Browsing by Subject "Counter-ions"
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Item Open Access Investigation of charge carriers in doped thiophene oligomers through theoretical modeling of their UV/Vis spectra(2008) Salzner, U.The nature of the charge carriers in conducting organic polymers (COPs) is a long standing problem. Polythiophene is one of the prototypes of COPs and intensively studied. Because doping leads to changes in UV/vis spectra that are characteristic of the absorbing species, UV/vis spectra of charged thiophene oligomers with up to 25 rings were calculated with time-dependent density functional theory. The credibility of the method was established by comparing the results with a variety of theoretical levels and with experiment. Effects due to counterions (Cl3-) and solvent (CH 2Cl2) were examined. It was found that TDDFT employing hybrid functionals is accurate enough to distinguish the absorbing species. The findings offer an explanation for the experimentally observed difference in UV-spectra of medium-sized and long oligomers upon doping. As chain lengths of the oligomers increase and energy levels get closer, configuration interaction leads to additional absorption peaks in the high energy sub-band region (at around 1.5-2.5 eV). Thus, long oligomers do not behave differently from medium-sized ones upon doping, only their spectra are different. At low doping levels radical cations (polarons) are produced. At higher doping levels, dications that harbor weakly interacting polaron pairs are formed. Bipolarons are predicted only on very short chains or at high doping levels. There is no bipolaron binding energy and disproportionation of monocations into dications and neutral species is energetically unfavorable. © 2008 American Chemical Society.Item Open Access Nature of charge carriers in long doped oligothiophenes: the effect of counterions(2008) Zamoshchik, N.; Salzner, U.; Bendikov, M.A series of oligothiophene dications doped with Cl3 - ions were studied using density functional theory (DFT) at the B3LYP/6-31G(d) level. The balance between the bipolaron and polaron pair states was addressed by studying the closed-shell singlet, open-shell singlet, and triplet states of oligothiophene divalent salts using the relative energies of the different isomers, differences between the singlet and triplet states, bond length alternation analysis, charge distribution analysis, and isodesmic reactions. We found that contribution of polaron pair state to the electronic structure of the oligothiophene divalent salts is not observed in 8T2+(Cl3́ -)2 (short oligothiophene salts), appears in 12T 2+(Cl3 -)2 (medium-sized oligothiophene salts), and becomes the dominant in 20T2+(Cl 3 -)2 (long oligothiophene salts). Bipolarons are intrinsically unstable with respect to dissociation into polaron pairs regardless of the presence of counterions. Thus, even in the presence of counterions, we did not observe any bipolaron stabilization energy, however, doping ions localize polarons. The singlet and triplet states are energetically degenerate for long oligothiophene divalent salts, such as 20T 2+(Cl3 -)2. © 2008 American Chemical Society.Item Open Access Response of polyelectrolyte layers to the SiO2 substrate charging as probed by XPS(2009) Conger, C. P.; Süzer, ŞefikA single layer of the Cationic polyelectrolyte poly(allyamine) hydrochloride (PAH) deposited, using the layer-by-layer technique, on a silicon substrate containing 5 nm oxide layer is investigated by XPS while applying an external potential bias to the sample to control and manipulate the charge built-up on the oxide layer. Under application of a -10 V bias, the oxide layer is positively charged due to Photoemission process, evidenced by the measured Si2p binding energy of 104.4 eV. Application of a +10 V bias attracts the low energy neutralizing electrons, stemming from a hot filament, and leads to a negatively charged oxide layer, also evidenced by the measured Si2p binding energy of 102.9 eV. The single polyelectrolyte overlayer also responds to this polarity change of the oxide layer underneath by displaying a somewhat larger shifts both in the C1s and Nls peaks. In addition to the shifts in the positions, the N1s peaks undergo a significant intensity depletion, mostly on the positively charged -N+ component. We interpret this intensity depletion to be the result of reorientation of some of the dangling positively charged groups by moving toward the negatively charged oxide underlayer. To our knowledge this is the first time that a chemically specific response to an electrical stimuli is reported using XPS. A bilayer LbL film consisting of PAH and PSS, exhibits even a larger charging shift, but this time no intensity alteration is observed, most probably due to locking of the -N+ groups by the -SO3 + counterions of the second layer. © 2009 American Chemical Society.