Low-lying Isomers Research Articles

Decoding the structural and electronic variations in M2Bn- (M = Sc, Y, La; n = 6–9) clusters: Insights for nanomaterial design

A series of low-lying energy isomers of M2Bn- (M = Sc, Y, La; n = 6–9) clusters were investigated using density functional theory. By conducting functional tests and comparing with reported experimental photoelectron spectra, we confirmed that when n = 6 − 8, their ground-state structures are nearly identical, differing only in the distance between the M atom and the boron skeleton. Moreover, for n = 7–8, all ground states exhibit consistent inverse-sandwich structures. However, for n = 9, three systems exhibit different types of ground-state structures: The Sc-doped system has a quasi-inverse-sandwich structure, the Y-doped system has two possible coexisting structures, and the La-doped system has an inverse-sandwich structure. Subsequent average binding energy analyses, chemical bonding analyses and stability analyses further elucidated the reasons. Our research provides theoretical insights for a deeper understanding of the various properties of clusters doped with different elements and for exploring potential building blocks for nanomaterials.

Photoelectron Spectroscopy and Theoretical Studies on the Structures and Properties of Ge4C- and Ge4CH- Clusters.

We investigate the structures and properties of Ge4C-/0 and Ge4CH-/0 clusters using anion photoelectron spectroscopy and theoretical calculations. Our calculations show that the first two low-lying isomers coexist in the experiments of Ge4C- and Ge4CH-. The first two low-lying isomers of Ge4C- have trigonal bipyramidal structures with the C atom on the equatorial plane and the top vertex, respectively. It is found that the first two low-lying isomers of Ge4CH- can be obtained by adding an H atom to the top and equatorial C atoms of Ge4C-, respectively. The AdNDP analyses reveal that the C atom in Ge4C forms one 4c-2e σ bond, two 4c-2e π bonds, and one 5c-2e σ bond with Ge atoms. The C atom in Ge4C interacts with an H- forming a C-H σ bond in Ge4CH-. AIMD simulation results indicate high dynamic stabilities of Ge4C and Ge4CH- at 300 and 500 K. Our results show that the structures and chemical bonding of Ge4B- and Ge4N+ are similar to those of Ge4C, while those of Ge4BH2- and Ge4NH resemble those of Ge4CH-.

Energetic and Kinetic Competition on the Stability of Pd13 Clusters: Ab Initio Molecular Dynamics Simulations.

Material stability is the focus on both experiments and calculations, which includes the energetic stability at the static state and the thermodynamic stability at the kinetic state. To show whether energetics or kinetics dominates on material stability, this study focuses on the Pd13 clusters, because of their observable magnetic moment in experiment. Energetically, the CALYPSO searching method and first-principles calculations find that Pd13(C2) is the ground state at 0 K while the static frequency calculations demonstrate that the icosahedron Pd13(Ih) becomes more favorable on free energy as temperature increases. However, their magnetic moments (8 μB) are not in agreement with the experimental value (<5.2 μB). Kinetically, ab initio molecular dynamics simulations reveal that Pd13(C3v) (6 μB) has supreme isomerization temperature and the other 11 low-lying isomers transform to Pd13(C3v) directly or indirectly, demonstrating that Pd13(C3v) has the maximum probability to be observed in experiment. The magnetic moment difference between experiment (<5.2 μB) and this calculation (6 μB) may be due to the spin multiplicities. Our result suggests that the magnetic moment disparity between theory and experiment (in Pd13 clusters) originates from the kinetic stability.

Structural Study of [Sc3O4(CO2)n]+ (n = 2, 3) Complexes by Infrared Photodissociation Spectroscopy and Density Functional Calculations.

