Molecular Orbital Theory Calculations Research Articles

Screening drug-induced liver injury through two independent parameters of lipid droplets and peroxynitrite with a π-extended coumarin-based NIR fluorescent probe

Drug-induced liver injury (DILI) or hepatotoxicity is a significant concern for public health. However, relying on a single biomarker for early DILI diagnosis poses a high risk of false positives. In this study, we reported a near-infrared fluorescent probe (BCOU-S), which enables independent visualization of LDs status and ONOO fluctuations. BCOU-S was constructed by combining a π-extended coumarin core as the NIR fluorophore and a methyl thioether group as the ONOO recognition site. BCOU-S could emit 655 nm NIR fluorescence excited at 518 nm, with a low detection limit of 27 nM and a large Stokes shift of 137 nm. The response mechanism to ONOO was confirmed by molecular orbital density function theory (DFT) and time-dependent DFT (TD-DFT) calculations. BCOU-S monitors LDs status through co-localization, oleic acid (OA) incubation, and starvation induction experiments. It sensitively distinguishes subtle changes in ONOO induced by different drugs in DILI cell models. In the acetaminophen (APAP)-induced DILI model, BCOU-S reveals significant LDs accumulation and increase in ONOO levels, establishing a clear time-effect and dose-effect relationship. Simultaneously monitoring ONOO levels and LDs accumulation, BCOU-S proves to be a more sensitive and effective tool for early DILI prevention, effectively avoiding false positives caused by changes in a single parameter. BCOU-S is a useful tool for further monitoring early DILI development.

Antibacterial and ct-DNA binding studies of new synthesized ruthenium (III) hydroxamate complexes: Design, synthesis, DFT calculations and in-vitro study

Ruthenium (III) complexes (1–5) with general composition [Ru(L1–4)3] and [Ru(HL5)3Cl3] where L1 = benzohydroximato (1), L2 = salicylhydroximato (2), L3 = acetohydroximato (3), L4 = hydroxyureato (4), HL 5 = N‑hydroxy-N-phenylbenzamide (5) were synthesized by reacting RuCl3·3H2O with respective hydroxamic acids in 1:3 molar ratio . The complexes were characterized using various techniques including ruthenium metal analysis, elemental analysis, UV–Vis, FT-IR, NMR (1H and 13C), and mass spectrometry. Antibacterial activity of the complexes was evaluated using the agar well diffusion method against ten pathogenic strains. The complexes showed significant inhibition zones and were more active than their corresponding ligands. DNA binding studies indicated intercalative binding mode, with hypochromism and red shift observed. Computational and structural parameters were determined using Frontier Molecular Orbital (FMO) energies and Density Functional Theory (DFT) calculations. The complexes demonstrated favorable molecular geometry, chemical reactivity, and biological activity.

Controllable synthesis of 3D superhydrophilic Cd(II) ion-imprinted polymer microspheres based on OV-POSS and bifunctional monomers synergy with superior selectivity for Cd(II) adsorption

Novel 3D porous Cd(II) ion-imprinted polymer (Cd(II)-IIP) microspheres based on octavinyl polyhedral oligomeric silsesquioxane (OV-POSS) were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization technique combined with the synergistic effect of N-hydroxymethylacrylamide (NMA) and 1-vinylimidazole (1-VI) as bifunctional monomers. RAFT polymerization could achieve a controllable synthesis of polymer networks on OV-POSS. The structure, composition and properties of Cd(II)-IIP were systematically investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, atomic force microscope, water contact angle and thermogravimetric analysis. The results showed that the adsorbent, with a water contact angle of 0 ° and superhydrophilicity, has a high potential for application in aqueous phase systems. Different parameters influencing the sorption performance of Cd(II)-IIP, such as OV-POSS ratio, functional monomers ratio, adsorbent dosage, pH and adsorption time were optimized. Under optimal conditions, the maximum adsorption amount of Cd(II)-IIP for Cd(II) was 80.21 mg/g, and the adsorption equilibrium state could be reached within 40 min. The sorption kinetics proved that the sorption was chemisorption and the rate-limiting step was intraparticle diffusion. Thermodynamic studies showed that Cd(II) sorption was a spontaneous endothermic process. Importantly, XPS analysis, density functional theory (DFT) and frontier molecular orbital (FMO) theory calculations showed that the sorption of Cd(II)-IIP was attributed to the coordination of O and N atoms with Cd(II) on NMA and1-VI, respectively. Actual water sample analysis results indicated that Cd(II)-IIP was an adsorbent of great application potential.

