Polarized basis sets for accurate calculations of static and dynamic electric properties of molecules

Abstract

We report on the development and testing of large polarized basis sets (LPolX, where X is the element symbol) for accurate calculations of linear and nonlinear electric properties of molecules. The method used to generate LPolX sets is based on our studies of the analytic dependence of Gaussian functions on external time-independent and time-dependent electric fields. At variance with the earlier investigations of small, highly compact (ZPolX) basis sets for moderately accurate calculations of electric properties of large molecules, the present goal is to obtain basis sets that are nearly saturated with respect to the selected class of electric properties and can be used for accurate studies of interaction-induced properties. This saturation makes the LPolX sets also useful in calculations of optical properties for chiral molecules. In this article, the LPolX sets are generated for X = H, C, N, O, and F, and examined in calculations of linear and nonlinear electric properties of four standard test systems: HF, N(2), CO, and HCN. The study of the performance of LPolX basis sets has been carried out at different levels of approximation ranging from the SCF HF method to highly correlated CCSD(T) approach. The results obtained in this study compare favorably with accurate reference data and show a high level of saturation of LPolX basis sets with respect to the polarization effect due to external electric fields.

Gaussian basis sets for molecular applications

“…For example, if an investigation is focused solely on the electric properties of molecules, then using a basis set that has been optimized specifically for that purpose is likely to produce very good results. [8] However, attempting to address all basis sets specialized for every different type of physicochemical property would represent a huge undertaking, hence this review will be mainly concerned with atom-centered, ' 'energy-optimized' ' basis sets, where the exponents are optimized to minimize an electronic energy. Such basis sets are considered to be more general-purpose, yet are often augmented with additional functions when considering specific problems (see later).…”

Importance of electron correlation effects and basis set superposition error in calculations of interaction energies and interaction-induced electric properties in hydrogen-bonded complexes: a model study

“…The LPol-n bases [10] belong to the family of the polarized sets derived by Sadlej and co-workers over the last decades [4][5][6][7][8][9]. The Pol set family, including the ZPol and the LPol sets, is designed for calculations of electric properties in molecular systems.…”

“…The resemblance of the solutions of the harmonic oscillator Schrödinger equation to the commonly used Gaussian-type orbitals in ab initio and DFT calculations leads to the model of generation of the polarization functions augmenting a properly chosen source set of basis functions. Recently, the model has been generalized to the case of a dynamic electric field perturbation [26], which resulted in the development of the LPol-n basis sets [10].…”

“…Another example of propertyoriented basis sets is the so-called polarized basis sets (Pol sets) developed for calculations of electric properties and originating from a simple physical model of a harmonic oscillator embedded in an external electric field [3]. Polarized sets have long tradition and span from the pioneer Pol basis sets [4][5][6], through the compact ZPol sets [7][8][9], to the recently reported LPol basis sets [10]. The ZPol basis sets are recommended for moderately accurate calculations of linear electric properties in large molecular systems [7][8][9].…”

“…The ZPol basis sets are recommended for moderately accurate calculations of linear electric properties in large molecular systems [7][8][9]. The LPol sets have been shown to compete with the much larger Dunning's sets in the evaluation of electric properties and of specific optical rotation in organic molecules [10][11][12].…”