In chemistry, a superatom is any cluster of atoms that seem to exhibit some of the properties of elemental atoms. [1]
Sodium atoms, when cooled from vapor, naturally condense into clusters, preferentially containing a magic number of atoms (2, 8, 20, 40, 58, etc.), with the outermost electron of each atom entering an orbital encompassing all the atoms in the cluster. Superatoms tend to behave chemically in a way that will allow them to have a closed shell of electrons, in this new counting scheme.[ citation needed ]
Certain aluminum clusters have superatom properties. These aluminium clusters are generated as anions (Al−
n with n = 1, 2, 3, … ) in helium gas and reacted with a gas containing iodine. When analyzed by mass spectrometry one main reaction product turns out to be Al
13I−
. [2] These clusters of 13 aluminium atoms with an extra electron added do not appear to react with oxygen when it is introduced in the same gas stream, indicating a halide-like character and a magic number of 40 free electrons. Such a cluster is known as a superhalogen. [3] [4] [5] [6] The cluster component in Al
13I−
ion is similar to an iodide ion or better still a bromide ion. The related Al
13I−
2 cluster is expected to behave chemically like the triiodide ion. [2]
Similarly it has been noted that Al
14 clusters with 42 electrons (2 more than the magic numbers) appear to exhibit the properties of an alkaline earth metal which typically adopt +2 valence states. This is only known to occur when there are at least 3 iodine atoms attached to an Al−
14 cluster, Al
14I−
3. The anionic cluster has a total of 43 itinerant electrons, but the three iodine atoms each remove one of the itinerant electrons to leave 40 electrons in the jellium shell. [7] [8]
It is particularly easy and reliable to study atomic clusters of inert gas atoms by computer simulation because interaction between two atoms can be approximated very well by the Lennard-Jones potential. Other methods are readily available and it has been established that the magic numbers are 13, 19, 23, 26, 29, 32, 34, 43, 46, 49, 55, etc. [9]
Superatom complexes are a special group of superatoms that incorporate a metal core which is stabilized by organic ligands. In thiolate-protected gold cluster complexes a simple electron counting rule can be used to determine the total number of electrons (ne) which correspond to a magic number via,
where N is the number of metal atoms (A) in the core, v is the atomic valence, M is the number of electron withdrawing ligands, and z is the overall charge on the complex. [19] For example the Au102(p-MBA)44 has 58 electrons and corresponds to a closed shell magic number. [20]
The halogens are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and tennessine (Ts), though some authors would exclude tennessine as its chemistry is unknown and is theoretically expected to be more like that of gallium. In the modern IUPAC nomenclature, this group is known as group 17.
In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to other atoms were fully ionic. It describes the degree of oxidation of an atom in a chemical compound. Conceptually, the oxidation state may be positive, negative or zero. While fully ionic bonds are not found in nature, many bonds exhibit strong ionicity, making oxidation state a useful predictor of charge.
In quantum mechanics, an excited state of a system is any quantum state of the system that has a higher energy than the ground state. Excitation refers to an increase in energy level above a chosen starting point, usually the ground state, but sometimes an already excited state. The temperature of a group of particles is indicative of the level of excitation.
In chemistry, catenation is the bonding of atoms of the same element into a series, called a chain. A chain or a ring shape may be open if its ends are not bonded to each other, or closed if they are bonded in a ring. The words to catenate and catenation reflect the Latin root catena, "chain".
Photosensitizers are light absorbers that alter the course of a photochemical reaction. They usually are catalysts. They can function by many mechanisms, sometimes they donate an electron to the substrate, sometimes they abstract a hydrogen atom from the substrate. At the end of this process, the photosensitizer returns to its ground state, where it remains chemically intact, poised to absorb more light. One branch of chemistry which frequently utilizes photosensitizers is polymer chemistry, using photosensitizers in reactions such as photopolymerization, photocrosslinking, and photodegradation. Photosensitizers are also used to generate prolonged excited electronic states in organic molecules with uses in photocatalysis, photon upconversion and photodynamic therapy. Generally, photosensitizers absorb electromagnetic radiation consisting of infrared radiation, visible light radiation, and ultraviolet radiation and transfer absorbed energy into neighboring molecules. This absorption of light is made possible by photosensitizers' large de-localized π-systems, which lowers the energy of HOMO and LUMO orbitals to promote photoexcitation. While many photosensitizers are organic or organometallic compounds, there are also examples of using semiconductor quantum dots as photosensitizers.
An electride is an ionic compound in which an electron serves the role of the anion. Solutions of alkali metals in ammonia are electride salts. In the case of sodium, these blue solutions consist of [Na(NH3)6]+ and solvated electrons:
Metal nitrosyl complexes are complexes that contain nitric oxide, NO, bonded to a transition metal. Many kinds of nitrosyl complexes are known, which vary both in structure and coligand.
