Are electrophilicity and electrofugality related concepts? A density functional theory study

It is proposed that the electrofugality of a fragment within a molecule is determined by its group nucleophilicity. The variation of electrofugality should be tightly related to the electron releasing ability of the substituent attached to the electrofuge moiety. This contribution closes the set of relationships between philicity and fugality quantities: while nucleofugality appears related to the group electrophilicity of the leaving group, electrofugality is related to the group nucleophilicity of the permanent group.     

Do anionic titanium dioxide nano‐clusters reach bulk band gap? A density functional theory study

The electronic properties of both neutral and anionic (TiO₂)_n (n = 1–10) clusters are investigated by extensive density functional theory calculations. The predicted electron detachment energies and excitation gaps of anionic clusters agree well with the original experimental anion photoelectron spectra (APES). It is shown that the old way to analyze APES tends to overestimate vertical excitation gaps (VGA) of large anionic clusters, due to the nature of multiple electronic origins for the higher APES bands. Moreover, the VGA of anionic TiO₂ clusters are evidently smaller than those of neutral clusters, which may also be the case for other metal oxide clusters with high electron affinity. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

A theoretical study of CO adsorption on gold by Hückel theory and density functional theory calculations

It is crucial to understand the nature of CO adsorption on gold so as to elucidate the mechanism of low-temperature CO oxidation on nanogold catalysts. We performed theoretical analysis of CO adsorption on gold by using Hückel theory and density functional theory (DFT) calculations. Hückel theory indicates that CO adsorption on gold is dominated by the electron distribution at the Au atom, which is greatly affected by neighboring Au atoms, coadsorbed or doping species. The increase of σ-bonding electrons should weaken the CO adsorption, while the increase of π-electrons should strengthen the adsorption. DFT calculations proved this prediction quantitatively for various systems, including CO adsorption on a Au(100)-hex surface with locally varying subsurface configurations and CO coadsorption with acceptor or donor species.     

A density functional theory investigation of CrSin (n=1–6) clusters

Clusters of the form CrSi_n (n=1–6) were investigated computationally using a density functional approach. In particular, geometry optimizations were carried out under the constraint of well-defined point group symmetries at the B3LYP level employing a pseudopotential method in conjunction with double zeta basis sets. In this article, the resulting total energies, Mulliken atomic net populations, overlap populations, fragmentation energies and geometries of CrSi_n (n=1–6) are presented and discussed, together with natural populations and natural electron configurations. In addition, we comment on the charge transfer within the clusters. From this analysis, the 3d orbital of the Cr atom in CrSi_n (n=1–6) cluster absorbs electrons. From this tendency, conclusions are drawn with respect to the electronic populations and the chemical bond between Si and Cr as well as Si and Si.     

Concurrent cyclopropanation by carbenes and carbanions? A density functional theory study on the reaction pathways

The mechanisms for the addition reactions of phenylhalocarbenes and phenyldihalomethide carbanions with acrylonitrile (ACN) and trimethylethylene (TME) have been investigated using an ab initio BH and HLYP/6-31G (d, p) level of theory. Solvent effects on these reactions have been explored by calculations that included a polarizable continuum model (PCM) for the solvent (THF). These model calculations show that for the addition of phenylhalocarbenes, a TME species may readily undergo addition reactions with carbenes while ACN has a high-energy barrier to overcome. It was also found that phenyldihalomethide carbanions do not readily add to the electron-rich TME. The cyclopropane yields only appear to occur via addition of PhCBr to TME. However, the cyclopropanation proceeds not only via slow addition of phenylhalocarbenes to ACN but also forms through the stepwise reaction of phenyldihalomethide carbanions with ACN. Our calculation results are in good agreement with experimental observations (Moss, R.A.; Tian, J.-Z. J. Am. Chem. Soc. 2005, 127, 8960) that indicate that the cyclopropanation of phenylhalocarbenes and phenyldihalomethide carbanions with ACN are concurrent in THF.     

A density functional theory study of the ��mythic�� Lindlar hydrogenation catalyst

A Lindlar catalyst is a popular heterogeneous catalyst that consists of 5?wt.% palladium supported on porous calcium carbonate and treated with various forms of lead and quinoline. The additives strategically deactivate palladium sites. The catalyst is widely used for the partial hydrogenation of acetylenic compounds in organic syntheses. Alkyne reduction is stereoselective, occurring via syn addition to give the cis-alkene. Even if it has been employed for about 60?years, there is a lack of molecular level understanding of the Lindlar catalyst. We have applied density functional theory simulations to understand the structure and the nature of the interplay between the multiple chemical modifiers in the Lindlar catalyst. Indeed, the poisons influence different parameters controlling selectivity to the alkene: Pb modifies the thermodynamic factor and hinders the formation of hydrides, while quinoline isolates Pd sites thus minimizing oligomerization.     

