Journal of Physical Chemistry B, Vol.111, No.44, 12844-12848, 2007
Charge-sensitive vibrations in p-chloranil: The strange case of the C = C antisymmetric stretching
We have combined DFT calculations with single-crystal polarized infrared spectra to reinvestigate the assig,nment of the C=C antisymmetric stretching mode b(2u)nu(18) of p-chloranil (CA). The frequency of this mode indeed seems to display a nonlinear dependence on the average charge on the CA molecule (rho), at variance with the behavior of the antisymmetric C=O stretching frequency. The DFT calculations show that the origin of the problem is a drastic, 2 orders of magnitude decrease of the infrared intensity of the C=C antisymmetric stretching upon electron addition. Therefore, no infrared band can be easily associated to this mode in charue-transfer (CT) solids with rho greater than or similar to 0.5. On the other hand, a linear relationship between o and the b(2u)nu(18) frequency is found in quasi-neutral CT complexes of CA.