Doublet Spin States Research Articles

Computational investigation for electronic, structural, linear/nonlinear optical responses for newly designed organometallic quantum dots

AbstractThe interaction of metallic ($$M^{ + 3}$$ M + 3 )-cations ($$M = {\text{Al}},{\text{Cu}},{\text{Zn}},{\text{In}},{\text{Ga}},{\text{Ge}},{\text{Sb}},{\text{Sn}}$$ M = Al , Cu , Zn , In , Ga , Ge , Sb , Sn ) with an active organic linker result in the formation of organometallic quantum dots (OMQDs). The B3LYP and WB97X interfaces via 6-311G++(d,p) route are used to test the stability, electrical, optical, and nonlinear-optics (NLO) properties. OMQD UV–Vis absorption spectra are computed. Some OMQD have singlet spin states, while others have doublet spin states. Cation mobility and the organic linker nature have a significant impact on both optical and NLO properties. For electron rush via the conduction domain, doublet spins provide more advanced turnabilities than singlets. For singlet-spin Cu-3HPHP QDs, an anomalous NLO response is endorsed. Both Zn-3HPHP and Sn-3HPHP QDs are recognized as the finest contenders. Zn-3HPHP and Sn-3HPHP appear to be the next covenant for highly efficient optoelectronics and avalanche photodetectors.

Effect of Anchoring Dynamics on Proton-Coupled Electron Transfer in the Ru(bda) Coordination Oligomer on a Graphitic Surface.

The oligomeric ruthenium-based water oxidation catalyst, Ru(bda), is known to be experimentally anchored on graphitic surfaces through CH-π stacking interactions between the auxiliary bda ([2,2'-bipyridine]-6,6'-dicarboxylate) ligand bonded to ruthenium and the hexagonal rings of the surface. This anchoring provides control over their molecular coverage and enables efficient catalysis of water oxidation to dioxygen. The oligomeric nature of the molecule offers multiple anchoring sites at the surface, greatly enhancing the overall stability of the hybrid catalyst-graphitic surface anode through dynamic bonding. However, the impact of this dynamic anchoring on the overall catalytic mechanism is still a topic of debate. In this study, a crucial proton-coupled electron transfer event in the catalytic cycle is investigated using DFT-based molecular dynamics simulations plus metadynamics. The CH-π stacking anchoring plays a critical role not only in stabilizing this hybrid system but also in facilitating the proton-coupled electron transfer event with possible vibronic couplings between the anchoring bonds motion and charge fluctuations at the catalyst - graphitic surface interface. Furthermore, this computational investigation displays the presence of a quartet spin state intermediate that can lead to the experimentally observed and thermodynamically more stable doublet spin state.

Radical Spin Polarization and Magnetosensitivity from Reversible Energy Transfer.

Molecular spins provide potential building units for future quantum information science and spintronic technologies. In particular, doublet (S = 1/2) and triplet (S = 1) molecular spin states have the potential for excellent optical and spin properties for these applications if useful photon-spin mechanisms at room temperature can be devised. Here we explore the potential of exploiting reversible energy transfer between triplet and doublet states to establish magnetosensitive luminescence and spin polarization. We investigate the dependence of the photon-spin mechanism on the magnitude and sign of the exchange interaction between the doublet and triplet spin components in amorphous and crystalline model systems. The design of a magnetic field inclination sensor is proposed from understanding the required "structure" (spin interactions) to "function" (magnetosensitivity).

Luminescent Radicals.

Organic radicals are attracting increasing interest as a new class of molecular emitters. They demonstrate electronic excitation and relaxation dynamics based on their doublet or higher multiplet spin states, which are different from those based on singlet-triplet manifolds of conventional closed-shell molecules. Recent studies have disclosed luminescence properties and excited state dynamics unique to radicals, such as highly efficient electron-photon conversion in OLEDs, NIR emission, magnetoluminescence, an absence of heavy atom effect, and spin-dependent and spin-selective dynamics. These are difficult or sometimes impossible to achieve with closed-shell luminophores. This review focuses on luminescent organic radicals as an emerging photofunctional molecular system, and introduces the material developments, fundamental properties including luminescence, and photofunctions. Materials covered in this review range from monoradicals, radical oligomers, and radical polymers to metal complexes with radical ligands demonstrating radical-involved emission. In addition to stable radicals, transiently formed radicals generated in situ by external stimuli are introduced. This review shows that luminescent organic radicals have great potential to expand the chemical and spin spaces of luminescent molecular materials and thus broaden their applicability to photofunctional systems.

