A Density-Based Basis-Set Correction for Wave Function Theory

<div><div><div><p>We report a universal density-based basis-set incom-<br>pleteness correction that can be applied to any wave<br>function method. The present correction, which ap-<br>propriately vanishes in the complete basis set (CBS)<br>limit, relies on short-range correlation density func-<br>tionals (with multi-determinant reference) from range-<br>separated density-functional theory (RS-DFT) to esti-<br>mate the basis-set incompleteness error. Contrary to<br>conventional RS-DFT schemes which require an ad hoc<br>range-separation parameter μ, the key ingredient here<br>is a range-separation function μ(r) that automatically<br>adapts to the spatial non-homogeneity of the basis-set<br>incompleteness error. As illustrative examples, we show how this density-based correction allows us to obtain CCSD(T) atomization and correlation energies near the CBS limit for the G2 set of molecules with compact Gaussian basis sets.</p></div></div></div>

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Evaluating Transition Metal Barrier Heights with the Latest DFT Exchange–Correlation Functionals – the MOBH35 Benchmark Dataset

10.26434/chemrxiv.7732262.v1 ◽

2019 ◽

Author(s):

Mark Iron ◽

Trevor Janes

Keyword(s):

Transition Metal ◽

Density Functional ◽

Computational Cost ◽

Basis Set ◽

Functional Theory ◽

Exchange Correlation ◽

Barrier Heights ◽

Complete Basis Set ◽

Complete Basis Set Limit ◽

Hybrid Functionals

A new database of transition metal reaction barrier heights – MOBH35 – is presented. Benchmark energies (forward and reverse barriers and reaction energy) are calculated using DLPNO-CCSD(T) extrapolated to the complete basis set limit using a Weizmann1-like scheme. Using these benchmark energies, the performance of a wide selection of density functional theory (DFT) exchange–correlation functionals, including the latest from the Truhlar and Head-Gordon groups, is evaluated. It was found, using the def2-TZVPP basis set, that the ωB97M-V (MAD 1.8 kcal/mol), ωB97X-V (MAD 2.1 kcal/mol) and SCAN0 (MAD 2.1 kcal/mol) hybrid functionals are recommended. The double-hybrid functionals PWPB95 (MAD 1.6 kcal/mol) and B2K-PLYP (MAD 1.8 kcal/mol) did perform slightly better but this has to be balanced by their increased computational cost.

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Benchmark of Simplified Time-Dependent Density Functional Theory for UV-Vis Spectral Properties of Porphyrinoids

10.26434/chemrxiv.9912860 ◽

2019 ◽

Author(s):

Kamal Batra ◽

Stefan Zahn ◽

Thomas Heine

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Large Scale ◽

Absolute Error ◽

Time Dependent ◽

Basis Set ◽

Basis Sets ◽

Functional Theory ◽

Framework Materials ◽

Dependent Density

<p>We thoroughly benchmark time-dependent density- functional theory for the predictive calculation of UV/Vis spectra of porphyrin derivatives. With the aim to provide an approach that is computationally feasible for large-scale applications such as biological systems or molecular framework materials, albeit performing with high accuracy for the Q-bands, we compare the results given by various computational protocols, including basis sets, density-functionals (including gradient corrected local functionals, hybrids, double hybrids and range-separated functionals), and various variants of time-dependent density-functional theory, including the simplified Tamm-Dancoff approximation. An excellent choice for these calculations is the range-separated functional CAM-B3LYP in combination with the simplified Tamm-Dancoff approximation and a basis set of double-ζ quality def2-SVP (mean absolute error [MAE] of ~0.05 eV). This is not surpassed by more expensive approaches, not even by double hybrid functionals, and solely systematic excitation energy scaling slightly improves the results (MAE ~0.04 eV). </p>

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Density Functional Theory and Complete Basis Set Ab Initio Computational Study of Five-, Six-, Seven- and Eight-hydrogen Coordinated Carbon Cations

Journal of Chemical Research ◽

10.1177/174751989902300824 ◽

1999 ◽

Vol 23 (8) ◽

pp. 502-503

Author(s):

Branko S. Jursic

Keyword(s):

Density Functional Theory ◽

Ab Initio ◽

Density Functional ◽

Computational Study ◽

Basis Set ◽

Functional Theory ◽

Complete Basis ◽

Complete Basis Set ◽

High Level

High level ab initio and density functional theory studies are performed on highly protonated methane species.

