Rational Design of Asymmetric Polymethines to Attain NIR(II) Bioimaging at >1100 nm

We report re-optimization of a recently proposed long-range corrected (LC) hybrid density functional [J.-D. Chai and M. Head-Gordon, J. Chem. Phys., 2008, 128, 084106] to include empirical atom-atom dispersion corrections. The resulting functional, omegaB97X-D yields satisfactory accuracy for thermochemistry, kinetics, and non-covalent interactions. Tests show that for non-covalent systems, omegaB97X-D shows slight improvement over other empirical dispersion-corrected density functionals, while for covalent systems and kinetics it performs noticeably better. Relative to our previous functionals, such as omegaB97X, the new functional is significantly superior for non-bonded interactions, and very similar in performance for bonded interactions.