Density-functional theory (hyper)polarizabilities of push-pull pi-conjugated systems: treatment of exact exchange and role of correlation.
The performance of the optimized effective potential procedure for exact exchange in calculating static electric-field response properties of push-pull pi-conjugated systems has been studied, with an emphasis on NO2-(CH=CH)n-NH2 chains. Good agreement with Hartree-Fock dipole moments and (hyper)polarizabilities is obtained; particularly noteworthy is the chain length dependence for beta/n. Thus, the problem that conventional density-functional theory functionals dramatically overestimate these properties is largely solved, although there remains a significant correlation contribution that cannot be accounted for with current correlation functionals.
Bulat
Felipe A
FA
Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Correo 22, Santiago, Chile.
Toro-Labbé
Alejandro
A
Champagne
Benoît
B
Kirtman
Bernard
B
Yang
Weitao
W