The catalytic transformation of CO2 into valuable products has garnered wide interest owing to both economic and environmental benefits, in which the chemical fixation of CO2 into carbonate structures represents a crucial step that occurs on the adsorbed catalyst surfaces. Transition metal oxides with acidic and basic active sites have exhibited potential in promoting the carbonation of weakly bound CO2 molecules. Here, the interactions between CO2 molecules and the Sc3O4+ cation in the gas phase are investigated by using infrared photodissociation spectroscopy in conjunction with quantum chemical calculations. Both end-on and various carbonate-containing configurations, including center and bridge carbonate structures, have been theoretically identified for the CO2-coordinated ion-molecule complexes. Based on the comparison between the experimental spectra and simulated spectra of low-lying isomers in the CO2 antisymmetric stretching vibrational frequency region, isomers characterized by a bridge carbonate core structure are demonstrated to be the major contributors to the observed spectra. Examination of potential energy surfaces reveals lower energy barriers and simpler reaction routes for the conversion of molecularly bound CO2 into a bridge carbonate moiety, providing reasonable explanations for their prevalence in the experiments.

Borozenes: Benzene-Like Planar Aromatic Boron Clusters.

ConspectusWith three valence electrons and four valence orbitals, boron (2s22p1) is an electron-deficient element, resulting in interesting chemical bonding and structures in both borane molecules and bulk boron materials. The electron deficiency leads to electron sharing and delocalization in borane compounds and bulk boron allotropes, characterized by polyhedral cages, in particular, the ubiquitous B12 icosahedral cage. During the past two decades, the structures and bonding of size-selected boron clusters have been elucidated via combined photoelectron spectroscopy and theoretical investigations. Unlike bulk boron materials, finite boron clusters have been found to possess 2D structures consisting of B3 triangles, dotted with tetragonal, pentagonal, or hexagonal holes. The discovery of the planar B36 cluster with a central hexagonal hole provided the first experimental evidence for the viability of 2D boron nanostructures (borophene), which have been synthesized on inert substrates. The B7-, B8-, and B9- clusters were among the first few boron clusters to be investigated by joint photoelectron spectroscopy and theoretical calculations, and they were all found to possess 2D structures with a central B atom inside a Bn ring. Recently, the B73- (C6v), B82- (D7h), and B9- (D8h) series of closed-shell species were shown to possess similar π bonding akin to that in the C5H5-, C6H6, and C7H7+ series, respectively, and the name "borozene" was coined to highlight their analogy to the classical aromatic hydrocarbon molecules.Among the borozenes, the D7h B82- species is unique for its high stability originating from both its double aromaticity and the fact that the B7 ring has the perfect size to host a central B atom. The B82- borozene has been realized experimentally in a variety of MB8 and M2B8 complexes. In particular, the B82- borozene has been observed to stabilize the rare valence-I oxidation state of lanthanides in LnB8- complexes, as well as a Cu2+ species in Cu2B8-. The B6 ring in B73- is too small to host a B atom, resulting in a slight out-of-plane distortion. Interestingly, the bowl-shaped B7 borozene is perfect for coordination to a metal atom, leading to the observation of a series of highly stable MB7 borozene complexes. On the other hand, the B8 ring is slightly too large to host the central B atom, such that a low-lying and low-symmetry isomer also exists for B9-. Even though most 2D boron clusters are aromatic, the B73-, B82-, and B9- borozenes are special because of their high symmetries and their analogy to the series of C5H5-, C6H6, and C7H7+ prototypical aromatic compounds. This Account discusses recent experimental and theoretical advances on the investigations of various borozene complexes. It is expected that many new borozene compounds can be designed and may be eventually synthesized.

Probing the geometric and electronic structure of rhodium oxide clusters (RhO)n− (n = 2–4) by anion photoelectron spectroscopy and theoretical calculations

The cluster configurations of (RhO)n− (n = 2–4) have been examined using photoelectron (PE) velocity-map imaging combined with density functional theory calculations. The PE spectra have provided the anion detachment energies (ADEs) information of three ground states, determined to be 2.40, 2.86, and 2.94 eV for n = 2–4, respectively. The geometric structures have been identified by comparing the density of states (DOS) spectra of several low-lying isomers with the PE spectra. The three cluster configurations consist of a Rhn (n = 2–4) core with isolated O atoms bonded to the core, exhibiting planar or quasi-planar geometries. The analysis of magnetic moments and spin densities indicated that the most stable three anions have high spin multiplicities of 4, 5, and 4 for n = 2–4, respectively, with the unpaired electrons delocalized on each of the Rh and O atoms.

