Diffuse Basis Functions for Relativistic s and d Block Gaussian Basis Sets

Abstract

Diffuse s, p, and d functions have been optimized for use with previously reported relativistic basis sets for the s and d blocks of the periodic table. The functions were optimized on the 4:1 weighted average of the s2 and p2 configurations of the anion, with the d shell in the d n+1 configuration for the d blocks. Exponents were extrapolated for groups 2 and 12, which have unstable or weakly bound anions. The diffuse basis sets have been tested by application to calculations of electron affinities of the group 11 elements (Cu, Ag, and Au), double electron affinities of the group 11 monocations, and potential energy curves of Mg2 and Ca2 van der Waals dimers, as well as some response properties of the group 1 anions (Rb–, Cs–, and Fr–), the group 2 elements (Sr, Ba, and Ra), and RbLi, CsLi, and FrLi molecules.

Formulation and Implementation of Frequency-Dependent Linear Response Properties with Relativistic Coupled Cluster Theory for GPU-Accelerated Computer Architectures

“…All coupled cluster linear-response calculations were carried out with a development version of the DIRAC code, , employing the uncontracted singly augmented valence double-ζ Dyall basis set s-aug-dyall.v2z for the heavy elements (Zn, Cd, Hg, Cs, I, , , and Te , ), and a similar uncontracted Dunning basis set aug-cc-pVDZ for the light elements (H, Li, Na, K, F, Cl, O, S, Se,, and Br). In most calculations, we utilized the exact two-component (X2C) relativistic Hamiltonian, where the spin–orbit operator takes the form of an effective one-electron operator.…”

Frequency-Dependent Quadratic Response Properties and Two-Photon Absorption from Relativistic Equation-of-Motion Coupled Cluster Theory

“…All EOM-CC quadratic response and TPA calculations were carried out with development versions (see revision number in SI) of the DIRAC code, , employing the uncontracted triply augmented valence triple-ζ Dyall basis set (defined as t-aug-dyall.v3z in inputs) for heavy elements (In, I, At, Xe, and Rn), , and an equivalent triply augmented uncontracted Dunning basis set (defined as t-aug-cc-pVTZ in inputs) for light elements (H, F, Cl, Ga, and Br) . − We utilized the exact two-component (X2C) relativistic Hamiltonian, and in some cases, to show the effect of relativity explicitly, we also provide results using the nonrelativistic Hamiltonian , (as activated by the .Levy-Leblond keyword). To study the effect of electron correlation, we performed quadratic response and TPA calculations based on mean-field methods such as HF and DFT (employing the B3LYP density functional approximation).…”

Benchmark Study of the Electronic States of the LiRb Molecule: Ab Initio Calculations with the Fock Space Coupled Cluster Approach

“…In terms of theoretical research, there is a notable number of papers concerning LiRb. These studies may be classified as follows: studies of electric properties [7,[22][23][24][25], computations of dispersion coefficients [1,[26][27][28][29], calculations of PECs and spectroscopic constants [30][31][32][33][34][35][36][37][38][39][40][41][42][43], and others [44][45][46][47][48][49][50][51]. Among those, the studies of PECs and spectroscopic constants are most relevant in terms of our research.…”