Electronic properties and collision cross sections of AgOkHm± (k, m = 1-4) aerosol ionic clusters.

Experimental evidence shows that hydroxylated metal ions are often produced during cluster synthesis by atmospheric pressure spark ablation. In this work, we predict the ground state equilibrium structures of AgOkHm± clusters (k and m = 1-4), which are readily produced when spark ablating Ag, using the coupled cluster with singles and doubles (CCSD) method. The stabilization energy of these clusters is calculated with respect to the dissociation channel having the lowest energy, by accounting perturbative triples corrections to the CCSD method. The interatomic interactions in each of the systems have been investigated using the frontier molecular orbital (FMO), natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) methods. Many of the ground states of these ionic clusters are found to be stable, corroborating experimental observations. We find that clusters having singlet spin states are more stable in terms of dissociation than the clusters that have doublet or triplet spin states. Our calculations also indicate a strong affinity of the ionic and neutral Ag atom towards water and hydroxyl radicals or ions. Many 3-center, 4-electron (3c/4e) hyperbonds giving rise to more than one resonance structure are identified primarily for the anionic clusters. The QTAIM analysis shows that the O-H and O-Ag bonds in the clusters of both polarities are respectively covalent and ionic. The FMO analysis indicates that the anionic clusters are more reactive than the cationic ones. Using the cluster structures predicted by the CCSD method, we calculate the collision cross sections of the AgOkHm± family, with k and m ranging from 1 to 4, by the trajectory method. In turn, we predict the electrical mobilities of these clusters when suspended in helium at atmospheric pressure and compare them with experimental measurements.

PyBEST: Improved functionality and enhanced performance

PyBEST: Improved functionality and enhanced performance

Nickel(II) and nickel(III) thiosemicarbazone and hydrazone complexes: An unexpected journey

In this study, the properties of nickel(II) thiosemicarbazone (complex 1) and nickel(III) (complex 2) hydrazone complexes were investigated using single crystal X-ray diffraction analysis, electron paramagnetic resonance, infrared spectroscopy, UV-Vis spectroscopy, molar conductivity and Density Functional Theory (DFT) calculations. The large difference in magnetic moments led us to suspect that we had obtained nickel complexes of different oxidation states (3.5 μB and 2.1 μB). This was verified after recording the Electron Paramagnetic Resonance (EPR) spectra for complex 2. The g value of 2.018 is consistent with a low spin (S = 1/2) Ni(III) species. DFT calculations are in agreement with the EPR data and show a doublet spin state of complex 2 with the unpaired electron practically completely located in the first coordination sphere (76.5%). All the findings show that the studied complex have different structural and electronic properties as a function of the oxidized state of nickel. In general, nickel(III) complexes are more difficult to obtain than nickel(II) complexes due to the stability of the nickel(II) oxidation state. Considering that this is the first Ni(III) hydrazone complex to be synthesised without an oxidising agent, its importance lies in providing insight into the fundamental properties and structure of Ni(III) hydrazone complexes. This could help to improve their synthesis and further investigate their applications.

Partial Oxidation of Methane to Methanol by Using Molecular O2 on Pd2+ Catalyst: An Insight from Theory

AbstractThe partial oxidation of methane to methanol using cationic Pd2 dimers is investigated by employing density functional theory (DFT) method. We used B3PW91 functional for geometry optimization, and frequency calculations of all species involved in [Pd2]++O2+2CH4 reaction. Furthermore, a density‐fitting triple zeta valence with single‐polarization (def2TZVP) is used in the calculation to determine the atomic orbitals of the atoms. We oxidized Pd2+ to [Pd2O2]+ using O2 and performed possible partial oxidation of methane to methanol on [Pd2O2]+ and [Pd2O]+ and explored various intermediates and transition states on the potential energy surface (PES) diagram. From Potential Energy Surface (PES) analysis, it is found that the [Pd2O2]+ in doublet spin state multiplicity (SM=2) following radical mechanism is the more preferred pathway for methane to methanol conversion.