Energetic and Electronic Properties of NpH0/+/– and PuH0/+/–

High-level correlated molecular orbital theory calculations have been performed to predict the thermodynamic and electronic properties of diatomic NpH0/+/- and PuH0/+/-. The excited states up to ∼10,000 cm-1 were predicted for these molecules at the multireference SO-CASPT2 level. The inclusion of spin-orbit effects is fundamental to predict the low-lying state ordering. NpH is predicted to have a 5Π0 ground state, and PuH has a 6Π1/2 ground state at the SO-CASPT2 level. The adiabatic electron affinities (AEAs) and ionization energies (IEs) of NpH and PuH were calculated to be 0.389 and 6.156 and 0.396 and 6.296 eV, respectively, using the Feller-Peterson-Dixon approach. The AEA increases going from AcH (0.425 eV) to ThH (0.820 eV) and decreases from ThH to PuH. The IEs of Pa-Np hydrides are close to ∼6.2 eV followed by an increase of 0.14 eV to PuH (6.296 eV). The An-H bond dissociation energy (BDE) decreases from 276.4 (AcH) to 107.1 (PuH) kJ/mol; the BDE(NpH) is ∼80 kJ/mol higher than that of PuH. Natural bond orbital calculations show that the bond character for these molecules is mainly ionic, An+H-. The additional electron in NpH- and PuH- populates the 6d orbital, and NpH+ and PuH+ are formed by the removal of a 7s electron. The current work in conjunction with prior work on the AcH to UH in different charge states provides insights into how these properties change across the actinide series.

A Two‐Dimensional Porphyrin Coordination Supramolecular Network Cathode for High‐Performance Aqueous Dual‐Ion Battery

AbstractIodine has great potential in the energy storage, but high solubility of I3− has seriously delayed its promotion. Benefited from abundant active sites and the open channel, two‐dimensional coordination supramolecular networks (2D CSNs) is considered to be a candidate for the energy storage. Herein, a 2D porphyrin‐CSN cathode named Zn‐TCPP for aqueous iodine dual‐ion battery (DIB) shows an excellent specific capacity of 278 mAh g−1, and a high energy density of 340 Wh kg−1 at 5 A g−1, as well as a durable cycle performance of 5000 cycles and a high Coulombic efficiency of 98 %. Molecular orbital theory, UV/VIS, Raman spectroscopy and density functional theory (DFT) calculations reveal charge‐transfer interaction between the donor of porphyrin nitrogen and the acceptor of I3−, and computational fluid dynamics (CFD) simulations demonstrate the contribution of 2D layered network structure of Zn‐TCPP to the penetration of I3−.

A Two-Dimensional Porphyrin Coordination Supramolecular Network Cathode for High-Performance Aqueous Dual-Ion Battery.

Iodine has great potential in the energy storage, but high solubility of I3 - has seriously delayed its promotion. Benefited from abundant active sites and the open channel, two-dimensional coordination supramolecular networks (2D CSNs) is considered to be a candidate for the energy storage. Herein, a 2D porphyrin-CSN cathode named Zn-TCPP for aqueous iodine dual-ion battery (DIB) shows an excellent specific capacity of 278 mAh g-1 , and a high energy density of 340 Wh kg-1 at 5 A g-1 , as well as a durable cycle performance of 5000 cycles and a high Coulombic efficiency of 98 %. Molecular orbital theory, UV/VIS, Raman spectroscopy and density functional theory (DFT) calculations reveal charge-transfer interaction between the donor of porphyrin nitrogen and the acceptor of I3 - , and computational fluid dynamics (CFD) simulations demonstrate the contribution of 2D layered network structure of Zn-TCPP to the penetration of I3 - .

