Hyperpolarizability of GaAs dimer is not negative

Abstract

We present a systematic study of the static electric hyperpolarizability of Ga(2)As(2). The authors rely on finite-field high-level ab initio calculations with carefully optimized basis sets. Their best values for the mean and the anisotropy of the dipole polarizability are alpha=158.57 and Deltaalpha=130.33e(2)a(0) (2)E(h) (-1). For the hyperpolarizability we propose an estimate gamma=(155+/-15)x10(3)e(4)a(0) (4)E(h) (-3), which does not agree with the negative value predicted by Lan et al. [J. Chem. Phys. 124, 094302 (2006)]. Density functional theory based methods yield values close to those predicted by conventional ab initio methods. The (hyper)polarizability components are particularly enhanced along the direction defined by the Ga-Ga axis.

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

“…The construction of molecule-specific, purpose-oriented basis sets for large molecular architectures or low-symmetry polyatomics is largely impractical. Nevertheless, previous work shows that for systems of reasonable size as atoms [23,53], atomic anions or cations [54,55], diatomics [56,57] and triatomics [58][59][60][61], symmetric polyatomics [62][63][64], and clusters [65][66][67][68], one can easily control the construction of the basis set in order to obtain suitable basis sets for electric property calculations.…”

Bond length dependence of the polarizability and hyperpolarizability of boron hydride

“…Although the construction of purpose-oriented basis sets for polarizability calculations has been the object of several investigations [51][52][53][54][55], there are no reliable criteria for the choice of basis sets in theoretical predictions of electric hyperpolarizabilities. Previous experience shows that for atoms [56][57][58][59], diatomics [60][61][62], triatomics [63][64][65], and small polyatomics [66][67][68][69], it is possible to design basis sets by systematically augmenting reliable substrates of GTFs. Different strategies must be adopted in the case of clusters [70] or sequences of clusters [71][72][73][74].…”

A systematic search for the structures, stabilities, and electronic properties of bimetallic Ca2-doped gold clusters: comparison with pure gold clusters

“…In light of previous research [63][64][65][66], Maroulis et al determined the level of calculation needed to compute accurate cluster polarizability values; their results showed that the DFT method can provide reasonable values. The effects of the basis set on cluster polarizability were also discussed by the group of Maroulis [66][67][68][69].…”

“…The effects of the basis set on cluster polarizability were also discussed by the group of Maroulis [66][67][68][69]. We obtained the polarizabilities of our systems with the same basis set as used for the optimizations, so that the calculations required were not excessively time-consuming.…”