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Inorganics
Special Issues
Applications of Density Functional Theory in Inorganic Chemistry
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Applications of Density Functional Theory in Inorganic Chemistry

A special issue of Inorganics (ISSN 2304-6740).

Deadline for manuscript submissions: closed (15 April 2019) | Viewed by 26738

Special Issue Editor

Prof. Dr. Athanassios C. Tsipis

E-Mail Website
Guest Editor
Laboratory of Inorganic and General Chemistry, Department of Chemistry, University of Ioannina, 45110 Ioannina, Greece
Interests: DFT; catalysis; anticancer drugs; photodynamic therapy; photophysical properties; intermolecular interactions; metallaromaticity
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Recent improvements in the design of faster and more efficient algorithms have placed powerful computational quantum chemistry tools in the hands of all chemists. Nowadays, Density Functional Theory (DFT) calculations can easily performed, even by non-specialists in the field. This computational tool has become as useful to the bench chemist as spectrometers and vacuum lines. Being practically a “virtual inorganic chemistry lab”, DFT has been applied to predict the behavior of a broad range of chemical, physical, and biological phenomena of importance in chemical reactivity, catalytic activity, bioactivity, photophysics, electronic and nuclear-magnetic resonance spectroscopy, linear and nonlinear optics, etc. This Special Issue aims to collect original, high quality DFT studies focused on diverse research areas in inorganic, organometallic and coordination chemistry. Potential topics include, but are not limited to, the following:

  • Structural, bonding and spectroscopic properties of inorganic compounds
  • Catalysis (mechanistic studies)
  • Bonding properties (electronic and bonding character)
  • Electronic spectroscopy (absorption and emission spectra)
  • Heavy-nucleus NMR spectroscopy
  • Small molecule activation
  • Organometallic reactivity
  • Bioinorganic chemistry

Prof. Dr. Athanassios C. Tsipis
Guest Editor

Manuscript Submission Information

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Keywords

  • DFT
  • catalysis
  • bonding
  • electronic spectroscopy
  • NMR spectroscopy
  • bioinorganic chemistry
  • small molecule activation
  • organometallic chemistry
  • inorganic chemistry

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Published Papers (6 papers)

