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, FA; Toro-Labbé, A; Champagne, B; Kirtman, B; Yang, W
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