In the present study, we performed nanosecond TRIR spectroscopy of PNA and its isotopomers (PNA-15NH2 and PNA-15NO2) in CD3CN and assigned the observed transient absorption bands to T1 PNA. The lifetime of the T1 state has been determined to be 430 ns with argon bubbling, which decreases to about one-third with oxygen bubbling. To interpret the IR spectrum of T1 PNA and extract structural information on the T1 state, we have simulated the IR spectra of PNA, PNA-15NH2, and PNA-15NO2 in both S0 and T1 states at the DFT/B3LYP computational level. We have compared three different molecular models, namely, the free gas-phase molecule, the PCM model, and the explicitly solvated model, among which the explicitly solvated model with two CD3CN molecules attached to the NH2
group (the PNA+2ACN model) has been found to give best agreement with experiment except for the doublet at around 1320 cm–1 This discrepancy has been completely removed by elongating the C–NH2 bond slightly (0.012 Å) from its equilibrium length, and the resulting ground-state IR spectra are in excellent agreement with the experimentally recorded spectra of PNA and its isotopomers in the whole spectral region studied. The IR spectra of the three PNA isotopomers using the PNA+2ACN model with slight elongation of the C–NH2 bond satisfactorily reproduced the experimental data. These results indicate that the T1 PNA has a partial quinoid structure, for which the conventional way of describing excited states of push–
pull molecules (i.e., the two-state models) breaks down.
1.230 Å 1.271 Å
Chapter V
Conclusions and Future
Prospects
In this Thesis, we have demonstrated that TRIR studies can advance our understanding of the structure and reactivity of transients species that play prominent roles in the functioning of OPVs. We have addressed the issue of charge recombination losses in solar cells by studying the BET reaction dynamics in the model system of Py and DCB. All the transient species involved in the BET (Py2•+, DCB•−, and ACN2–) have been well characterized and a simple reaction scheme has been proposed that accounts for the observed BET dynamics. We have found that ACN plays a dual role as solvent and a reactant that mediates BET from DCB•− to Py2•+. The BET reaction scheme shown here can have significant implications because ACN is commonly used solvent for redox couple in DSSC. Moreover, Baheti and co-workers [116] recently used Py-based dye molecules in DSSC and Maggio and co-workers [46] theoretically demonstrated the importance of orbital symmetry in minimizing the charge recombination in DSSCs. The TRIR study can be extended to more realistic systems of solar cell devices.
We have also elucidated the T1 state of PNA. It has been well characterized using TRIR spectroscopy combined with DFT/B3LYP calculations with the explicit solvation model. The T1
state of PNA has been shown to exhibit a partial quinoid structure in contrast to the zwitterionic CT structure in the two-state model. This results challenges our understanding of excited states and thus it is necessary to characterize the excited state of several other molecules of this type using TRIR and explicit solvation model.
The present comprehensive TRIR study will provide us with molecular-level understanding of condensed-phase PET reactions and may even change our perceptions about excited-state structure and reactivity. We believe that further investigation along this line will pave a new way to develop efficient materials in the future.
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