Computational Predictions of the Hydrolysis of 2,4,6-Trinitrotoluene (TNT) and 2,4-Dinitroanisole (DNAN).

Hydrolysis is a common transformation reaction that can affect the environmental fate of many organic compounds. In this study, three proposed mechanisms of alkaline hydrolysis of 2,4,6-trinitrotoluene (TNT) and 2,4-dinitroaniline (DNAN) were investigated with plane-wave density functional theory (DFT) combined with ab initio and classical molecular dynamics (AIMD/MM) free energy simulations, Gaussian basis set DFT calculations, and correlated molecular orbital theory calculations. Most of the computations in this study were carried out using the Arrows web-based tools. For each mechanism, Meisenheimer complex formation, nucleophilic aromatic substitution, and proton abstraction reaction energies and activation barriers were calculated for the reaction at each relevant site. For TNT, it was found that the most kinetically favorable first hydrolysis steps involve Meisenheimer complex formation by attachment of OH- at the C1 and C3 arene carbons and proton abstraction from the methyl group. The nucleophilic aromatic substitution reactions at the C2 and C4 arene carbons were found to be thermodynamically favorable. However, the calculated activation barriers were slightly lower than in previous studies, but still found to be ΔG‡ ≈ 18 kcal/mol using PBE0 AIMD/MM free energy simulations, suggesting that the reactions are not kinetically significant. For DNAN, the barriers of nucleophilic aromatic substitution were even greater (ΔG‡ > 29 kcal/mol PBE0 AIMD/MM). The most favorable hydrolysis reaction for DNAN was found to be a two-step process in which the hydroxyl first attacks the C1 carbon to form a Meisenheimer complex at the C1 arene carbon C1-(OCH3)OH-, and subsequently, the methoxy anion (-OCH3) at the C1 arene carbon dissociates and the proton shuttles from the C1-OH to the dissociated methoxy group, resulting in methanol and an aryloxy anion.

Characteristics and radiolysis behavior of polyvinylchloride under accelerated proton and γ-irradiation

The effect of high energy protons and γ-irradiation on the structural properties, surface-energies, and toxicological properties of polyvinyl chloride (PVC) were studied due to the role PVC products play in many technologies including the nuclear industry. Accelerated 1–4 MeV protons impacting on PVC in vacuum lead to the formation of polyenyl radicals as shown by EPR and to an increase in free surface energy due to functionalization of the surface of the irradiated polymer. γ-irradiation leads to the formation of unsaturated bonds, carbonyl and hydroxyl groups as shown by IR and to the release of HCl. Correlated molecular orbital theory calculations of reaction thermodynamics were used to aid in the development of a mechanism in the absence of oxygen. The formation and accumulation of chromophores and auxochromic groups during γ-radiolysis of PVC leads to a gradual change of the initial white color of the polymer to yellow and then to brown and black with high sensitivity. A mixture of powdered PVC and silicate glue was used to determine the profile of a 60Co γ-radiation beam on targets with a complex relief. γ-irradiated polymer does not have a local irritating effect due to a single application to the skin of mice in an adhesive mixture at a concentration of up to 5000 mg/kg. γ-radiolysis of PVC powder in air with a dose of up to 1400 kGy does not affect its acute toxicity when administered intragastrically to BDF1 mice. PVC and its γ-irradiated analogs are non-toxic at doses ≤5000 mg/kg.

Observation of Selectively Populated Monohalide Excited States from the Reactions of Group 3 Metal (Sc, Y, and La) Monomers and Dimers with Halogen-Containing Molecules.

