Gaussian basis sets for use in correlated molecular calculations. IX. The atoms gallium through krypton

Abstract

Valence correlation consistent and augmented correlation consistent basis sets have been determined for the third row, main group atoms gallium through krypton. The methodology, originally developed for the first row atoms, was first applied to the selenium atom, resulting in the expected natural groupings of correlation functions ͑although higher angular momentum functions tend to be relatively more important for the third row atoms as they were for the second row atoms͒. After testing the generality of the conclusions for the gallium atom, the procedure was used to generate correlation consistent basis sets for all of the atoms gallium through krypton. The correlation consistent basis sets for the third row main group atoms are as follows: cc-pVDZ: (14s11p6d)/͓5s4p2d͔; cc-pVTZ: (20s13p9d1 f)/͓6s5p3d1 f ͔; cc-pVQZ: (21s16p12d2 f 1g)/ ͓7s6p4d2 f 1g͔; cc-pV5Z: (26s17p13d3 f 2g1h)/͓8s7p5d3 f 2g1h͔. Augmented sets were obtained by adding diffuse functions to the above sets ͑one for each angular momentum present in the set͒, with the exponents of the additional functions optimized in calculations on the atomic anions. Test calculations on the atoms as well as selected molecules with the new basis sets show good convergence to an apparent complete basis set limit.

Efficient Temperature-Dependent Green’s Function Methods for Realistic Systems: Using Cubic Spline Interpolation to Approximate Matsubara Green’s Functions

“…This is due to the fact that the spread of Hamiltonian eigenvalues increases as larger basis sets are used. Thus, the fastest decay of ||D G1 || F is observed in cc-pVDZ [59] basis with 27 basis function and the slowest in the aug-cc-pVQZ [59] with 97 functions. Note that even when a basis with a pseudopotential that has only basis functions describing the valence orbitals is employed, to be in the linear regime requires more than 10,000 frequencies.…”

Reexamination of the calculation of two-center, two-electron integrals over Slater-type orbitals. III. Case study of the beryllium dimer

“…Then, additional uncontracted functions are used to describe the electronic correlation, see the works of Dunning [45][46][47][48][49][50][51][52][53] as a representative example. We found that GTO basis sets designed according to this principle somewhat lack flexibility for the l = 0 partial wave, especially in the molecular environment, since the number of uncontracted 1s orbitals is typically small.…”

“…Since the seminal work of Dunning and co-workers [45][46][47][48][49][50][51][52][53] it has been known that to allow for a reliable extrapolation towards CBS, basis sets need to be constructed according to the correlation consistency principle. Roughly speaking, it ensures that at a given stage all functions which give approximately the same energy contributions are simultaneously included.…”

“…It will be shown that contributions of the two-electron relativistic corrections are small and GTOs basis sets are sufficient to meet the prescribed accuracy requirements. For calculations of the two-electron relativistic corrections we used modified aug-cc-pCVXZ series of GTOs basis sets [45][46][47][48][49][50][51][52][53]. To improve the quality of the wavefunction the standard set of 1s GTOs orbitals was replaced by a new one comprising 23 1s functions.…”

Identification of mixed bromidochloridotellurate anions in disordered crystal structures of (bdmim)2[TeX2Y4] (X, Y=Br, Cl; bdmim=1-butyl-2,3-dimethylimidazolium) by combined application of Raman spectroscopy and solid-state DFT calculations

“…Gas phase optimizations of all isomers of different [TeXnY6-n] 2-(X = Cl, Y = Br) anions were carried out using the PBE0 density functional [38][39][40][41] and correlation consistent basis sets of triple--valence quality (aug-cc-pVTZ for Cl and Br, and aug-cc-pVTZ-PP for Te) [42][43][44]. The program package [45].…”