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Estimating the adsorption energy of element 113 on a gold surface

Open Physics ◽

10.2478/s11534-013-0311-4 ◽

2013 ◽

Vol 11 (11) ◽

Cited By ~ 3

Author(s):

Alexander Rusakov ◽

Yuriy Demidov ◽

Andréi Zaitsevskii

Keyword(s):

Adsorption Energy ◽

Cluster Size ◽

Density Functional ◽

Gold Surface ◽

Gold Clusters ◽

Basis Sets ◽

Energy Estimates ◽

First Principle ◽

Gaussian Basis Sets ◽

Functional Theory

AbstractWe report first-principle based studies of element 113 (E113) interactions with gold aimed primarily at estimating the adsorption energy in thermochromatographic experiments. The electronic structure of E113-Aun systems was treated within the accurate shape-consistent small core relativistic pseudopotential framework at the level of non-collinear relativistic density functional theory (RDFT) with specially optimised Gaussian basis sets. We used gold clusters with up to 58 atoms to simulate the adsorption site on the stable Au(111) surface. Stabilization of the E113-Aun binding energy and the net Bader charge of E113 and the neighboring Au atoms with respect to n indicated the cluster size used was appropriate. The resulting adsorption energy estimates lie within the 1.0–1.2 eV range, substantially lower than previously reported values.

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Complete basis set, gaussian and density functional theory study of molecular aggregates of beryllium hydride and boron hydride as a chain terminated in the polymerization of beryllium hydride

Journal of Molecular Structure THEOCHEM ◽

10.1016/s0166-1280(98)00379-0 ◽

1999 ◽

Vol 467 (1) ◽

pp. 7-23 ◽

Cited By ~ 4

Author(s):

B.S. Jursic

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Basis Set ◽

Boron Hydride ◽

Density Functional Theory Study ◽

Molecular Aggregates ◽

Functional Theory ◽

Complete Basis ◽

Complete Basis Set ◽

A Chain

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Hybrid density functional theory and quadratic complete basis set ab initio computational study of structural properties, vibrational spectra, and bond dissociation energy for methyl aluminum and methyl gallium

Journal of Molecular Structure THEOCHEM ◽

10.1016/s0166-1280(97)00262-5 ◽

1998 ◽

Vol 428 (1-3) ◽

pp. 61-66 ◽

Cited By ~ 39

Author(s):

Branko S. Jursic

Keyword(s):

Density Functional Theory ◽

Ab Initio ◽

Vibrational Spectra ◽

Density Functional ◽

Computational Study ◽

Basis Set ◽

Hybrid Density Functional Theory ◽

Functional Theory ◽

Complete Basis Set ◽

Hybrid Density Functional

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THEORETICAL STUDIES ON BOND DISSOCIATION ENERGIES FOR SOME THIOL COMPOUNDS BY DENSITRY FUNCTIONAL THEORY AND CBS-Q METHOD

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633608004258 ◽

2008 ◽

Vol 07 (05) ◽

pp. 943-951 ◽

Cited By ~ 2

Author(s):

XIAO-HONG LI ◽

ZHENG-XIN TANG ◽

ABRAHAM F. JALBOUT ◽

XIAN-ZHOU ZHANG ◽

XIN-LU CHENG

Keyword(s):