The chemiluminescent reactions of the group 3 metals Sc and Y with F2, Cl2, Br2, ClF, ICl (Sc), IBr (Y), and SF6 and La with F2, SF6, Cl2, and ClF have been studied at low pressures (6 × 10-6 to 4 × 10-4 Torr) using a beam-gas arrangement and extended to the 10-3 Torr multiple collision pressure range. Contrary to previous reports, the observed chemiluminescent spectra are primarily attributed to emission from the metal monohalides. Extensive pressure and temperature dependence studies and high-level correlated molecular orbital theory calculations of the bond dissociation energies support this conclusion and the attribution of the chemiluminescence. Evidence for the "selective" production of a monohalide excited electronic state is obtained for several of the Sc and Y reactions. All reactions producing the metal monofluorides are first order with respect to the oxidant, while reactions producing the monochlorides and monobromides are found to be "faster than first order" with respect to the oxidant. This difference is associated with the metal halide bond dissociation energies and the metal halide product internal density of states. Analysis of the temperature dependence for six representative reactions indicates that the "selective" excited-state formation of the metal monohalides proceeds via a direct mechanism with negligible activation energy. We compare and contrast the present results with previous experiments and interpretations which have assigned the selective emission from these systems to the group 3 dihalides produced in a two-step reaction sequence analogous to an electron jump process. The current results suggest a distinctly different interpretation of the observed processes in these systems. The observed selectivity observed in these studies is remarkable given the significant number of known and potential excited states in the scandium and yttrium halides as well as their different electronic configurations.

Photophysical Properties of Naphthalene-oxacalix[m]arene and Recognition of Fullerene C60.

Three different pore sizes of oxacalix[m]arene[n]pyrimidines modified with a naphthalene substituent were synthesized and characterized by HRMS, 1H NMR, and single-crystal analysis (8OA and 8OA-N). Steady-state spectroscopy indicates these naphthalene-oxacalix[m]arenes exhibit good fluorescence properties, which isattributed to the locally excited (LE) state emission, and electrochemical results show that the photoinduced electron transfer (PET) process occurs from the naphthalene substituent to the linked pyrimidine. Nanosecond transient absorption spectra, singlet oxygen quantum yields (ΦΔ4OA-N = 45.1%, ΦΔ6OA-N = 56.6%, and ΦΔ8OA-N = 65.7%) and theoretical calculations demonstrate that the torsion angle between the donor (naphthalene) and the acceptor (pyrimidine) promotes intersystem crossing (ISC), and the lifetime of the triplet state reaches ca. 8 ms. Interestingly, all three host molecules (4OA-N, 6OA-N, and 8OA-N) showed a high affinity for fullerene C60, and significant binding constants in the range of 4.10–6.68 × 104 M–1 were obtained by fluorescence titration; in contrast, previous reports indicated that the similar oxacalix[m]arene[n]pyrimidine scaffold could not efficiently complex with C60. In the frontier molecular orbital theory calculations of the supramolecular system of 4OA-N@C60, the HOMO is distributed on 4OA-N and the LUMO is localized on fullerene. The calculation results further demonstrated that there are strong interactions between the host and the fullerene guest, which is consistent with the result of the experiments. The characteristic photophysical properties of these novel naphthyl-decorated oxacalix[m]arene[n]pyrimidines broaden their application field, and the stable host–guest system with fullerene can be applied to supramolecular chemistry.

Composite Correlated Molecular Orbital Theory Calculations of Ring Strain for Use in Predicting Polymerization Reactions.

Strained ring systems play an important role in synthesis and can be characterized by the ring strain energy (RSE). The RSE of 3, 4, 5, and 6 membered saturated and unsaturated ring systems containing N, O, P, and S heteroatoms and H, F, SiMe3 , and SO2 Me substituents were calculated at the G3(MP2) composite correlated molecular orbital theory level using up to 5 models to predict the RSE. Generally, the RSE decreased as ring size increased with a substantial decrease from 4 to 5 membered rings. Replacement of a ring CH2 with P or S reduced the RSE, consistent with less angle strain. The RSE for unsaturated systems were generally greater than for saturated systems due to increased angle strain. No general trends were found with respect to substituent effects. The RSE values suggest that 3-pyrroline and 2-pyrroline and their derivatives may be able to support ring opening metathesis polymerization and warrant further study.

