Additional Supporting Information may be found in the online version of this article.


Figure 1S. Variations of BLA (Å) (left) and Mulliken atomic spin densities (a.u.) per repeat unit (right) in MEHPPV oligomer computed at LC-wPBE/6–31G* level for the optimal positive polaronic state (P+) in vacuum and solvent. The equilibrium state is calculated for five different geometrical conformations: trans, trans-SK (6-3), trans-SK (7-2), cis-LK (4-4) and cis-LK (5-3) as shown in Figure 1. The dashed line represents the defect position on the chain.

Figure 2S. Same as Figure 1S but for the optimal negative polaronic state (P-).

Figure 3S. Mulliken atomic spin densities (a.u.) per repeat unit (right) of the MEH-PPV oligomer consisting of 10 repeat units in the trans-SK (6-3) and trans-SK (7-2) conformations for positive (P+) and negative (P-) polarons in their optimal geometries as well as the native geometries of the opposite charged states. The calculations are performed at LC-wPBE/6–31G* level in the presence of solvent. We have used a notation "(X,Y)" in the legend, where X denotes the fully relaxed state of the system, while Y denotes the state for which spin is calculated.

Figure 4S. (A) BLA (Å) of vinyl units of the initial states for MEH-PPV oligomer in its trans-SK (6-3) conformation for Figure 4S (B). In Figure 4S (B), the P+ and P- states are optimzied for all these different configurations as depicted here. These nine initial geometries are named according to the specific location of the distorted vinyl bond on the chain from one end to another.

Figure 4S. (B) The top panel display the BLA (Å) of MEH-PPV oligomer in trans-SK (6-3) geometrical configuration for the P+ and P- polaronic excitations calculated at LC-wPBE/6–31G* level in the presence of the solvent. The BLA is shown for 9 distinct initial states presented in Figure 4S (A). The middle panel displays the BLA plots for the global and local maxima (GM and LM) for P+ and P- states along with their corresponding transition states (TS). The bottom panels sketch the respective energy picture.

Figure 5S. Density of Kohn-Sham states of MEH-PPV oligomer comprised of 10 repeat units computed using various geometrical conformations at LC-wPBE/6–31G* level for S0, P+ and P- states calculated using the SCF. The alpha (α) and beta (β) molecular orbitals (MOs) of each spin states are shown separately (represented by the same color). The darker (lighter) shades in the figure correspond to the occupied (O) and virtual (V) orbitals, respectively. Both vacuum (left) and solvent (right) calculations are shown.

Table 1S. Binding energies (eV) of PPV and MEH-PPV oligomers for P+ and P- excitations for trans, trans-SK (6-3), trans-SK (7-2), cis-LK (4-4) and cis-LK (5-3) conformations calculated at LC-wPBE/6–31G* level both in vacuum (V) and in solvent (S). The difference between the total energy of the excitation (X) in the S0 geometry and that in its corresponding fully relaxed geometry is reported.

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