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Research

14 pages, 600 KiB  
Article
Assessment of Double-Hybrid Density Functional Theory for Magnetic Exchange Coupling in Manganese Complexes
by Dimitrios A. Pantazis
Inorganics 2019, 7(5), 57; https://doi.org/10.3390/inorganics7050057 - 26 Apr 2019
Cited by 22 | Viewed by 4953
Abstract
Molecular systems containing magnetically interacting (exchange-coupled) manganese ions are important in catalysis, biomimetic chemistry, and molecular magnetism. The reliable prediction of exchange coupling constants with quantum chemical methods is key for tracing the relationships between structure and magnetic properties in these systems. Density [...] Read more.
Molecular systems containing magnetically interacting (exchange-coupled) manganese ions are important in catalysis, biomimetic chemistry, and molecular magnetism. The reliable prediction of exchange coupling constants with quantum chemical methods is key for tracing the relationships between structure and magnetic properties in these systems. Density functional theory (DFT) in the broken-symmetry approach has been employed extensively for this purpose and hybrid functionals with moderate levels of Hartree–Fock exchange admixture have often been shown to perform adequately. Double-hybrid density functionals that introduce a second-order perturbational contribution to the Kohn–Sham energy are generally regarded as a superior approach for most molecular properties, but their performance remains unexplored for exchange-coupled manganese systems. An assessment of various double-hybrid functionals for the prediction of exchange coupling constants is presented here using a set of experimentally characterized dinuclear manganese complexes that cover a wide range of exchange coupling situations. Double-hybrid functionals perform more uniformly compared to conventional DFT methods, but they fail to deliver improved accuracy or reliability in the prediction of exchange coupling constants. Reparametrized double-hybrid density functionals (DHDFs) perform no better, and most often worse, than the original B2-PLYP double-hybrid method. All DHDFs are surpassed by the hybrid-meta-generalized gradient approximation (GGA) TPSSh functional. Possible directions for future methodological developments are discussed. Full article
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
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10 pages, 2010 KiB  
Article
Electronic Structure of Cubane-Like Vanadium–Nitrogen Cationic Clusters [V4N4]+ and [V6N6]+
by Piao He, Jian-Guo Zhang and John E. McGrady
Inorganics 2019, 7(4), 52; https://doi.org/10.3390/inorganics7040052 - 12 Apr 2019
Viewed by 3822
Abstract
Density Functional Theory and Complete Active Space Self-Consistent Field (CASSCF) methodologies are used to explore the electronic structure of the cationic V–N clusters, [V4N4]+ and [V6N6]+, that have been identified in recent [...] Read more.
Density Functional Theory and Complete Active Space Self-Consistent Field (CASSCF) methodologies are used to explore the electronic structure of the cationic V–N clusters, [V4N4]+ and [V6N6]+, that have been identified in recent mass spectrometric experiments. Our calculations indicate that both clusters are based on cubane-like fragments of the rock-salt lattice. In the smaller [V4N4]+ cluster, the V–V bonding is delocalized over the tetrahedron, with net bond orders of 1/3 per V–V bond. In [V6N6]+, in contrast, the V–V bonding is strongly localized in the central V2N2 unit, which has a short V=V double bond. CASSCF calculations reveal that both localized and delocalized V–V bonds are highly multi-configurational. Full article
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
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14 pages, 3491 KiB  
Article
The Lowest-Energy Isomer of C2Si2H4 Is a Bridged Ring: Reinterpretation of the Spectroscopic Data Based on DFT and Coupled-Cluster Calculations
by Jesse J. Lutz and Larry W. Burggraf
Inorganics 2019, 7(4), 51; https://doi.org/10.3390/inorganics7040051 - 11 Apr 2019
Viewed by 3227
Abstract
The lowest-energy isomer of C 2 Si 2 H 4 is determined by high-accuracy ab initio calculations to be the bridged four-membered ring 1,2-didehydro-1,3-disilabicyclo[1.1.0]butane (1), contrary to prior theoretical and experimental studies favoring the three-member ring silylsilacyclopropenylidene (2). These [...] Read more.
The lowest-energy isomer of C 2 Si 2 H 4 is determined by high-accuracy ab initio calculations to be the bridged four-membered ring 1,2-didehydro-1,3-disilabicyclo[1.1.0]butane (1), contrary to prior theoretical and experimental studies favoring the three-member ring silylsilacyclopropenylidene (2). These and eight other low-lying minima on the potential energy surface are characterized and ordered by energy using the CCSD(T) method with complete basis set extrapolation, and the resulting benchmark-quality set of relative isomer energies is used to evaluate the performance of several comparatively inexpensive approaches based on many-body perturbation theory and density functional theory (DFT). Double-hybrid DFT methods are found to provide an exceptional balance of accuracy and efficiency for energy-ordering isomers. Free energy profiles are developed to reason the relatively large abundance of isomer 2 observed in previous measurements. Infrared spectra and photolysis reaction mechanisms are modeled for isomers 1 and 2, providing additional insight about previously reported spectra and photoisomerization channels. Full article
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
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14 pages, 1019 KiB  
Article
Comparative Study of Complexes of Rare Earths and Actinides with 2,6-Bis(1,2,4-triazin-3-yl)pyridine
by Attila Kovács, Christos Apostolidis and Olaf Walter
Inorganics 2019, 7(3), 26; https://doi.org/10.3390/inorganics7030026 - 26 Feb 2019
