NLO‐X (X = I–III): New Gaussian basis sets for prediction of linear and nonlinear electric properties

Abstract

New adjusted Gaussian basis sets are proposed for first and second rows elements (H, B, C, N, O, F, Si, P, S, and Cl) with the purpose of calculating linear and mainly nonlinear optical (L-NLO) properties for molecules. These basis sets are new generation of Thakkar-DZ basis sets, which were recontracted and augmented with diffuse and polarization extrabasis functions. Atomic energy and polarizability were used as reference data for fitting the basis sets, which were further applied for prediction of L-NLO properties of diatomic, H 2 , N 2 , F 2 , Cl 2 , BH, BF, BCl, HF, HCl, CO, CS, SiO, PN, and polyatomic, CH 4 , SiH 4 , H 2 O, H 2 S, NH 3 , PH 3 , OCS, NNO, and HCN molecules. The results are satisfactory for all electric properties tested; dipole moment (m), polarizability (a), and first hyperpolarizability (b), with an affordable computational cost. Three new basis sets are presented and called as NLO-I (ADZP), NLO-II (DZP), and NLO-III (VDZP). The NLO-III is the best choice to predict L-NLO properties of large molecular systems, because it presents a balance between computational cost and accuracy. The average errors for b at B3LYP/NLO-III level were of 8% for diatomic molecules and 14% for polyatomic molecules that are within the experimental uncertainty.

Predicting Pt‐195 NMR chemical shift using new relativistic all‐electron basis set

“…The exponents of these polarization functions were adjusted manually to minimize the UHF‐DKH atomic energy in the presence of an electric field ( a.u.) …”

Dipole moments of conjugated donor–acceptor substituted systems: calculations vs. experiments

“…9 The second approach suggests adjusting basis sets for H, C, N and O atoms to reproduce the experimental dipole moments, polarizabilities and hyperpolarizabilities. 11,12 Using B3LYP functional with NLOIII basis set afforded DM and hyperpolarizability of polyatomic molecules in good agreement with the experiments. 11 Another experimental approach closely related to the dipole moment determinations and serving as an alternative quantitative evaluation of the electron density distribution within molecules is variable temperature NMR spectroscopy (dynamic NMR or D-NMR).…”

Assessment of a Computational Protocol for Predicting Co-59 NMR Chemical Shift

“…Finally, the basis set was augmented with the addition of three sets of f-polarization functions, with the exponents being adjusted in order to minimize the atomic energy at the UHF-DKH2 level in the presence of an electric field (z = 0.01 a.u.) [49]. This calculation was also performed in GAUSSIAN 16 Rev.…”