Master equation modeling of water dissociation in small ionic water clusters: Ag+(H2O) n , n = 4-6.

We model temperature-dependent blackbody infrared radiative dissociation (BIRD) rate coefficients of Ag+(H2O) n , n = 4-6, a system with loosely bound water molecules. We employ a master equation modeling (MEM) approach with consideration of absorption and emission of blackbody radiation, comparing single and multiple-well descriptions. The unimolecular dissociation rate coefficients are obtained using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory, employing two approaches to model the sum of states in the transition state, the rigid activated complex (RAC) and the phase space limit (PSL) approach. A genetic algorithm is used to find structures of low-lying isomers for the kinetic modeling. We show that the multiple-well MEM approach with PSL RRKM in the All Wells and Transition States Are Relevant (AWATAR) variant provides a reliable description of Ag+(H2O) n BIRD, in agreement with previously published experimental data. Higher-lying isomers contribute significantly to the overall dissociation rate coefficient, underlying the importance of the multiple-well ansatz in which all isomers are treated on the same footing.

Dual External Field Strategy in Regulating the Superhalogen Characteristics of the Non-Noble Metal Constituted Tantalum Oxide Clusters.

The identification of the non-noble metal constituted TaO cluster as a potential analogue to the noble metal Au is significant for the development of tailored materials. It leverages the superatom concept to engineer properties with precision. However, the impact of incrementally integrating TaO units on the electronic configurations and properties within larger TaO-based clusters remains to be elucidated. By employing the density functional theory calculations, the global minima and low-lying isomers of the TanOn (n = 2-5) clusters were determined, and their structural evolution was disclosed. In the cluster series, Ta5O5 was found to possess the highest electron affinity (EA) with a value of 2.14 eV, based on which a dual external field (DEF) strategy was applied to regulate the electronic property of the cluster. Initially, the electron-withdrawing CO ligand was affixed to Ta5O5, followed by the application of an oriented external electric field (OEEF). The CO ligation was found to be able to enhance the Ta5O5 cluster's electron capture capability by adjusting its electron energy levels, with the EA of Ta5O5(CO)4 peaking at 2.58 eV. Subsequently, the introduction of OEEF further elevated the EA of the CO-ligated cluster. Notably, OEEF, when applied along the +x axis, was observed to sharply increase the EA to 3.26 eV, meeting the criteria for superhalogens. The enhancement of EA in response to OEEF intensity can be quantified as a functional relationship. This finding highlights the advantage of OEEF over conventional methods, demonstrating its capacity for precise and continuous modulation of cluster EAs. Consequently, this research has adeptly transformed tantalum oxide clusters into superhalogen structures, underscoring the effectiveness of the DEF strategy in augmenting cluster EAs and its promise as a viable tool for the creation of superhalogens.

Revisiting the Structure and Bonding in Li5H6- and the Exploration of Reactivity: Planar Pentacoordinate Hydrogen.