Best practices in catalysis: A perspective

Catalysis, from its roots in petrochemical refining and conversion, has emerged as a transdisciplinary field that now encompasses synthesis of materials and molecules that enable applications in energy conversion and storage, environmental remediation, medicine, plastics, and fertilizer production, among numerous others. A handful of disciplines can claim relevance and success over such an extended period of time and continue to claim a preeminent role in defining the state-of-the-art in science and technology. Syncretic and rapid advancements in formulation and spectroscopic characterization of materials and molecules useful as catalysts, high-level density functional and molecular orbital theory calculations, and a strong foundation in concepts of physical chemistry, thermodynamics, and chemical kinetics offer new and abundant opportunities at the present day for addressing the grand challenge of controlling chemical transformations using catalysis. We examine what we have learned of concepts that underpin heterogeneous catalysis but more importantly, how we learned to archive our knowledge in context of a set of best practices and standards that have emerged in the course of our learnings—ones we seek to highlight herein. Our perspective emphasizes concepts in synthesis, characterization, kinetics, and theory, because these four elements combined enable description of molecular acts that happen on surfaces and how fast they occur. In revisiting best practices in heterogeneous catalysis in these sub-fields and in authorship and peer review we aspire to augment clarity, reproducibility, and rigor in the science and practice of catalysis.

π-Extended Boron Difluoride [NՈNBF2] Complex, Crystal Structure, Liquid NMR, Spectral, XRD/HSA Interactions: A DFT and TD-DFT Study

The novel tetrahedral 10-(4-carboxyphenyl)-2,8-diethyl-5,5-difluoro-1,3,7,9-tetramethyl-5H-di-pyrrolo[1,2-c:2’,1’-f][1,3,2]diazaborinin-4-ium-5-uide [NՈNBF2] BODIPY complex was prepared in a very good yield and via one-pot synthesis. The desired [NՈNBF2] has been used as a model complex for XRD/HSA interactions and DFT/B3LYP/6-311G(d,p) computations. The tetrahedral geometry around the boron center was demonstrated by DFT optimization and XRD-crystallography. The 1H, 11B, and 19F-NMR spectra were used also to support the high symmetrical BODIPY via π-extended phenomena. Moreover, the values of the DFT-calculated structural bond lengths/angles and DFT-IR were matched to the corresponding experimental XRD and IR parameters, respectively. The crystal lattice interactions were correlated to Hirshfeld surface analysis (HSA) calculations. Calculations of the Mulliken Atomic Charge (MAC), Natural Population Analysis (NPA), Global reactivity descriptors (GRD), and Molecular Electrostatic Potential (MEP) quantum parameters were performed to support the XRD/HSA interactions result. Analysis of the predicted Density of States (DOS), molecular orbital, and time-dependent density functional theory (TD-DFT) calculations have been combined to explain the experimental UV-vis spectra and electron transfer behavior in [NՈNBF2] complex using MeOH and other four solvents.

Th2O-, Th2Au-, and Th2AuO1,2- Anions: Photoelectron Spectroscopic and Computational Characterization of Energetics and Bonding.

The observation and characterization of the anions: Th2O-, Th2Au-, and Th2AuO1,2- is reported. These species were studied through a synergetic combination of anion photoelectron spectroscopy and ab initio correlated molecular orbital theory calculations at the CCSD(T) level with large correlation-consistent basis sets. To better understand the energetics and bonding in these anions and their corresponding neutrals, a range of smaller diatomic to tetratomic species were studied computationally. Correlated molecular orbital theory calculations at the CCSD(T) level showed that in most of these cases, there are close-lying anions and neutral clusters with different geometries and spin states and are consistent with the experimentally observed spectra. Thus, comparison of experimentally determined and computationally predicted vertical detachment energies and electron affinities for different optimized geometries and spin states shows excellent agreement to within 0.1 eV. The structures for both the neutrals and anions have a significant ionic component to the bonding because of the large electron affinity of the Au atom and modest ionization potentials for Th2, Th2O, and Th2O2. The analysis of the bonding for the Th-Th bonds from the molecular orbitals is consistent with this ionic model. The results show that there is a wide variation in the bond distance from 2.7 to 3.5 Å for the Th-Th bonds all of which are less than twice the atomic radius of Th of 3.6 Å. The bond distances encompass bond orders from 4 to 0. There can be different bond orders for the same bond distance depending on the nature of the ionic bonding suggesting that one may not be able to correlate the bond order with the bond distance in these types of clusters. In addition, the presence of an Au atom may provide a unique probe of the bonding in such clusters because of its ability to accept an electron from clusters with modest ionization potentials.

