All-electron segmented contraction basis sets of triple zeta valence quality for the fifth-row elements

Martins, L.S.C.; Jorge, F.E.; Machado, S.F.

doi:10.1080/00268976.2015.1040095

Cited by 39 publications

(31 citation statements)

References 53 publications

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“…For completeness, the integration plane is shown in the Supporting Information. These calculations were performed with the functionals BP86, , PBE, PBE0, B3LYP, , TPSS, ,, TPSSh, , CAM-B3LYP, − , ωB97X-D, − , and LC-ωPBE. − , def(2)-TZVP basis sets , together with effective core potentials , as well as more sophisticated scalar-relativistic all-electron approaches (DLU-X2C) ,,, using the Jorge-TZP-DKH , and Dyall-VTZ ,,, basis sets were employed. The SCF procedure takes 22 (Jorge-TZP-DKH, 179 iterations) and 127 min (Dyall-VTZ, 88 iterations) with the PBE functional, whereas 0.6 and 7.5 min are required for the pNMR shieldings, respectively, using 8 OpenMP threads of an Intel Xeon Gold 6212U CPU @ 2.40 GHz and exploiting D 3h point group symmetry.…”

Section: Resultsmentioning

confidence: 99%

“…Tailored grids (gridsize 4a) were used for the numerical integration of the exchange-correlation terms in case of the latter calculations, whereas gridsize 4 was used for nonrelativistic calculations. , Errors are measured with respect to the large even-tempered basis set of ref . The nonrelativistic studies include the def2, pcSseg, and the pcJ bases, whereas the scalar-relativistic calculations utilize uncontracted Dyall bases , together with fully decontracted correlation-consistent bases ,,, as well as the x2c-type, ,, the Jorge-DZP-DKH, − and Jorge-TZP-DKH basis set, ,, as well as the decontracted ANO-RCC , and ANO-R bases . The ccJ-pVXZ (X = D, T, Q) and the Jorge bases were taken from the Basis Set Exchange Library , and decontracted if needed.…”

Section: Theorymentioning

confidence: 99%

“…SCF convergence thresholds were set to 10 –8 E h for all calculations and gridsize 4 was used for the numerical integration of the exchange-correlation terms. , For the DLU-X2C calculations, gridsize 4a was used and the RI- J approximation was not used. Here, Dyall’s VTZ basis ,,, as well as the Jorge-TZP-DKH basis sets , were employed. The latter was taken from the Basis Set Exchange Library. , Calculations were performed within the finite nucleus model for both the scalar potential and the vector potential .…”

Section: Theorymentioning

confidence: 99%

“…169,170 Errors are measured with respect to the large even-tempered basis set of ref 171. The nonrelativistic studies include the def2, 165 pcSseg, 172 and the pcJ 162 bases, whereas the scalar-relativistic calculations utilize uncontracted Dyall bases 173,174 together with fully decontracted correlation-consistent bases 156,157,175,176 as well as the x2c-type, 168,171,177 the Jorge-DZP-DKH, 178−180 and Jorge-TZP-DKH basis set, 178,181,182 as well as the decontracted ANO-RCC 159,183 and ANO-R bases. 184 The ccJ-pVXZ (X = D, T, Q) and the Jorge bases were taken from the Basis Set Exchange Library 185,186 and decontracted if needed.…”

Section: ■ Introductionmentioning

confidence: 99%

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Paramagnetic NMR Shielding Tensors and Ring Currents: Efficient Implementation and Application to Heavy Element Compounds

2021

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We present an efficient implementation of paramagnetic NMR shielding tensors and shifts in a nonrelativistic and scalar-relativistic density functional theory framework. For the latter, we make use of the scalar exact two-component Hamiltonian in its local approximation, and generally we apply the well established (multipole-accelerated) resolution of the identity approximation and the seminumerical exchange approximation. The perturbed density matrix of a paramagnetic NMR shielding calculation is further used to study the magnetically induced current density and ring currents of open-shell systems as illustrated for [U@Bi 12 ] 3− . [U@Bi 12 ] 3− features delocalized highest occupied molecular orbitals and sustains a net diatropic ring current of ca. 18 nA/T through the Bi 12 torus similar to the allmetal aromatic heavy-element cluster [Th@Bi 12 ] 4− .

