TY - JOUR
AU - Shedge, Sapana Vitthal
AU - Wesolowski, Tomasz A.
TI - Nonuniform Continuum Model for Solvatochromism Based on Frozen-Density Embedding Theory
PY - 2014
JF - ChemPhysChem
JA - ChemPhysChem
SN - 1439-4235
VL - 15
IS - 15
SP - 3291
EP - 3300
L1 - http://onlinelibrary.wiley.com/doi/10.1002/cphc.201402351/pdf
L3 - http://doi.wiley.com/10.1002/cphc.201402351
M3 - 10.1002/cphc.201402351
UR - http://dx.doi.org/10.1002/cphc.201402351
KW - density functional calculations
KW - molecular dynamics
KW - molecular modeling
KW - solvatochromism
KW - UV/Vis spectroscopy
N2 - Frozen-density embedding theory (FDET) provides the formal framework for multilevel numerical simulations, such that a selected subsystem is described at the quantum mechanical level, whereas its environment is described by means of the electron density (frozen density; ÏB(Â rÂ â) ) The frozen densityÂ ÏB(Â rÂ â)Â is usually obtained from some lower-level quantum mechanical methods applied to the environment, but FDET is not limited to such choices forÂ ÏB(Â rÂ â). The present work concerns the application of FDET, in whichÂ ÏB(Â rÂ â)Â is the statistically averaged electron density of the solvent . The specific soluteâsolvent interactions are represented in a statistical manner in . A full self-consistent treatment of solvated chromophore, thus involves a single geometry of the chromophore in a given state and the corresponding . We show that the coupling between the two descriptors might be made in an approximate manner that is applicable for both absorption and emission. The proposed protocol leads to accurate (error in the range of 0.05â
eV) descriptions of the solvatochromic shifts in both absorption and emission.
ID - 1433
ER -