Cited by 18 | Viewed by 4138
Abstract
Complexes of group III metals (rare earth and actinides) with 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (BTP) have been investigated by computational (DFT) and, in limited cases, by experimental (FT-IR, X-ray) techniques with the goal of determining the characteristics of metal–ligand interactions. The DFT calculations using the M062X [...] Read more.
Complexes of group III metals (rare earth and actinides) with 2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (BTP) have been investigated by computational (DFT) and, in limited cases, by experimental (FT-IR, X-ray) techniques with the goal of determining the characteristics of metal–ligand interactions. The DFT calculations using the M062X exchange-correlation functional revealed that metal–ligand distances correlate with the ionic radii of the metals, in agreement with available X-ray diffraction results on the Sc, Y, La, U, and Pu complexes. A related blue-shift trend could be observed in seven characteristic bands in the IR spectra associated with metal–ligand vibrations. The computations uncovered considerable charge transfer interactions, particularly in the actinide complexes, as important covalent contributions to the metal–ligand bonding. The covalent character of the metal–ligand bonds decreases in the actinides, from U to Cm. Full article
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
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36 pages, 9108 KiB  
Article
Survey of the Geometric and Electronic Structures of the Key Hydrogenated Forms of FeMo-co, the Active Site of the Enzyme Nitrogenase: Principles of the Mechanistically Significant Coordination Chemistry
by Ian Dance
Inorganics 2019, 7(1), 8; https://doi.org/10.3390/inorganics7010008 - 15 Jan 2019
Cited by 27 | Viewed by 4379
Abstract
The enzyme nitrogenase naturally hydrogenates N2 to NH3, achieved through the accumulation of H atoms on FeMo-co, the Fe7MoS9C(homocitrate) cluster that is the catalytically active site. Four intermediates, E1H1, E2H [...] Read more.
The enzyme nitrogenase naturally hydrogenates N2 to NH3, achieved through the accumulation of H atoms on FeMo-co, the Fe7MoS9C(homocitrate) cluster that is the catalytically active site. Four intermediates, E1H1, E2H2, E3H3, and E4H4, carry these hydrogen atoms. I report density functional calculations of the numerous possibilities for the geometric and electronic structures of these poly-hydrogenated forms of FeMo-co. This survey involves more than 100 structures, including those with bound H2, and assesses their relative energies and most likely electronic states. Twelve locations for bound H atoms in the active domain of FeMo-co, including Fe–H–Fe and Fe–H–S bridges, are studied. A significant result is that transverse Fe–H–Fe bridges (transverse to the pseudo-threefold axis of FeMo-co and shared with triply-bridging S) are not possible geometrically unless the S is hydrogenated to become doubly-bridging. The favourable Fe–H–Fe bridges are shared with doubly-bridging S. ENDOR data for an E4H4 intermediate trapped at low temperature, and interpretations in terms of the geometrical and electronic structure of E4H4, are assessed in conjunction with the calculated possibilities. The results reported here yield a set of 24 principles for the mechanistically significant coordination chemistry of H and H2 on FeMo-co, in the stages prior to N2 binding. Full article
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
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19 pages, 3094 KiB  
Article
Decomposition of d- and f-Shell Contributions to Uranium Bonding from the Quantum Theory of Atoms in Molecules: Application to Uranium and Uranyl Halides
by Jonathan Tanti, Meghan Lincoln and Andy Kerridge
Inorganics 2018, 6(3), 88; https://doi.org/10.3390/inorganics6030088 - 30 Aug 2018
Cited by 20 | Viewed by 4902
Abstract
The electronic structures of a series of uranium hexahalide and uranyl tetrahalide complexes were simulated at the density functional theoretical (DFT) level. The resulting electronic structures were analyzed using a novel application of the Quantum Theory of Atoms in Molecules (QTAIM) by exploiting [...] Read more.
The electronic structures of a series of uranium hexahalide and uranyl tetrahalide complexes were simulated at the density functional theoretical (DFT) level. The resulting electronic structures were analyzed using a novel application of the Quantum Theory of Atoms in Molecules (QTAIM) by exploiting the high symmetry of the complexes to determine 5f- and 6d-shell contributions to bonding via symmetry arguments. This analysis revealed fluoride ligation to result in strong bonds with a significant covalent character while ligation by chloride and bromide species resulted in more ionic interactions with little differentiation between the ligands. Fluoride ligands were also found to be most capable of perturbing an existing electronic structure. 5f contributions to overlap-driven covalency were found to be larger than 6d contributions for all interactions in all complexes studied while degeneracy-driven covalent contributions showed significantly greater variation. σ-contributions to degeneracy-driven covalency were found to be consistently larger than those of individual π-components while the total π-contribution was, in some cases, larger. Strong correlations were found between overlap-driven covalent bond contributions, U–O vibrational frequencies, and energetic stability, which indicates that overlap-driven covalency leads to bond stabilization in these complexes and that uranyl vibrational frequencies can be used to quantitatively probe equatorial bond covalency. For uranium hexahalides, degeneracy-driven covalency was found to anti-correlate with bond stability. Full article
(This article belongs to the Special Issue Applications of Density Functional Theory in Inorganic Chemistry)
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