energy gradient. We test the implementation for different chemical systems in which molecular excited-state potential-energy curves are affected by another subsystem. It is demonstrated that the analytical implementation for the evaluation of excitation-energy gradients yields results in close agreement with data from numerical differentiation. In addition, we show that our analytical results are numerically more stable and thus preferable over the numerical ones.

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Phys Chem Chem Phys Assunto da revista: BIOFISICA / QUIMICA Ano de publicação: 2016 Tipo de documento: Article País de afiliação: Suíça

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Phys Chem Chem Phys Assunto da revista: BIOFISICA / QUIMICA Ano de publicação: 2016 Tipo de documento: Article País de afiliação: Suíça