Spin‐tautomery of endohedral Y@C60 complex

AbstractNew conception of spin‐tautomery was developed based on the results of quantum chemical investigation of the endohedral Y@C60 complex. The embedding energies of yttrium into the fullerene cavity, dipole moments, polarizabilities, and IR spectra in the doublet and quartet spin states were calculated by the density‐functional theory quantum chemical methods. The degeneracy degree of the state of the complex is retained upon doublet–quartet excitation, since a twofold increase in the number of electron spin projections is compensated by a twofold decrease in the number of equivalent potential energy minima. The non‐conservation of spin by an endohedral complex with a heavy atom makes it possible to interpret the interconversion of doublet and quartet states as a non‐degenerate spin‐tautomery.

First-Principles Study of MoS2, WS2, and NbS2 Quantum Dots: Electronic Properties and Hydrogen Evolution Reaction

The electronic and catalytic properties of two-dimensional MoS2, WS2, and NbS2 quantum dots are investigated using density functional theory investigations. The stability of the considered structures is confirmed by the positive binding energies and the real vibrational frequencies in the infrared spectra. The ab initio molecular dynamics simulations show that these nanodots are thermally stable at 300 K with negligible changes in the potential energy and metal–S bonds. The pristine nanodots are semiconductors with energy gaps ranging from 2.6 to 3 eV. Edge sulfuration significantly decreases the energy gap of MoS2 and WS2 to 1.85 and 0.75 eV, respectively. The decrease is a result of the evolution of low-energy molecular orbitals by the passivating S-atoms. The energy gap of NbS2 is not affected, which could be due to the spin doublet state. Molecular electrostatic potentials reveal that the edge sulfur/transition metal atoms are electrophilic/nucleophilic sites, while the surface atoms are almost neutral sites. MoS2 quantum dots show an interestingly low change in the hydrogen adsorption free energy ~0.007 eV, which makes them competitive for hydrogen evolution catalysts.

Dissociation dynamics of anionic carbon monoxide in dark states.

A resonant system consisting of an excess electron and a closed-shell atom or molecule, as a temporary negative ion, is usually in doublet-spin states that are analogous to bright states of photoexcitation of the neutral. However, anionic higher-spin states, noted as dark states, are scarcely accessed. Here, we report the dissociation dynamics of CO- in dark quartet resonant states that are formed by electron attachments to electronically excited CO (a3Π). Among the dissociations to O-(2P) + C(3P), O-(2P) + C(1D), and O-(2P) + C(1S), the latter two are spin-forbidden in the quartet-spin resonant states of CO-, while the first process is preferred in 4Σ- and 4Π states. The present finding sheds new light on anionic dark states.

Theoretical Study of Hydroxylation of α- and β-Pinene by a Cytochrome P450 Monooxygenase Model

Previous studies on biocatalytic transformations of pinenes by cytochrome P450 (CYP) enzymes reveal the formation of different oxygenated products from a single substrate due to the multistate reactivity of CYP and the many reactive sites in the pinene scaffold. Up until now, the detailed mechanism of these biocatalytic transformations of pinenes have not been reported. Hereby, we report a systematic theoretical study of the plausible hydrogen abstraction and hydroxylation reactions of α- and β-pinenes by CYP using the density functional theory (DFT) method. All DFT calculations in this study were based on B3LYP/LAN computational methodology using the Gaussian09 software. We used the B3LYP functional with corrections for dispersive forces, BSSE, and anharmonicity to study the mechanism and thermodynamic properties of these reactions using a bare model (without CYP) and a pinene-CYP model. According to the potential energy surface and Boltzmann distribution for radical conformers, the major reaction products of CYP-catalyzed hydrogen abstraction from β-pinene are the doublet trans (53.4%) and doublet cis (46.1%) radical conformer at delta site. The formation of doublet cis/trans hydroxylated products released a total Gibbs free energy of about 48 kcal/mol. As for alpha pinene, the most stable radicals were trans-doublet (86.4%) and cis-doublet (13.6%) at epsilon sites, and their hydroxylation products released a total of ~50 kcal/mol Gibbs free energy. Our results highlight the likely C-H abstraction and oxygen rebounding sites accounting for the multi-state of CYP (doublet, quartet, and sextet spin states) and the formation of different conformers due to the presence of cis/trans allylic hydrogen in α-pinene and β-pinene molecules.

Biotransformation of Bisphenol by Human Cytochrome P450 2C9 Enzymes: A Density Functional Theory Study.