Recently, Guha and co-workers (Sarmah, K.; Kalita, A.; Purkayastha, S.; Guha, A. K. Pushing The Extreme of Multicentre Bonding: Planar Pentacoordinate Hydride. Angew. Chem. Int. Ed. 2024, e202318741) reported a highly intriguing bonding motif: planar pentacoordinate hydrogen (ppH) in Li5H6-, featuring C2v symmetry in the singlet state with two distinct H-Li (center-ring) bond distances. We herein revisited the potential energy surface of Li5H6- by using a target-oriented genetic algorithm. Our investigation revealed that the lowest-energy structure of Li5H6- exhibits a ppH configuration with very high D5h symmetry and a 1A1' electronic state. We did not find any electronic effect like Jahn-Teller distortion that could be responsible for lowering its symmetry. Moreover, our calculations demonstrated significant differences in the relative energies of other low-lying isomers. An energetically very competitive planar tetracoordinate hydrogen (ptH) isomer is also located, but it corresponds to a very shallow minimum on the potential energy surface depending on the used level of theory. Chemical bonding analyses, including AdNDP and EDA-NOCV, uncover that the optimal Lewis structure for Li5H6- involves H- ions stabilized by the Li5H5 crown. Surprisingly, despite the dominance of electrostatic interactions, the contribution from covalent bonding is also significant between ppH and the Li5H5 moiety, derived from H-(1s) → Li5H5 σ donation. Magnetically induced current density analysis revealed that due to minimal orbital overlap and the highly polar nature of the H-Li covalent interaction, the ppH exhibits local diatropic ring currents around the H centers, which fails to result in a global aromatic ring current. The coordination of Li5H6- with Lewis acids, BH3 and BMe3, instantly converts the ppH configuration to (quasi) ptH. These Lewis acid-bound ptH complexes show high electronic stability and high thermochemical stability against dissociation and, therefore, will be ideal candidates for the experimental realization.

Structural characterizations of histidine-containing tripeptides complexed with zinc and cadmium dications using IRMPD spectroscopy and theoretical calculations

Metalated gas-phase complexes, M2+(HisAlaAla), M2+(AlaHisAla), and M2+(AlaAlaHis), where M = Zn and Cd, were examined using infrared multiple photon dissociation (IRMPD) spectroscopy with light from a free-electron laser (FEL). These complexes were chosen because they provide model systems for metal binding to proteins. Complementary simulated annealing calculations were performed to determine energetically low-lying conformers and isomers of these structures. Quantum chemical calculations were used to optimize the structures at the B3LYP level of theory using 6-311+G(d,p) and def2-TZVP basis sets for zinc and cadmium complexes, respectively. IRMPD and calculated linear absorption spectra were compared to evaluate which structures are present. Relative energies of the various species were evaluated using single-point energy calculations for low-lying structures at the B3LYP, B3P86, and MP2(full) levels using 6-311+G(2d,2p) and def2-TZVPP basis sets. For species with histidine at a terminal position (AAH or HAA), the conformations that best reproduce the IRMPD spectra are charge-solvated (CS) conformers, where the metal dication binds to the amine and carbonyl groups of the peptide backbone and to the nitrogen of the histidine side chain, along with contributions from an iminol structure for AAH. The species with the histidine in the center position (AHA) adopt an iminol structure, where the metal dication binds to the backbone iminol nitrogens, the α-amine, π-imine, and the carbonyl of the C-terminus.

Laser spectroscopy of triply charged 229Th isomer for a nuclear clock.

Thorium-229 (229Th) possesses an optical nuclear transition between the ground state (229gTh) and low-lying isomer (229mTh). A nuclear clock based on this nuclear-transition frequency is expected to surpass existing atomic clocks owing to its insusceptibility to surrounding fields1-5. In contrast to other charge states, triply charged 229Th (229Th3+) is the most suitable for highly accurate nuclear clocks because it has closed electronic transitions that enable laser cooling, laser-induced fluorescence detection and state preparation of ions1,6-8. Although laser spectroscopic studies of 229Th3+ in the nuclear ground state have been performed8, properties of 229mTh3+, including its nuclear decay lifetime that is essential to specify the intrinsic linewidth of the nuclear-clock transition, remain unknown. Here we report the trapping of 229mTh3+ continuously supplied by a 233U source and the determination of nuclear decay half-life of the isolated 229mTh3+ to be through nuclear-state-selective laser spectroscopy. Furthermore, by determining the hyperfine constants of 229mTh3+, we reduced the uncertainty of the sensitivity of the 229Th nuclear clock to variations in the fine-structure constant by a factor of four. These results offer key parameters for the 229Th3+ nuclear clock and its applications in the search for new physics.

Size effects and electronic properties of zinc-doped boron clusters Zn (n = 1-15).