Structures,stabilities, and electronic properties of Al n Au (n = 1–15) clusters: A density functional study

We present density functional calculations of Al _n Au clusters for n = 1–15. The growth pattern for Al _n Au (n = 1–7, 12, 14, 15) clusters is the Au atom occupying a peripheral position of Al _n clusters, and the growth pattern for Al _n Au (n = 8, 10 and 13) clusters is Au-substituted Al _n+1 clusters. It is found that the Au atom replaces the surface atom of an Al _n+1 cluster and occupies a peripheral position. In addition, the ground state structures of Al _n Au clusters are more stable than pure Aln clusters. It is found that the Al₁₃Au cluster exhibits high stability.     

Theoretical study of methane adsorption and C─H bond activation over Fe-embedded graphene: Effect of external electric field

The effect of an external electric field (EF) on the methane adsorption and its activation on iron-embedded graphene (Fe-GPs) are investigated by using the M06-L density functional method. The EF is applied in the perpendicular direction to the graphene in the range of −0.015 to +0.015 a.u. with the interval of 0.005 a.u. The effects of EF on the adsorption, transition state and product complexes of the methane activation reaction are revealed. The binding energies of methane on Fe site in Fe-GPs are increased from −12.9 to −15.3, −18.1 and −21.5 kcal/mol for the negative EF of −0.005, −0.010 and −0.015, respectively. By applying positive EF, the activation barriers for methane activation are reduced in range of 3–8 kcal/mol (around 12–31%) and the reaction energies are more exothermic. The positive EF kinetically favors the reaction compared to the system without EF. The adsorption and activation of methane on Fe-GPs can be easily tuned by adjusting the external electric field for various applications. © 2019 Wiley Periodicals, Inc.     

Structural,electronic, and optical properties of Cd-halide-based inorganic LiCdX3 (X = F,Cl) perovskites for photovoltaic applications: A density functional theory study

Halide base perovskite LiCdX₃ (X = F, Cl) is tested by CASTEP (Cambridge Serial Total Energy Package) based on density function theory (DFT). The presented discussion is to explore the structural, electronic, and optical properties of LiCdX₃ (X = F, Cl). The calculated values of the lattice parameter are found to be 3.8 Å and 5.27 Å of LiCdF₃ and LiCdCl₃ respectively. The ideal structure of LiCdX₃ (X = F, Cl) is cubic and dynamically stable. Electronic properties show that materials are semiconductors. The results from band structure are further evaluated by the total and partial density of states. The partial and total density of states confirms the degree of localization of electrons. In optical properties, the highest absorption coefficient is observed in LiCdCl₃. The material is half metallic and has a narrow indirect band gap which may be used in photovoltaic applications.     

CH4 dissociation on Co（0001）: A density functional theory study

CH4 dissociation on Co(0001) surfaces is an important step, which has been investigated at the level of density functional theory. It is found that CH4 is unfavorable to adsorb on Co(0001), while CH4 favores to dissociate to CH3, CH2 and CH on Co(0001) surface by sequential dehydrogenation. In the whole process of CH4 dehydrogenation, CH4 dissociate to CH3 and H is the rate-determining step. The calculated results show that CH2 and CH exist mainly on Co(0001) surface, while the dehydrogenation of CH into C and H is difficult.     

Quantum-chemical study of methane dehydrogenation on neutral,cationic, and anionic clusters Pt2–5 by DFT method

Russian Journal of General Chemistry -     

Near-infrared-emitting phthalocyanines. A combined experimental and density functional theory study of the structural, optical, and photophysical properties of Pd(II) and Pt(II) α-butoxyphthalocyanines