Bisphenol A (BPA, 2,2-bis-(4-hydroxyphenyl)propane) is used as a precursor in the synthesis of polycarbonate and epoxy plastics; however, its availability in the environment is causing toxicity as an endocrine-disrupting chemical. Metabolism of BPA and their analogues (substitutes) is generally performed by liver cytochrome P450 enzymes and often leads to a mixture of products, and some of those are toxic. To understand the product distributions of P450 activation of BPA, we have performed a computational study into the mechanisms and reactivities using large model structures of a human P450 isozyme (P450 2C9) with BPA bound. Density functional theory (DFT) calculations on mechanisms of BPA activation by a P450 compound I model were investigated, leading to a number of possible products. The substrate-binding pocket is tight, and as a consequence, aliphatic hydroxylation is not feasible as the methyl substituents of BPA cannot reach compound I well due to constraints of the substrate-binding pocket. Instead, we find low-energy pathways that are initiated with phenol hydrogen atom abstraction followed by OH rebound to the phenolic ortho- or para-position. The barriers of para-rebound are well lower in energy than those for ortho-rebound, and consequently, our P450 2C9 model predicts dominant hydroxycumyl alcohol products. The reactions proceed through two-state reactivity on competing doublet and quartet spin state surfaces. The calculations show fast and efficient substrate activation on a doublet spin state surface with a rate-determining electrophilic addition step, while the quartet spin state surface has multiple high-energy barriers that can also lead to various side products including C4-aromatic hydroxylation. This work shows that product formation is more feasible on the low spin state, while the physicochemical properties of the substrate govern barrier heights of the rate-determining step of the reaction. Finally, the importance of the second-coordination sphere is highlighted that determines the product distributions and guides the bifurcation pathways.

Galvinoxyl-inspired dinitronyl nitroxide: structural, magnetic, and theoretical studies

A novel galvinoxyl-inspired dinitronyl nitroxide shows a ground doublet spin state and a unique electron configuration.

Coordination and Spin States in Fe+(C2H2)n Complexes Studied with Selected-Ion Infrared Spectroscopy.

Fe+(acetylene)n ion-molecule complexes are produced in a supersonic molecular beam with pulsed laser vaporization. These ions are mass selected and studied with infrared photodissociation spectroscopy in the C-H stretching region, complemented by computational chemistry calculations. All C-H stretch vibrations are shifted to frequencies lower than the vibrations of isolated acetylene because of the charge transfer that occurs between the metal ion and the molecules. Complexes in the size range of n = 1-4 are found to have structures with individual acetylene molecules bound to the core metal ion via cation-π interactions. The coordination is completed with four ligands in a structure close to a distorted tetrahedron. Larger complexes in the range of n = 5-8 have external acetylene molecules solvating this n = 4 core ion via CH-π bonding to inner-shell ligands. DFT computations predict that quartet spin states are more stable for all complex sizes, but infrared spectra for quartet and doublet spin states are quite similar, precluding definitive determination of the spin states. There is no evidence for any of these complexes having acetylenes coupled into reacted structures. This is consistent with computed thermochemistry, which finds significant activation barriers to such reactions.

Josephson current via spin and orbital states of a tunable double quantum dot

Supercurrent transport is experimentally studied in a Josephson junction hosting a double quantum dot (DQD) with tunable symmetries. The QDs are parallel-coupled to two superconducting contacts and can be tuned between strong inter-dot hybridization and a ring geometry where hybridization is suppressed. In both cases, we observe supercurrents when the two interacting orbitals are either empty or filled with spins, or a combination. However, when each QD hosts an unpaired spin, the supercurrent depends on the spin ground state. It is strongly suppressed for the ring geometry with a spin-triplet ground state at zero external magnetic field. By increasing the QD hybridization, we find that a supercurrent appears when the ground state changes to spin-singlet. In general, supercurrents are suppressed in cases of spin doublet ground state, but an exception occurs at orbital degeneracy when the system hosts one additional spin, as opposed to three, pointing to a broken particle-hole symmetry.

Revealing metabolic path of Ketamine catalyzed by CYP450 via quantum mechanical approach

Ketamine is essential medication used in anesthesia. This drug is metabolized by CYP450 enzyme, found in human liver. After metabolism they form product called metabolites. It takes more time or less time to forming the product. So it is essential to investigate the mechanism of reaction, duration of reaction and side effects of formed metabolite. A reaction involves reactant complex, transition state, intermediate state and product. The present work concluded the barrier energies of these complexes that reveals the metabolic path of Ketamine via aliphatic hydroxylation step catalyzed by CYP450 enzyme. In current study, theoretical methods are utilized to investigate the mechanism, involved energetics, electronic reorganizations, structural information, barrier heights and Density Functional Theory (DFT) descriptors of the reactant & product, during the course of the reaction to elucidate the formation of product. The reaction is performed on two spin surfaces one is doublet another is quartet. It is concluded barrier height of transition states (TS) with single imaginary frequency (i1549.92 cm−1 and i1205.31 cm−1) for doublet (16.07 kcal/mol) and quartet (16.61 kcal/mol) spin states, respectively. The present study is very much successful to understand the metabolic path of ketamine due to reliability and accuracy of results. These results will be very helpful for experimentalist to finding the transition state of reaction and theoretical researchers in filed of drug discovery to finding new drugs.