Multimodal Structure Solution with 19F NMR Crystallography of Spin Singlet Molybdenum Oxyfluorides.

Complex crystal structures with subtle atomic-scale details are now routinely solved using complementary tools such as X-ray and/or neutron scattering combined with electron diffraction and imaging. Identifying unambiguous atomic models for oxyfluorides, needed for materials design and structure-property control, is often still a considerable challenge despite their advantageous optical responses and applications in energy storage systems. In this work, NMR crystallography and single-crystal X-ray diffraction are combined for the complete structure solution of three new compounds featuring a rare triangular early transition metal oxyfluoride cluster, [Mo3O4F9]5-. After framework identification by single-crystal X-ray diffraction, 1D and 2D solid-state 19F NMR spectroscopy supported by ab initio calculations are used to solve the structures of K5[Mo3O4F9]·3H2O (1), K5[Mo3O4F9]·2H2O (2), and K16[Mo3O4F9]2[TiF6]3·2H2O (3) and to assign the nine distinct fluorine sites in the oxyfluoride clusters. Furthermore, 19F NMR identifies selective fluorine dynamics in K16[Mo3O4F9]2[TiF6]3·2H2O. These dual scattering and spectroscopy methods are used to demonstrate the generality and sensitivity of 19F shielding to small changes in bond length, on the order of 0.01 Å or less, even in the presence of hydrogen bonding, metal-metal bonding, and electrostatic interactions. Starting from the structure models, the nature of chemical bonding in the molybdates is explained by molecular orbital theory and electronic structure calculations. The average Mo-Mo distance of 2.505 Å and diamagnetism in 1, 2, and 3 are attributed to a metal-metal bond order of unity along with a 1a21e4 electronic ground state configuration for the [Mo3O4F9]5- cluster, leading to a rare trimeric spin singlet involving d2 Mo4+ ions. The approach to structure solution and bonding analysis is a powerful strategy for understanding the structures and chemical properties of complex fluorides and oxyfluorides.

Synthesis and evaluation of antioxidant activity of some novel hydroxypyridinone derivatives: a DFT approach for explanation of their radical scavenging activity.

Background and purpose:Reactive oxygen species (ROSs) are continuously produced as byproducts of cell metabolism. Free radicals are an unstable form of ROSs with the tendency to react readily with biomolecules such as amino acids, lipids and DNA. These reactions lead to oxidative damages to the cell. Oxidative stress occurs when the concentration of the ROSs exceeds the capacity of antioxidative protection systems of the body. 5-Hydroxypyridin-4-one derivatives can chelate Fe2+ and Fe3+ due to their α-hydroxyketone moiety. Also, tautomerism in hydroxypyridinone ring leads to enough level of aromaticity resulting in a catechol-like behavior that provides them with good chelating and radical scavenging properties.Experimental approach:Different compounds were synthesized with 5-hydroxypyridine-4-one moiety as the core. The antioxidant properties of molecules were evaluated experimentally by DPPH scavenging method and theoretically using DFT/B3LYP with a 6-31++G (d,p) basis set. Electronic properties were investigated using frontier molecular orbital theory calculations. Furthermore, global descriptive parameters were obtained to find the chemical reactivity of molecules. The natural bond orbital analysis was performed to investigate charge distribution and hydrogen bonding.Findings/Results:Structures of the synthesized compounds were confirmed using IR, 1H-NMR, and 13C-NMR spectral analyses. Among all the synthesized compounds, Va and Vb showed the best antioxidant effect experimentally and computationally.Conclusion and implications:Results of this study were valuable in terms of synthesis, in silico, and in vitro antioxidant evaluations and can be useful for future investigations about the design of novel 5-hydroxypyridin- 4-one derivatives possessing iron-chelating and radical scavenging abilities.