To gain a deeper understanding of zinc-doped boron clusters, theoretical calculations were performed to investigate the size effects and electronic properties of zinc-doped boron clusters. The study of the electronic properties, spectral characteristics, and geometric structures of Zn (n = 1-15) is of great significance in the fields of semiconductor materials science, material detection, and improving catalytic efficiency. The results indicate that Zn (n = 1-15) clusters predominantly exhibit planar or quasi-planar structures, with the Zn atom positioned in the outer regions of the framework. The second stable structure of Zn is a three-dimensional configuration, indicating that the structures of zinc-doped boron clusters begin to convert from the planar or quasi-planar structures to the 3D configurations. The second low-energy structure of Zn is a novel configuration. Relative stability analyses show that the Zn has better chemical stability than other clusters with a HOMO-LUMO gap of 2.79 eV. Electric charge analysis shows that part electrons on zinc atoms are transferred to boron atoms, and electrons prefer to cluster near the framework. According to the electron localization function, it gets harder to localize electrons as the equivalent face value drops, and it's challenging to see covalent bond formation between zinc and boron atoms. The spectrograms of Zn (n = 1-15) exhibit distinct properties and notable spectral features, which can be used as a theoretical basis for the identification and confirmation of boron clusters doped with single-atom transition metals. The calculations were performed using the ABCluster global search technique combined with density functional theory (DFT) methods. The selected low-energy structures were subjected to geometric optimization and frequency calculations at the PBE0/6-311 G(d) level to ensure structural stability and eliminate any imaginary frequencies. To acquire more precise relative energies, we performed single-point energies calculations for the low-lying isomers of Zn (n = 1-15) at the CCSD(T)/6-311 G(d)//PBE0/6-311 G(d) level of theory. All calculations were performed using Gaussian 09 software. To facilitate analysis, we utilized software tools such as Multiwfn, and VMD.

Master equation modeling of blackbody infrared radiative dissociation (BIRD) of hydrated peroxycarbonate radical anions.

Molecular cluster ions, which are stored in an electromagnetic trap under ultra-high vacuum conditions, undergo blackbody infrared radiative dissociation (BIRD). This process can be simulated with master equation modeling (MEM), predicting temperature-dependent dissociation rate constants, which are very sensitive to the dissociation energy. We have recently introduced a multiple-well approach for master equation modeling, where several low-lying isomers are taken into account. Here, we experimentally measure the BIRD of CO4●-(H2O)1,2 and model the results with a slightly modified multiple-well MEM. In the experiment, we exclusively observe loss of water from CO4●-(H2O), while the BIRD of CO4●-(H2O)2 leads predominantly to loss of carbon dioxide, with water loss occurring to a lesser extent. The MEM of two competing reactions requires empirical scaling factors for infrared intensities and the sum of states of the loose transition states employed in the calculation of unimolecular rate constants so that the simulated branching ratio matches the experiment. The experimentally derived binding energies are ΔH0(CO4●--H2O) = 45 ± 3kJ/mol, ΔH0(CO4●-(H2O)-H2O) = 41 ± 3kJ/mol, and ΔH0(CO2-O2●-(H2O)2) = 37 ± 3kJ/mol. Quantum chemical calculations on the CCSD(T)/aug-cc-pVTZ//CCSD/aug-cc-pVDZ level, corrected for the basis set superposition error, yield binding energies that are 2-5kJ/mol higher than experiment, within error limits of both experiment and theory. The relative activation energies for the two competing loss channels are as well fully consistent with theory.

Conformational Preference of Lithium Polysulfide Clusters Li2Sx (x = 4-8) in Lithium-Sulfur Batteries.

Structures are of fundamental importance for diverse studies of lithium polysulfide clusters, which govern the performance of lithium-sulfur batteries. The ring-like geometries were regarded as the most stable structures, but their physical origin remains elusive. In this work, we systematically explored the minimal structures of Li2Sx (x = 4-8) clusters to uncover the driving force for their conformational preferences. All low-lying isomers were generated by performing global searches using the ABCluster program, and the ionic nature of the Li···S interactions was evidenced with the energy decomposition analysis based on the block-localized wave function (BLW-ED) approach and further confirmed with the quantum theory of atoms in molecule (QTAIM). By analysis of the contributions of various energy components to the relative stability with the references of the lowest-lying isomers, the controlling factor for isomer preferences was found to be the polarization interaction. Notably, although the electrostatic interaction dominates the binding energies, it contributes favorably to the relative stabilities of most isomers. The Li+···Li+ distance is identified as the key geometrical parameter that correlates with the strength of the polarization of the Sx2- fragment imposed by the Li+ cations. Further BLW-ED analyses reveal that the cooperativity of the Li+ cations primarily determines the relative strength of the polarization.