Effect of methyl substituents on the preferred conformations of Bis(pentadienyl) open metallocenes

Density functional theory (DFT) methods indicated that the preferred geometries, spin states, and energetics of unsubstituted bis(pentadienyl)metal open sandwich complexes (C5H7)2M of the first row transition metals (M = Ti to Ni) are similar to those of the corresponding substituted and more stable (2,4-Me2C5H5)2M open sandwich complexes with 2,4-dimethylpentadienyl ligands. Structures with two fully bonded pentahapto η5-C5H7 ligands are energetically preferred for iron and for the transition metals to the left of iron in the Periodic Table. However, for the electron-rich first-row transition metals cobalt and nickel, structures with at least one trihapto η3-C5H7 ligand are preferred in order to prevent the electron configuration of the central metal atom from exceeding the favored 18-electrons. For the manganese systems (C5H7)2Mn and (2,4-Me2C5H5)2Mn the presence of the two methyl substituents is found to have little effect on the complicated potential energy surface with low-energy structures in the doublet, quartet, and sextet spin states.

Mechanistic insights into the chemistry of compound I formation in heme peroxidases: quantum chemical investigations of cytochrome c peroxidase.

Peroxidases are heme containing enzymes that catalyze peroxide-dependant oxidation of a variety of substrates through forming key ferryl intermediates, compounds I and II. Cytochrome c peroxidase (Ccp1) has served for decades as a chemical model toward understanding the chemical biology of this heme family of enzymes. It is known to feature a distinctive electronic behaviour for its compound I despite significant structural similarity to other peroxidases. A water-assisted mechanism has been proposed over a dry one for the formation of compound I in similar peroxidases. To better identify the viability of these mechanisms, we employed quantum chemistry calculations for the heme pocket of Ccp1 in three different spin states. We provided comparative energetic and structural results for the six possible pathways that suggest the preference of the dry mechanism energetically and structurally. The doublet state is found to be the most preferable spin state for the mechanism to proceed and for the formation of the Cpd I ferryl-intermediate irrespective of the considered dielectric constant used to represent the solvent environment. The nature of the spin state has negligible effects on the calculated structures but great impact on the energetics. Our analysis was also expanded to explain the major contribution of key residues to the peroxidase activity of Ccp1 through exploring the mechanism at various in silico generated Ccp1 variants. Overall, we provide valuable findings toward solving the current ambiguity of the exact mechanism in Ccp1, which could be applied to peroxidases with similar heme pockets.

Transient dynamics of a magnetic impurity coupled to superconducting electrodes: Exact numerics versus perturbation theory

Impurities coupled to superconductors offer a controlled platform to understand the interplay between superconductivity, many-body interactions, and nonequilibrium physics. In the equilibrium situation, local interactions at the impurity induce a transition from the spin-singlet to the spin-doublet ground state, resulting in a supercurrent sign reversal ($0\text{\ensuremath{-}}\ensuremath{\pi}$ transition). In this work, we apply the exact time-dependent density matrix renormalization group method to simulate the transient dynamics of such superconducting systems. We also use a perturbative approximation to analyze their properties at longer times. These two methods agree for a wide range of parameters. In a phase-biased situation, the system gets trapped in a metastable state characterized by a lower supercurrent compared to the equilibrium case. We show that local Coulomb interactions do not provide an effective relaxation mechanism for the initially trapped quasiparticles. In contrast, other relaxation mechanisms, such as coupling to a third normal lead, make the impurity spin relax for parameter values corresponding to the equilibrium 0 phase. For parameters corresponding to the equilibrium $\ensuremath{\pi}$ phase the impurity converges to a spin-polarized stationary state. Similar qualitative behavior is found for a voltage-biased junction, which provides an effective relaxation mechanism for the trapped quasiparticles in the junction.