Trends of the bonding effect on the performance of DFT methods in electric properties calculations: A pattern recognition and metric space approach on some XY₂ (X = O, S and Y = H, O, F, S, Cl) molecules

Abstract

A test set of 10 molecules (open and ring forms of ozone and sulfur dioxide as well as water and hydrogen sulfide and their respective fluoro- and chloro-substituted analogs) of specific atmospheric interest has been formed as to assess the performance of various density functional theory methods in (hyper)polarizability calculations against well-established ab initio methods. The choice of these molecules was further based on (i) the profound change in the physics between isomeric systems, e.g., open (C(2v)) and ring (D(3h)) forms of ozone, (ii) the relation between isomeric forms, e.g., open and ring form of sulfur dioxide (both of C(2v) symmetry), and (iii) the effect of the substitution, e.g., in fluoro- and chloro-substituted water analogs. The analysis is aided by arguments chosen from the information theory, graph theory, and pattern recognition fields of Mathematics: In brief, a multidimensional space is formed by the methods which are playing the role of vectors with the independent components of the electric properties to act as the coordinates of these vectors, hence the relation between different vectors (e.g., methods) can be quantified by a proximity measure. Results are in agreement with previous studies revealing the acceptable and consistent behavior of the mPW1PW91, B3P86, and PBE0 methods. It is worth noting the remarkable good performance of the double hybrid functionals (namely: B2PLYP and mPW2PLYP) which are for the first time used in calculations of electric response properties.

Applying Conventional Ab Initio and Density Functional Theory Approaches to Electric Property Calculations. Quantitative Aspects and Perspectives

“…Pattern recognition has long found application in Chemistry [93]. Our use of such techniques extends the application of pattern recognition (PR) to a hitherto unreached field: computational quantum chemistry (CQC The above-mentioned methodology has found application in various quantum chemistry problems [94][95][96]. We give here only a few essential points and definitions.…”

Dynamic (hyper)polarizabilities of the ozone molecule: Coupled cluster calculations including vibrational corrections

“…[24][25][26] However, to our knowledge, there are no theoretical results at this level for frequency-dependent hyper(polarizabilities). [24][25][26] However, to our knowledge, there are no theoretical results at this level for frequency-dependent hyper(polarizabilities).…”

“…[9][10][11][12][13][14] Despite the small number of electrons, ozone is not a simple molecule to treat theoretically. [24][25][26] Results of density functional theory, many-body perturbation theory, and coupled cluster calculations based on the finite-field scheme, with especially constructed basis sets, have been reported for the static (hyper)polarizabilities a) Permanent address: Coordenação de Física, Departamento II, Instituto Federal de Goiás, Goiânia, Goiás 74055-110, Brazil. [15][16][17] Coupled cluster, configuration interaction, and multiconfigurational calculations revealed that the inclusion of the connected triple and even quadruple excitations is essential to yield results in good agreement with experiments for the equilibrium geometry, vibrational frequencies, and dissociation energy.…”

Charge distribution, electric multipole moments, static polarizability and hyperpolarizability of silene

“…As little relevant information exists in the literature, we focus carefully on the performance of the theoretical methods. To this end, we employ a graph-theoretic method based on generalized metrics [20] which has been successfully applied to a variety of molecular property studies [21][22][23][24].…”