Can Density Functional Theory Be Trusted for High-Order Electric Properties? The Case of Hydrogen-Bonded Complexes

Abstract

This work reports on an extensive assessment of the performance of a wide palette of density functional approximations in predicting the (high-order) electric properties of hydrogen-bonded complexes. To this end, we compute the electronic and vibrational contributions to the electric polarizability and the first and second hyperpolarizabilities, using the CCSD(T)/aug-cc-pVTZ level of theory as reference. For all the studied properties, the average absolute errors below 20% can only be obtained using the CAM-B3LYP functional, while LC-BLYP and MN15 are shown to be only slightly less accurate (average absolute errors not exceeding 30%). Among Minnesota density functionals, i.e., M06, M06-2X, and MN15, we only recommend the latter one, which quite accurately predicts the electronic and vibrational (hyper)polarizabilities. We also analyze the optimal tuning of the range-separation parameter μ for the LC-BLYP functional, finding that this approach does not bring any systematic improvement in the predictions of electronic and vibrational (hyper)polarizabilities and the accuracy of computed properties is largely system-dependent. Finally, we report huge errors in predicting the vibrational second hyperpolarizability by ωB97X, M06, and M06-2X functionals. Based on the explicit evaluation of anharmonic terms contributing to the second hyperpolarizability, this failure is traced down to a poor determination of third- and fourth-order energy derivatives with respect to normal modes. These results reveal serious flaws of some density functional approximations and suggest caution in selecting the appropriate functional to calculate not only electronic and vibrational (hyper)polarizabilities but also other molecular properties that contain vibrational anharmonic contributions

R.Z. acknowledges financial support by the Polish National Science Centre (Grant No. 2015/19/B/ST4/01881). M.M. acknowledges the Slovak Research and Development Agency (project no. APVV-15-0105) and CMST COST Action CM1405 MOLIM: MOLecules In Motion. J.M.L. and E.M. are grateful for financial support from the Spanish MINECO CTQ2014-52525-P (E.M. and J.M.L.) and EUIN2017-88605 (E.M.), and to the Catalan DIUE 2014SGR931 (J.M.L.). S.P.S. acknowledges the Basque Government for funding through a predoctoral fellowship (PRE 2018 2 0200)