10.1021/ct5003994.s001
Thibaud Etienne
Thibaud
Etienne
Xavier Assfeld
Xavier
Assfeld
Antonio Monari
Antonio
Monari
Toward a Quantitative
Assessment of Electronic Transitions’ Charge-Transfer Character
American Chemical Society
2014
ground state
TDDFT
attachment density
electron density
ϕ S assessment
charge density variation
novel index
ϕ S
report studies
attachment densities overlap
detachment density
Quantitative Assessment
topological descriptor
2014-09-09 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Toward_a_Quantitative_Assessment_of_Electronic_Transitions_Charge_Transfer_Character/2256478
We hereby report studies devoted
to a topological descriptor of
photoinduced electronic charge density variation. Our novel index,
symbolized as ϕ<sub><i>S</i></sub>, consists in the
detachment and attachment densities overlap, where the detachment
density physically depicts the electron density removed from the ground
state of a molecule during the transition while the attachment density
consists in the rearranged density in the excited state. Our method
provides a simple and efficient way to quantitatively evaluate how
easy the charge-separation is made upon the chromophore’s light
absorption. Furthermore, this model can be applied for instance to
address a comment on new push–pull dyes charge-transfer ability
in order to assess their potentiality as candidates for light absorption-based
devices. Moreover, the ϕ<sub><i>S</i></sub> assessment
allows us to perform some methodological diagnostic tests concerning
the use of long-range corrected exchange–correlation functional
in a time-dependent density functional theory (TDDFT) framework. This
paper relates the ϕ<sub><i>S</i></sub> descriptor’s
mathematical foundations from various perspectives (detachment/attachment
densities or natural transition orbitals), together with its application
to several types of chromophores. Connections and divergences with
a formerly proposed index are finally evidenced.