Time-dependent density-functional theory investigation of the formation of the charge transfer excited state for a series of aromatic donor–acceptor systems. Part II

Abstract

Articles you may be interested inA long-range-corrected density functional that performs well for both ground-state properties and time-dependent density functional theory excitation energies, including charge-transfer excited states J. Chem. Phys. 130, 054112 (2009); 10.1063/1.3073302 Time-dependent density functional theory study on intramolecular charge transfer and solvent effect of dimethylaminobenzophenone A global investigation of excited state surfaces within time-dependent density-functional response theory Time-dependent density-functional theory investigation of the formation of the charge transfer excited state for a series of aromatic donor-acceptor systems. Part I

Enhanced Dual Visible Light Fluorescence from the 2,2‘-Dipyridyl Tungsten Alkylidyne Complex [W(⋮CC6H4NMe2-4)(O2CCF3)(CO)2{κ2-2,2‘-(NC5H4)2}]: An Organometallic Twisted Intramolecular Charge Transfer State

“…Although Lin's emission was weak to moderate, even at 77 K, it was reported to have no detectable long lifetime (which we take to imply as a sub-10 ns time scale from the experimental parameters given), as opposed to a coexisting nontwisted excited state (planar intramolecular charge transfer, PICT), which showed fluorescence at λ em = 439 nm (5 ≤ τ ≤ 25 ns) and an associated long-lived (τ = 700 ms) π−π* emission at λ em = 453 nm at 77 K. The mechanism of the distortion involved a simple 90° twisting of the NMe 2 group relative to the planar hyperconjugated architecture of the diphenylhexatriene backbone. These photophysical experimental results have been supported by a range of high-level computational calculations, including time-dependent density functional theory studies, on organic aromatic acceptor−donor chromophores, 4-ZC 6 H 4 NR 2 (Z = acceptor group, e.g., CN, NO 2 , R = Me) . We propose a similar 1 TICT state for the complexes 3 − 5 (Scheme ), which is consistent with that of the organic analogue 4-Me 2 NC 6 H 4 (CHCH) 3 C 6 H 4 NO 2 -4, although the organometallic tungsten complexes clearly emit very strongly in solution at ambient temperatures.…”

Pyrrolidine‐based dye‐sensitized solar cells: A time‐dependent density functional theory investigation of the excited state electronic properties

“…The continuous improvements in central processing unit (CPU) resources now allow the study, at correlated levels of approximation, of the absorption spectra of large molecular species such as the dyes of DSSCs. For UV/Vis calculations, one of the most popular approach remains the time‐dependent density functional theory (TDDFT), that commonly provides accurate results for a reasonable computational effort, especially when hybrid functionals are used 15–20. “Cyanine‐like” structures, such as PYR derivatives, show a large CT character electronic excitations (and sometimes a multideterminental nature) which makes them difficult to study with DFT that tends to overestimate CT effects.…”