Investigation of Pb-B Bonding in PbB2(BO)n- (n = 0-2): Transformation from Aromatic PbB2- to Pb[B2(BO)2]-/0 Complexes with BB Triple Bonds.

Boron has been found to be able to form multiple bonds with lead. To probe Pb-B bonding, here we report an investigation of three Pb-doped boron clusters, PbB2-, PbB3O-, and PbB4O2-, which are produced by a laser ablation cluster source and characterized by photoelectron spectroscopy and ab initio calculations. The most stable structures of PbB2-, PbB3O-, and PbB4O2- are found to follow the formula, [PbB2(BO)n]- (n = 0-2), with zero, one, and two boronyl ligands coordinated to a triangular and aromatic PbB2 core, respectively. The PbB2- cluster contains a BB double bond and two Pb-B single bonds. The coordination of BO is observed to weaken Pb-B bonding but strengthen the BB bond in [PbB2(BO)n]- (n = 1, 2). The anionic [PbB2(BO)2]- and its corresponding neutral closed-shell [PbB2(BO)2] contain a BB triple bond. A low-lying Y-shaped isomer is also observed for PbB4O2-, consisting of a central sp2 hybridized B atom bonded to two boronyl ligands and a PbB unit.

Global minimum and a heap of low-lying isomers with planar tetracoordinate carbon in the CAl3MgH2- system.

A global minimum and a heap of low-lying isomers with planar tetracoordinate carbon (ptC) are identified in the CAl3MgH2- system by computational quantum chemical investigations. The nature of the chemical bonding in the global minimum ptC isomer is examined using the conceptual quantum chemical tools. The atoms in molecule (AIM) analysis reveals that the global minimum isomer possesses a ptC geometry. Additionally, the adaptive natural density partitioning (AdNDP), electron localization function (ELF), and nucleus-independent chemical shifts (NICS) analysis corroborate the presence of delocalization in the ptC isomer. The delocalization of electron density in the global minimum ptC isomer contributes to attaining structural stability. The results also suggest that the bridging hydrogen plays a crucial role in stabilizing the ptC system. Furthermore, the ab initio molecular dynamics study supports the structural stability of the ptC isomer.

Searching for stable copper borozene complexes in CuB7- and CuB8.

Copper has been shown to be an important substrate for the growth of borophenes. Copper-boron binary clusters are ideal platforms to study the interactions between copper and boron, which may provide insight about the underlying growth mechanisms of borophene on copper substrates. Here we report a joint photoelectron spectroscopy and theoretical study on two copper-doped boron clusters, CuB7- and CuB8-. Well resolved photoelectron spectra are obtained for the two clusters at different wavelengths and are used to understand the structures and bonding properties of the two CuBn- clusters. We find that CuB8- is a highly stable borozene complex, which possesses a half-sandwich structure with a Cu+ species interacting with the doubly aromatic η8-B82- borozene. The CuB7- cluster is found to consist of a terminal copper atom bonded to a double-chain B7 motif, but it has a low-lying isomer composed of a half-sandwich structure with a Cu+ species interacting with an open-shell η7-B72- borozene. Both ionic and covalent interactions are found to be possible in the binary Cu-B clusters, resulting in different structures.

Transition Metal Behavior of Heavier Alkaline Earth Elements in Doped Monocyclic and Tubular Boron Clusters.

