Development of new pseudopotential methods: Improved model core potentials for the first‐row transition metals

Lovallo, Christopher C.; Kłobukowski, Mariusz

doi:10.1002/jcc.10251

Cited by 38 publications

(27 citation statements)

References 21 publications

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“…The calculations were first performed using model compounds 2a* , 2d* , 3a* , and 3d* where the PMe 3 and NHC ligands were replaced with proto analogues [PH 3 and N , N′ ‐dihydroimidazolidin‐2‐ylidene (H 2 ‐NHC)], to examine the energy required to break the Au–R and Au–L bonds. All calculations were carried out using the ωB97X‐D functional, and the iMCP‐SR2 model core potentials and basis sets . Scalar‐relativistic model core potentials are known to provide satisfactory description for heavy elements like Au .…”

Section: Resultsmentioning

confidence: 99%

Controlling the Thermal Stability and Volatility of Organogold(I) Compounds for Vapor Deposition with Complementary Ligand Design

et al. 2019

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Atomic layer deposition (ALD) of gold is being studied by multiple research groups, but to date no process using non‐energetic co‐reactants has been demonstrated. In order to access milder co‐reactants, precursors with higher thermal stability are required. We set out to uncover how structure and bonding affect the stability and volatility of a family of twelve organogold(I) compounds using a combination of techniques: X‐ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and density functional theory (DFT). Small, unsubstituted phosphonium ylide ligands bind more strongly to Au(I) than their silyl‐substituted analogues, but the utility of both these ligands suffers due to their poor volatility and substantial thermal decomposition. Pentafluorophenyl (C6F5) is introduced as a new, very electronegative ligand for gold vapor deposition precursors, and it was found that the disadvantage to volatility due to π‐stacking and other intermolecular interactions in the solid state was overshadowed by dramatic improvements to kinetic and thermodynamic stability. We introduce a new figure of merit to compare and rank the suitability of these and other complexes as precursors for vapor deposition. Finally, DFT calculations on four compounds that have high figures of merit show a linear correlation between the gold‐coordinative ligand bond dissociation energies and the observed decomposition temperatures, highlighting and justifying this design strategy.

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Section: Resultsmentioning

confidence: 99%

Controlling the Thermal Stability and Volatility of Organogold(I) Compounds for Vapor Deposition with Complementary Ligand Design

et al. 2019

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“…In the past few years, many efforts have been made on generating a consistent set of ab initio ECPs and improving their quality in order to make the accuracy and reliability of ECP based valence-electron calculations able to approach all-electron calculations19–23.…”

Section: Introductionmentioning

confidence: 99%

Assessment of the “6-31+G** + LANL2DZ” Mixed Basis Set Coupled with Density Functional Theory Methods and the Effective Core Potential: Prediction of Heats of Formation and Ionization Potentials for First-Row-Transition-Metal Complexes

2009

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Computational chemists have long demonstrated great interest in finding ways to reliably and accurately predict the molecular properties for transition metal containing complexes. This manuscript is a continuation of our validation efforts of Density Functional Theory (DFT) methods when applied to transition metal containing systems (K. E. Riley; K. M. Merz, Jr. J. Phys. Chem. 2007, 111, 6044-6053). In our previous work we examined DFT using all-electron basis sets, but approaches incorporating effective core potentials (ECPs) are effective in reducing computational expense. With this in mind, our efforts were expanded to include evaluation of the performance of the basis set derived to approximate such an approach as well on the same set of density functionals. Indeed, employing an ECP basis such as LANL2DZ for transition metals, while using all-electron basis sets for all other non-transition-metal atoms has become more and more popular in computations on transition metal containing systems. In this study, we assess the performance of twelve different DFT functionals, from GGA, hybrid-GGA, meta-GGA and hybrid-meta-GGA classes respectively, along with the 6-31+G** + LANL2DZ (on the transition metal) mixed basis set on predicting two important molecular properties: heats of formation and ionization potentials, for 94 and 58 systems containing first row transition metals from Ti to Zn, which are all in the third row of the periodic table. An interesting note is that the inclusion of the exact exchange term in density functional methods generally increases the accuracy of ionization potentials prediction for the hybrid-GGA methods but decreases the reliability of determining the heats of formation for transition metal containing complexes for all hybrid density functional methods. The hybrid-GGA functional B3LYP gives the best performance on predicting the ionization potentials while the meta-GGA functional TPSSTPSS provides the most reliable and accurate results for heats of formation calculations. TPSSTPSS, a meta-GGA functional, which was constructed from first principles and subject to known exact constraints just like in an "ab initio" way, is successful in predicting both the ionization potentials and the heats of formation for transition metal containing systems.

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“…The current MCPs were parameterized using a scalar relativistic wavefunction, but our previous iMCPs [37][38][39] have both non-and scalar relativistic versions, and this would allow us to predict the effect of relativity on bond length and interaction energy. A sample calculation was done with XeAgCl.…”

Section: Resultsmentioning

confidence: 99%

Comparison of xenon and radon metal halides

Lovallo

Kłobukowski

2015

Chemical Physics Letters

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Development of new pseudopotential methods: Improved model core potentials for the first‐row transition metals

Cited by 38 publications

References 21 publications

Controlling the Thermal Stability and Volatility of Organogold(I) Compounds for Vapor Deposition with Complementary Ligand Design

Controlling the Thermal Stability and Volatility of Organogold(I) Compounds for Vapor Deposition with Complementary Ligand Design

Assessment of the “6-31+G** + LANL2DZ” Mixed Basis Set Coupled with Density Functional Theory Methods and the Effective Core Potential: Prediction of Heats of Formation and Ionization Potentials for First-Row-Transition-Metal Complexes

Comparison of xenon and radon metal halides

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