Effect of interchain coupling on conducting polymer luminescence: excimers in derivatives of poly(phenylene vinylene)

Optical excitation of a chain in a polymer film may result in formation of an excimer, a superposition of on-chain excitons and charge-transfer excitons on the originally excited chain and a neighboring chain. The excimer emission is red-shifted compared to that of an on-chain exciton by an amount depending on the interchain coupling $t_\perp$. Setting up the excimer wavefunction and calculating the red shift, we determine average $t_\perp$ values, referred to a monomer, of 0.52 eV and 0.16 eV for poly(2,5-hexyloxy $p$-phenylene cyanovinylene), CN-PPV, and poly[2-methoxy, 5-(2'-ethyl-hexyloxy)-1, 4 p-phenylene vinylene], MEH-PPV, respectively, and use them to determine the effect of interchain distance on the emission.