The structural, optical, and photophysical properties of 1,4,8,11,15,18,22,25-octabutoxyphthalocyaninato-palladium(II), PdPc(OBu)(8), and the newly synthesized platinum analogue PtPc(OBu)(8) are investigated combining X-ray crystallography, static and transient absorption spectroscopy, and relativistic zeroth-order regular approximation (ZORA) Density Functional Theory (DFT)/Time Dependent DFT (TDDFT) calculations where spin-orbit coupling (SOC) effects are explicitly considered. The results are compared to those previously reported for NiPc(OBu)(8) (J. Phys. Chem. A 2005, 109, 2078) in an effort to highlight the effect of the central metal on the structural and photophysical properties of the group 10 transition metal octabutoxyphthalocyanines. Different from the nickel analogue, PdPc(OBu)(8) and PtPc(OBu)(8) show a modest and irregular saddling distortion of the macrocycle, but share with the first member of the group similar UV-vis spectra, with the deep red and intense Q-band absorption experiencing a blue shift down the group, as observed in virtually all tetrapyrrolic complexes of this triad. The blue shift of the Q-band along the MPc(OBu)(8) (M = Ni, Pd, Pt) series is interpreted on the basis of the metal-induced electronic structure changes. Besides the intense deep red absorption, the title complexes exhibit a distinct near-infrared (NIR) absorption due to a transition to the double-group 1E (π,π*) state, which is dominated by the lowest single-group (3)E (π,π*) state. Unlike NiPc(OBu)(8), which is nonluminescent, PdPc(OBu)(8) and PtPc(OBu)(8) show both deep red fluorescence emission and NIR phosphorescence emission. Transient absorption experiments and relativistic spin-orbit TDDFT calculations consistently indicate that fluorescence and phosphorescence emissions occur from the S(1)(π,π*) and T(1)(π,π*) states, respectively, the latter being directly populated from the former, and the triplet state decays directly to the S(0) surface (the triplet lifetime in deaerated benzene solution was 3.04 μs for Pd and 0.55 μs for Pt). Owing to their triplet properties, PdPc(OBu)(8) and PtPc(OBu)(8) have potential for use in photodynamic therapy (PDT) and are potential candidates for NIR light emitting diodes or NIR emitting probes.     

Density functional theory study of the structures,electronic states and stabilities of Al n Pt (n = 1–15) clusters

The binding energy, dissociation energy, ionization potentials, electron affinities, gap and stability of small Al _n Pt (n = 1–15) clusters, in comparison with pure aluminum clusters have been systematically investigated by means of density functional calculations at the B3LYP level. The growth patten for Al _n Pt clusters is that the Pt atom substituted the surface atom of the Al _{n + 1} clusters for n < 13. Starting from n = 13, the Pt atom completely falls into the center of the Al-frame. The Pt atom substituted the center atom of the Al _{n + 1} clusters to form the Pt-encapsulated Aln geometries for n > 13. We also find that the impurity Pt atom causes local structural distortion due to different atomic radii and different bonding characteristics. The clusters with total atom numbers of 2, 7, and 11 exhibit high stability.     

A density functional study for the isomers of anionic sulfur clusters Sn− (n=3–20)

The signals of anionic sulfur clusters are intense in the mass spectrum of sulfur clusters generated in direct laser vaporization. We have acquired numerous isomers of sulfur clusters by means of the B3LYP DFT method. According to total energies, the most stable S_n⁻ (n=3–13) isomers are predicted. The helical S_n (n=14–20) structures are also calculated. Most of the anionic clusters are with chain configurations; the ring clusters with threefold atom(s) are higher in total energy. The most stable forms of isomers, from S₉⁻ to S₁₃⁻, show helical configurations that are completely different from those of the corresponding neutral and cationic clusters.     

CH and Chalogen bond dissociation energies for fluorinated and chlorinated methane evaluated with hybrid B3LYP density functional theory methods and their comparison with experimental data and the CBS-Q ab initio computational approach

The CH and Chalogen bond dissociation energies (BDEs) were computed with the hybrid B3LYP/6-311 + G(2d,2p) theory model for chlorinated and fluorinated methane. All computed values were substantially lower (5–10 kcal mol⁻¹) than the experimental values. To obtain better agreement, a correlation factor was introduced. When this factor was applied, excellent agreement between the B3LYP/6-311 + G(2d,2p) computed energies and the experimental BDEs was observed. On the other hand, the CBS-Q ab initio computational approach generated BDEs which are in good agreement with experimental values without a correction factor.     

The density functional theory study CO oxidation catalyzed by subnanometer AlAg n (n = 1–3) clusters

The efficiency of AlAg _n (n = 1–3) alloy clusters toward CO oxidation is demonstrated from first-principles theory. It is found that these subnanometer species transform into reaction complexes which catalyze CO oxidation through the Langmuir–Hinshelwood path. It is shown that mixing two different metals (Al and Ag) can have beneficial effects on the catalytic activity and the alloyed AlAg₃ cluster is proposed as the best effective nanocatalysts.     

Communication: Competition between π···π interaction and halogen bond in solution: a combined 13C NMR and density functional theory study

Competition between π···π interaction and halogen bond in solution has been investigated by using carbon nuclear magnetic resonance spectroscopy ((13)C NMR) combined with density functional theory calculation. Both experimental and theoretical results clearly show that there are no C-Cl···π or C-Br···π halogen bonds and only the π···π interactions exist in the binary liquid mixtures of C(6)D(6) with C(6)F(5)Cl and C(6)F(5)Br, respectively. The case is totally different for the binary liquid mixtures of C(6)D(6) with C(6)F(5)I in which the C-I···π halogen bonds not the π···π interactions are present. The important role of entropy in the competition between π···π interaction and halogen bond in solution was also discussed.