Density Functional ◽

Computational Cost ◽

Basis Set ◽

Basis Sets ◽

Q Method ◽

Bond Dissociation Energies ◽

Functional Theory ◽

Thiol Compounds ◽

Bond Dissociation ◽

Dissociation Energies

Quantum chemical calculations are used to estimate the bond dissociation energies (BDEs) for 15 thiol compounds. These compounds are studied by employing the hybrid density functional theory (B3LYP, B3PW91, B3P86, PBE0) methods and the complete basis set (CBS-Q) method together with 6-311G** basis set. It is demonstrated that B3P86 and CBS-Q methods are accurate for computing the reliable BDEs for thiol compounds. In order to test whether the non-local BLYP method suggested by Fu et al.19 is general for our study and whether B3P86 method has a low basis set sensitivity, the BDEs for seven thiol compounds are also calculated using BLYP/6-31+G* and B3P86 method with 6-31+G*, 6-31+G**, and 6-311+G** basis sets for comparison. The obtained results are compared with the available experimental results. It is noted that B3P86 method is not sensitive to the basis set. Considering the inevitable computational cost of CBS-Q method and the reliability of the B3P86 calculations, B3P86 method with a moderate or a larger basis set may be more suitable to calculate the BDEs of the C–SH bond for thiol compounds.

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Complete basis set, hybrid-density functional theory study, and natural bond orbital interpretations of the conformational behavior of halocarbonyl, thiocarbonyl, and selenocarbonyl isocyanates

Canadian Journal of Chemistry ◽

10.1139/v2012-002 ◽

2012 ◽

Vol 90 (4) ◽

pp. 333-343 ◽

Cited By ~ 1

Author(s):

Seiedeh Negar Mousavi ◽

Davood Nori-Shargh ◽

Hooriye Yahyaei ◽

Kobra Mazrae Frahani

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Energy Difference ◽

Basis Set ◽

Hybrid Density Functional Theory ◽

Total Dipole Moment ◽

Functional Theory ◽

Complete Basis Set ◽

Conformation Stability ◽

Hybrid Density Functional

Complete basis set CBS-QB3, hybrid-density functional theory (B3LYP/Def2-TZVPP) based methods and NBO interpretation were used to investigate the impacts of the stereoelectronic effects and electrostatic and steric interactions on the conformational properties of halocarbonyl isocyanates (halo = F (1), Cl (2), and Br (3)), halothiocarbonyl isocyanates (halo = F (4), Cl (5), and Br (6)), and haloselenocarbonyl isocyanates(halo = F (7), Cl (8), and Br (9)). Both methods showed that the Z-conformations of compounds 1, 4, and 7 are more stable than their corresponding E conformations, but the stability of the E conformations, when compared with the corresponding Z conformations, increases from compound 1 to compound 3, compound 4 to compound 6, and also from compound 7 to compound 9. The NBO analysis showed that the generalized anomeric effect (GAE) is in favor of the Z conformations of compounds 1, 4, and 7. The GAE values calculated (i.e., GAEE–GAEZ) increase from compound 1 to compound 3, compound 4 to compound 6, and also from compound 7 to compound 9. On the other hand, there are none of the same trends between the calculated total dipole moment and the Gibbs free energy difference values between the E and Z conformations (i.e., ΔμE–Z and ΔGE–Z) of compounds 1–3, 4–6, and 7–9. Accordingly, the GAE succeeds in accounting for the increase of the E conformation stability from compound 1 to compound 3, compound 4 to compound 6, and also from compound 7 to compound 9. Therefore, the GAE associated with the electron delocalization, not the total dipole moment changes (i.e., ΔμE–Z), is a reasonable indicator of the total energy difference in compounds 1–3, 4–6, and 7–9. There is a direct correlation between the calculated GAE and Δ[r2–6(E) – r2–6(Z)] parameters. Importantly, there are interesting through-space electron delocalizations (LP2X6→π*C4–O5) that justify the increase of the E conformation stability from compound 1 to compound 3, compound 4 to compound 6, and also from compound 7 to compound 9, when compared with their corresponding Z conformations. The correlations between the GAE, bond orders, total steric exchange energies (TSEE), ΔGZ–E, ΔμE–Z, structural parameters, and conformational behaviors of compounds 1–9 were investigated.

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