Quantum chemical calculations are carried out to design highly symmetric-doped boron clusters by employing the transition metal behavior of heavier alkaline earth (Ae = Ca, Sr, and Ba) metals. Following an electron counting rule, a set of monocyclic and tubular boron clusters capped by two heavier Ae metals were tested, which leads to the highly symmetric Ae2B8, Ae2B18, and Ae2B30 clusters as true minima on the potential energy surface having a monocyclic ring, two-ring tubular, and three-ring tubular boron motifs, respectively. Then, a thorough global minimum (GM) structural search reveals that a monocyclic B8 ring capped with two Ae atoms is indeed a GM for Ca2B8 and Ba2B8, while for Sr2B8 it is a low-lying isomer. Similarly, the present search also unambiguously shows the most stable isomers of Ae2B18 and Ae2B30 to be highly symmetric two- and three-ring tubular boron motifs, respectively, capped with two Ae atoms on each side of the tube. In these Ae-doped boron clusters, in addition to the electrostatic interactions, a substantial covalent interaction, specifically the bonding occurring between (n - 1)d orbitals of Ae and delocalized orbitals of boron motifs, provides the essential driving force behind their highly symmetrical structures and overall stability.

Theoretical Studies on the Isomerization Kinetics of Low-Lying Isomers of the SiC4H2 System.

The low-lying isomers of SiC4H2 are investigated to understand the kinetics of isomerization pathways using density functional theory. In our earlier work, we studied the various possible isomers (J. Phys. Chem. A, 2020, 124, 987-1002) and the chemical bonding of low-lying isomers of SiC4H2 (J. Phys. Chem. A, 2022, 126, 9366-9374). Among them, four isomers, 1-ethynyl-3-silacycloprop-1-en-3-ylidene (1), 3-silapent-1,4-diyn-3-ylidene (2), 1-silapent-1,2,3,4-tetraen-1-ylidene (4), and 1-silapent-2,4-diyn-1-ylidene (5) have already been identified in the laboratory. The previously known theoretical isomer 2-methylene-1-silabicyclo[1.1.0]but-1(3)-en-4-ylidene (3) and the newly identified unknown isomer through the present kinetic studies 5-silabicyclo[2.1.0]pent-1(4),2-dien-5-ylidene (N6) remain elusive in the laboratory to date. The isomerization pathways of the low-lying isomers of SiC4H2 are predicted through the transition state structures. Intrinsic reaction coordinate analysis identifies the minimum energy reaction pathways connecting the transition state from one isomer to another of the investigated system. The present kinetic data reveal the isomerization of global minimum energy isomer 1 to thermodynamically stable low-lying isomers, 2 and 5. Interestingly, isomer 3 interconverts to the experimentally known low-energy isomer 4, the second most thermodynamically stable isomer among them. The thermodynamic and kinetic parameters of the low-lying isomers of SiC4H2 are also documented in this work. The rate coefficient and equilibrium constant for isomerization reactions are calculated using the Rice-Ramsperger-Kassel-Marcus theory. The equilibrium constant delineates the difficulties in forming N6 and 3 through the isomerization pathways. Furthermore, ab initio molecular dynamics studies dictate the stability of low-lying isomers of SiC4H2 within the time scale of the simulation.

Structural and optical properties of the Agn-tyrosine complexes (n = 3-12): a density functional theory study.

We study the optical properties of Agn (n = 3-12) neutral clusters and their coordination with a tyrosine (Tyr) molecule. A global search strategy coupled with density functional theory (DFT) computations explored the potential energy surface. Adsorption energy calculations predicted that Tyr coordination stabilizes the metal clusters, favouring the Agn-Tyr complexes with an even number of silver atoms. For the Agn low-lying isomers, the general shape and the major transitions of the calculated time dependent-DFT (TD-DFT) absorption spectra align with those of previous reports measured in an argon environment. We use the analysis of non-covalent interactions to identify the specific interactions between each silver cluster and functional groups of Tyr. The TD-DFT absorption spectra for the Agn-Tyr complexes showed that Tyr significantly modifies the optical properties of the coordinated silver clusters and affects the smaller systems to a greater extent. The optical absorption results of the bare Agn clusters and the Agn-Tyr complexes are compared and discussed in detail.