Additivity and Transferability of Atomic Contributions to Molecular Second Dipole Hyperpolarizabilities

Abstract

Large basis set ab initio calculations of the dipole polarizabilities and second hyperpolarizabilities of a large set of organic molecules have been carried out and the results have been used to assess additivity and transferability of atomic contributions to the overall molecular response tensors. Reasonable estimates of the mean second hyperpolarizability response can be obtained from summing atomic parameters obtained here, though the reliability of the estimates is worse than what is found for dipole polarizabilities. Individual tensor elements are not as well determined from transferable, additive contributions, which means that the orientational nature of the response is more subject to local bonding features.

Distributed Atomic Polarizabilities of Amino Acids and their Hydrogen-Bonded Aggregates

“…[13][14][15][16][17][18][19][20][21] Bader and co-workers 22 adopted the topological partitioning of the electron density within the Quantum Theory of Atoms in Molecules (QTAIM). The method has been successfully applied for the evaluation of intermolecular interaction energies [23][24][25] and the transferability of electrostatic properties in n-alkanes.…”

An ab initio study of CX3‐substitution (X = H, F, Cl, Br, I) effects on the static electric polarizability and hyperpolarizability of diacetylene

“…Diacetylene is currently of interest due to the increasing importance of acetylenic chemistry20. Its electric properties have been studied at various levels of theory21–24. Several experimental studies of the hyperpolarizability of diacetylene derivatives have been reported recently25–27.…”

Hybridization effect upon the vibrational second hyperpolarizability: An ab initio study of acetylene, ethylene, and ethane

“…These high‐level ab initio determinations contribute also to building a database that will be used for estimating the hyperpolarizabilities of unknown compounds within approximate models such as the bond or atom additivity schemes. Such bond/atom characteristics have already been obtained for the electronic hyperpolarizabilities either from theoretical or THG experimental 38, 39 investigations.…”