Acetonitrile
Solution Effect on Ru N749 Dye Adsorption and Excitation at TiO<sub>2</sub> Anatase Interface
Yoshitaka Tateyama
Masato Sumita
Yusuke Ootani
Koharu Aikawa
Ryota Jono
Liyuan Han
Keitaro Sodeyama
10.1021/jp5004006.s001
https://acs.figshare.com/articles/journal_contribution/Acetonitrile_Solution_Effect_on_Ru_N749_Dye_Adsorption_and_Excitation_at_TiO_sub_2_sub_Anatase_Interface/2269846
We investigated stable structures
and photoexcitation character of Ru N749 dye (black dye (BD)) adsorption
to TiO<sub>2</sub> anatase (101) interface immersed in bulk acetonitrile
(AN) solution, a most representative electrode interface in dye-sensitized
solar cells (DSCs). Density-functional-theory-based molecular dynamics
(DFT-MD) with explicit solvent molecules was used to take into account
the fluctuations of solvation shells and adsorbed molecules. We demonstrated
that BD adsorption via deprotonated carboxylate two anchors (d2) is
the most stable at the interface, while the one protonated carboxyl
anchor (p1) has the average energy only slightly higher than the d2.
This indicates that the p1 state can still coexist with the d2 under
equilibrium. It is in contrast with the calculated large stability
of the p1 in vacuo. Inhomogeneous charge distribution and anchor fluctuation
enhanced by AN solution causes this d2 stabilization. The calculated
projected densities of states and the photoabsorption spectra clearly
show that the d2 state has larger driving force of the electron injection
into the TiO<sub>2</sub>, whereas the photoabsorption in the wavelength
region over 800 nm, a characteristic of BD sensitizer, is mainly
attributed to the p1 state even in the AN solution. Consequently,
the better performance of BD DSC can be understood in terms of the
cosensitizer framework of the d2 and p1 states.
2014-07-31 00:00:00
p 1 state
bulk acetonitrile
2 stabilization
cosensitizer framework
p 1
representative electrode interface
Ru N 749 dye
BD DSC
solution causes
TiO 2 Anatase InterfaceWe
protonated carboxyl anchor
photoabsorption spectra
wavelength region
800 nm
electron injection
BD sensitizer
BD adsorption
2 state
deprotonated carboxylate
anchor fluctuation
Acetonitrile Solution Effect
molecule
Ru N 749 Dye Adsorption
p 1 states
photoexcitation character
solvation shells
Inhomogeneous charge distribution