TY - JOUR
AU - Wesolowski, Tomasz A.
TI - Embedding potentials for excited states of embedded species
PY - 2014
JF - The Journal of Chemical Physics
JA - The J. Chem. Phys.
SN - 0021-9606
VL - 140
IS - 18
SP - 18
L1 - http://scitation.aip.org/deliver/fulltext/aip/journal/jcp/140/18/1.4870014.pdf?itemId=/content/aip/journal/jcp/140/18/10.1063/1.4870014&mimeType=pdf&containerItemId=content/aip/journal/jcp
L2 - http://scitation.aip.org/content/aip/journal/jcp/140/18/10.1063/1.4870014
L3 - http://scitation.aip.org/content/aip/journal/jcp/140/18/10.1063/1.4870014
M3 - 10.1063/1.4870014
UR - http://dx.doi.org/10.1063/1.4870014
KW - wave functions
KW - excited states
KW - ground states
KW - density functional theory
KW - excitation energies
N2 - Frozen-Density-Embedding Theory (FDET) is a formalism to obtain the upper bound of the ground-state energy of the total system and the corresponding embedded wavefunction by means of Euler-Lagrange equations [T. A. Wesolowski, Phys. Rev. A77(1), 012504 (2008)]. FDET provides the expression for the embedding potential as a functional of the electron density of the embedded species, electron density of the environment, and the field generated by other charges in the environment. Under certain conditions, FDET leads to the exact ground-state energy and density of the whole system. Following Perdew-Levy theorem on stationary states of the ground-state energy functional, the other-than-ground-state stationary states of the FDET energy functional correspond to excited states. In the present work, we analyze such use of other-than-ground-state embedded wavefunctions obtained in practical calculations, i.e., when the FDET embedding potential is approximated. Three computational approaches based on FDET, that assure self-consistent excitation energy and embedded wavefunction dealing with the issue of orthogonality of embedded wavefunctions for different states in a different manner, are proposed and discussed.
ID - 1421
ER -