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Section: Resultsmentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Paramagnetic NMR Shielding Tensors and Ring Currents: Efficient Implementation and Application to Heavy Element Compounds

2021

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“…To test the sensitivity of SOC corrections to method and basis set, the SOC corrections were compared for the two-component method implemented in Turbomole (activated $soghf keyword in the control file) using relativistic effective core potentials, [87,[113][114][115] with the basis sets dhf-QZVPP-2c [116] and the DKH Hamiltonian using the basis set by Martins, Jorge, and Machado, which we refer to below as Jorge-TZP-DKH. [117] This all-electron basis set was designed for the DKH Hamiltonian and obtained from the basis set exchange web server. [118][119][120] An excellent description of DKH theory can be found in the account by Reiher.…”

Section: Zero-point Vibrational and Relativistic Correctionsmentioning

confidence: 99%

Dioxygen Binding to all 3d, 4d, and 5d Transition Metals from Coupled‐Cluster Theory

Moltved

Kepp

2020

ChemPhysChem

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Understanding how transition metals bind and activate dioxygen (O 2) is limited by experimental and theoretical uncertainties, making accurate quantum mechanical descriptors of interest. Here we report coupled-cluster CCSD(T) energies with large basis sets and vibrational and relativistic corrections for 160 3d, 4d, and 5d metal-O 2 systems. We define four reaction energies (120 in total for the 30 metals) that quantify OÀ O activation and reveal linear relationships between metal-oxygen and OÀ O binding energies. The CCSD(T) data can be combined with thermochemical cycles to estimate chemisorption and physisorption energies for each metal from metal oxide embedding energies, in good correlation with atomization enthalpies (R 2 = 0.75). Spin-geometry variations can break the linearities, of interest to circumventing the Sabatier principle. Pt, Pd, Co, and Fe form a distinct group with the weakest O 2 binding. R 2 up to 0.84 between surface adsorption energies and our energies for MO 2 systems indicate relevance also to real catalytic systems.

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Spherical Aromaticity of Tetrahedral Pnictogens Through Off‐Nucleus Isotropic Magnetic Shielding

Al-Yassiri

2022

ChemPhysChem

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This work revealed the spherical aromaticity of some inorganic E4 cages and their protonated E4H+ ions (E=N, P, As, Sb, and Bi). For this purpose, we employed several evaluations like (0D‐1D) nucleus independent chemical shift (NICS), multidimensional (2D‐3D) off‐nucleus isotropic shielding σiso(r), and natural bond orbital (NBO) analysis. The magnetic calculations involved gauge‐including atomic orbitals (GIAO) with two density functionals B3LYP and WB97XD, and basis sets of Jorge‐ATZP, 6‐311+G(d,p), and Lanl2DZp. The Jorge‐ATZP basis set showed the best consistency. Our findings disclosed non‐classical aromatic characters in the above molecules, which decreased from N to Bi cages. Also, the results showed more aromaticity in E4 than E4H+. The NBO analysis attributed the aromaticity in the above molecules to the residual density of the overlapping σ‐bonding orbitals. So, the aromaticity in these molecules is unlike the classical aromaticity that is associated with electron delocalization. Scanning 1D σiso(r) variation along E−E bonds indicated a lowering in the shielding trend from N to Bi cages. The 3D results showed a similar decrease in the relative volumetric diffusion of the magnetic activity, whereas the volumetric ratio of V1ppm/V2ppm is almost constant for all the E4 cages.

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All-electron segmented contraction basis sets of triple zeta valence quality for the fifth-row elements

Cited by 39 publications

References 53 publications

Paramagnetic NMR Shielding Tensors and Ring Currents: Efficient Implementation and Application to Heavy Element Compounds

Paramagnetic NMR Shielding Tensors and Ring Currents: Efficient Implementation and Application to Heavy Element Compounds

Dioxygen Binding to all 3d, 4d, and 5d Transition Metals from Coupled‐Cluster Theory

Spherical Aromaticity of Tetrahedral Pnictogens Through Off‐Nucleus Isotropic Magnetic Shielding

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