From Benzene to Graphene: Exploring the Electronic Structure of Single-Layer and Bilayer Graphene Using Polycyclic Aromatic Hydrocarbons

In this work, two exercises are described that are designed to teach students about the evolution and behavior of the electronic bands of graphene and bilayer graphene. These exercises involve performing extended Huckel molecular orbital theory calculations on polyacenes and polycyclic aromatic hydrocarbons. In the first exercise, students investigate how the molecular orbitals of polyacenes converge into bands as polyacene size increases. Further, students learn that long-range interactions cause frontier-orbital crossing as the size of the polyacene increases. In the second exercise, the concepts of band structures, band crossing, and k-space are explored using the results of frontier orbital calculations on π-stacked dimers of polycyclic aromatic hydrocarbons, which represent molecular analogues of layered 2D materials. The results of these calculations show how the geometry and layer–layer offset of the dimer system can affect its electronic structure, and the results can be extrapolated to provide a framework for understanding why subtle changes in the relative orientations of the layers in bilayer graphene can produce qualitative changes in the electronic properties. These calculations are easily implemented with Python or with widely available algebraic manipulation software such as Maple or Mathematica. These exercises are accessible to students who have experience with extended Huckel molecular orbital theory and are suitable for inclusion in the physical chemistry curriculum at the upper-level undergraduate or introductory graduate level.

(Invited) Molecular-Level Analysis of Electrodeposition Processes Using Theoretical Calculations and Surface Enhanced Raman Microscopy

Electrodeposition process has been widely applied to various areas to form functional thin films and nanostructures. In order to understand the deposition process from molecular level to achieve further precise control, we employ theoretical calculation and surface enhanced Raman scattering (SERS). For the theoretical calculation to study the deposition reaction mechanism, molecular orbital and density functional theory calculations were applied to investigate the behaver of the species at the electrode surface, and various factors such as solvation effect and catalytic activity of the surface were also analysed. In addition, SERS equipped with confocal microscopy was used for in situ analysis of the reaction processes at the electrode surface. For this we applied plasmon sensors [1] to achieve very high sensitivity analysis. Furthermore multi-confocal type SERS microscopy was employed for mapping and imaging analysis. By using these techniques, various systems have been analysed and modelling of their reaction processes has been carried out. This work was financially supported in part by “Development of Systems and Technology for Advanced Measurement and Analysis,” Japan Science and Technology Agency, and Grant-in-Aid for Scientific Research, MEXT, Japan. [1] M. Yanagisawa, M. Saito, M. Kunimoto, T. Homma, Appl. Phys. Express, 9 , 122002 (2016).

Reversible Solution π-Dimerization and Long Multicenter Bonding in a Stable Phenoxyl Radical.

Reversible solution π-dimerization is observed in the stable neutral phenoxyl radical 2,6-bis-(8-quinolylamino)-4-(tert-butyl)phenoxyl baqp and is spectroscopically characterized. This behavior, not previously observed for π-extended phenoxyl radicals, is relevant to the formation of long multicenter bonding in the π-dimer at low temperature akin to previously reported phenalenyl radicals. Our experimental data are supported in a quantitative manner by results from density functional theory (DFT) and ab initio molecular orbital theory calculations. Our theoretical results indicate that the solution dimer features strong bonding interactions between the two phenoxyl rings but that the stability of the dimer is also related to dispersion interactions between the flanking nearly parallel quinolyl rings.

Ground-state molecular and electronic structures of group-IV nanoribbons, nanorings and nanotubes.

Based on ab initio molecular orbital (MO) theory and first-principles band calculations, we systematically study the ground-state molecular and electronic structures of group-IV nanoribbons (NRBs), nanorings (NRGs) and nanotubes (NTBs) by substituting the honeycomb skeletal atoms with C, Si or Ge atoms. We then explore the energetics in the ground-state singlet-triplet (ST) crossover, particularly focusing on the configuration hybridization by electron correlation.