How accurate are static polarizability predictions from density functional theory? An assessment over 132 species at equilibrium geometry

Abstract

Static polarizabilities are the first response of the electron density to electric fields, and are therefore important for predicting intermolecular and molecule-field interactions. They also offer a global measure of the accuracy of the treatment of excited states by density functionals in a formally exact manner. We have developed a database of benchmark static polarizabilities for 132 small species at equilibrium geometry, using coupled cluster theory through triple excitations (extrapolated to the complete basis set limit), for the purpose of developing and assessing density functionals. The performance of 60 popular and recent functionals are also assessed, which indicates that double hybrid functionals perform the best, having RMS relative errors in the range of 2.5-3.8%. Many hybrid functionals also give quite reasonable estimates with 4-5% RMS relative error. A few meta-GGAs like mBEEF and MVS yield performance comparable to hybrids, indicating potential for improved excited state predictions relative to typical local functionals. Some recent functionals however are found to be prone to catastrophic failure (possibly as a consequence of overparameterization), indicating a need for caution in applying these.

The Role of Computational Chemistry in the Experimental Determination of the Dipole Moment of Molecules in Solution

“…More specifically, with the larger basis set aug‐cc‐pvtz the deviation is of 2.0 % in the case of the system I and ‐ 0.3 % for the system II. Hence, the agreement of the computed polarizability in solution is of the same level of accuracy as obtained for the case of isolated molecule …”

“…Hence, the agreement of the computed polarizability in solution is of the same level of accuracy as obtained for the case of isolated molecule. [12,13]…”

“…This choice allows to explore the basis set dependence of these electronic properties. We note that DFT‐B3LYP/aug‐cc‐pvtz level is able to assure a good agreement between theoretical and experimental results for dipole moments and electronic polarizabilities of isolated molecules . To reduce the computational effort, the vibrational polarizabilities have been computed from eq.…”

“…On the other side, the methods of computational quantum chemistry allow the calculation of the electric dipole moment of molecules both in the gas phase, [9][10][11][12][13][14] and in solution with the use of solvation models. [15][16][17][18][19][20][21] However, the comparison between the quantum chemical computed dipole moment of solvated molecules with the Onsager experimental dipole moment is hampered by several approximations of the Onsager model.…”

ACCDB: A collection of chemistry databases for broad computational purposes

“…For more details of all the subsets of every database, as well as references to their original sources, and a better overview of their overlaps, see also the Supporting Information. [7,12,[22][23][24][25][26][27][30][31][32][33][34][35][36][37][38][39][40]46,48, Automation Software ACCDB contains 10,049 geometry files-in xyz format, and appropriately named, including charge and spin multiplicity data-collected in one directory called "Geometries." Each file requires a single-point energy calculation, usually performed with quantum chemistry software engines, such as Gaussian [175] or Q-Chem.…”