You are here

Quasi-Atomic Bond Analyses in the Sixth Period: I. Relativistic Accurate Atomic Minimal Basis Sets for the Elements Cesium to Radon

TitleQuasi-Atomic Bond Analyses in the Sixth Period: I. Relativistic Accurate Atomic Minimal Basis Sets for the Elements Cesium to Radon
Publication TypeJournal Article
Year of Publication2019
AuthorsSchoendorff, G, West, AC, Schmidt, M, Ruedenberg, K, Gordon, MS
JournalJournal of Physical Chemistry A
Volume123
Pagination5242-5248
Date Published06
Type of ArticleArticle
ISBN Number1089-5639
Accession NumberWOS:000473251700006
Keywordschemistry, consistent-field method, direct configuration-interaction, douglas-kroll, molecular-orbitals, multiple active spaces, natural orbitals, occupations, physics, states, valence virtual orbitals, variable
Abstract

Full-valence relativistic accurate atomic minimal basis set (AAMBS) orbitals are developed for the sixth-row elements from cesium to radon, including the lanthanides. Saturated primitive atomic basis sets are developed and subsequently used to form the AAMBS orbitals. By virtue of the use of a saturated basis, properties computed based on the AAMBS orbitals are basis set independent. In molecules, the AAMBS orbitals can be used to construct valence virtual orbitals (VVOs) that provide chemically meaningful ab initio lowest unoccupied molecular orbitals (LUMOs) with basis set independent orbital energies. The optimized occupied molecular orbitals complemented with the VVOs form a set of full-valence molecular orbitals. They can be transformed into a set of oriented quasi-atomic orbitals (QUAOs) that provide information on intramolecular bonding via an intrinsic density analysis. In the present work, the development of the AAMBS for the sixth row is presented.

DOI10.1021/acs.jpca.9b04023
Custom 1

Chemical Physics

Alternate JournalJ. Phys. Chem. A