In chemistry, a Zintl phase is a product of a reaction between a group 1 or group 2 and main group metal or metalloid. It is characterized by intermediate metallic/ionic bonding. Zintl phases are a subgroup of brittle, high-melting intermetallic compounds that are diamagnetic or exhibit temperature-independent paramagnetism and are poor conductors or semiconductors.
Lithium superoxide is an unstable inorganic salt with formula LiO2. A radical compound, it can be produced at low temperature in matrix isolation experiments, or in certain nonpolar, non-protic solvents. Lithium superoxide is also a transient species during the reduction of oxygen in a lithium–air galvanic cell, and serves as a main constraint on possible solvents for such a battery. For this reason, it has been investigated thoroughly using a variety of methods, both theoretical and spectroscopic.
In chemistry, a (redox) non-innocent ligand is a ligand in a metal complex where the oxidation state is not clear. Typically, complexes containing non-innocent ligands are redox active at mild potentials. The concept assumes that redox reactions in metal complexes are either metal or ligand localized, which is a simplification, albeit a useful one.
Transition metal dinitrogen complexes are coordination compounds that contain transition metals as ion centers the dinitrogen molecules (N2) as ligands.
In enzymology, carbon monoxide dehydrogenase (CODH) (EC 1.2.7.4) is an enzyme that catalyzes the chemical reaction
A stannide can refer to an intermetallic compound containing tin combined with one or more other metals; an anion consisting solely of tin atoms or a compound containing such an anion, or, in the field of organometallic chemistry an ionic compound containing an organotin anion
John Dudley Corbett was an American chemist who specialized in inorganic solid-state chemistry. At Iowa State and Ames Lab, Corbett lead a research group that focused on the synthesis and characterization of two broad classes of materials, notably Zintl phases and condensed transition metal halide clusters. Both classes of materials are important for their uses, for instance thermoelectrics, and for the theoretical advances they made possible by working to understand their complex bonding and electronic properties.
Nanoclusters are atomically precise, crystalline materials most often existing on the 0-2 nanometer scale. They are often considered kinetically stable intermediates that form during the synthesis of comparatively larger materials such as semiconductor and metallic nanocrystals. The majority of research conducted to study nanoclusters has focused on characterizing their crystal structures and understanding their role in the nucleation and growth mechanisms of larger materials. These nanoclusters can be composed either of a single or of multiple elements, and exhibit interesting electronic, optical, and chemical properties compared to their larger counterparts.
In chemistry, a chalcogen bond (ChB) is an attractive interaction in the family of σ-hole interactions, along with halogen bonds. Electrostatic, charge-transfer (CT) and dispersion terms have been identified as contributing to this type of interaction. In terms of CT contribution, this family of attractive interactions has been modeled as an electron donor ) interacting with the σ* orbital of a C-X bond of the bond donor. In terms of electrostatic interactions, the molecular electrostatic potential (MEP) maps is often invoked to visualize the electron density of the donor and an electrophilic region on the acceptor, where the potential is depleted, referred to as a σ-hole. ChBs, much like hydrogen and halogen bonds, have been invoked in various non-covalent interactions, such as protein folding, crystal engineering, self-assembly, catalysis, transport, sensing, templation, and drug design.
Susan M. Kauzlarich is an American chemist and is presently a distinguished professor of chemistry at the University of California, Davis. At UC Davis, Kauzlarich leads a research group focused on the synthesis and characterization of Zintl phases and nanoclusters with applications in the fields of thermoelectric materials, magnetic resonance imaging, energy storage, opto-electronics, and drug delivery. Kauzlarich has published over 250 peer-reviewed publications and has been awarded several patents. In 2009, Kauzlarich received the annual Presidential Award for Excellence in Science, Mathematics and Engineering Mentoring, which is administered by the National Science Foundation to acknowledge faculty members who raise the membership of minorities, women and disabled students in the science and engineering fields. In January 2022 she became Deputy Editor for the scientific journal, Science Advances. She gave the Edward Herbert Boomer Memorial Lecture of the University of Alberta in 2023.
Metal cluster compounds are a molecular ion or neutral compound composed of three or more metals and featuring significant metal-metal interactions.
Alkaline earth octacarbonyl complexes are a class of neutral compounds that have the general formula M(CO)8 where M is a heavy Group 2 element (Ca, Sr, or Ba). The metal center has a formal oxidation state of 0 and the complex has a high level of symmetry belonging to the cubic Oh point group. These complexes are isolable in a low-temperature neon matrix, but are not frequently used in applications due to their instability in air and water. The bonding within these complexes is controversial with some arguing the bonding resembles a model similar to bonding in transition metal carbonyl complexes which abide by the 18-electron rule, and others arguing the molecule more accurately contains ionic bonds between the alkaline earth metal center and the carbonyl ligands. Complexes of Be(CO)8 and Mg(CO)8 are not synthetically possible due to inaccessible (n-1)d orbitals. Beryllium has been found to form a dinuclear homoleptic carbonyl and magnesium a mononuclear heteroleptic carbonyl, both with only two carbonyl ligands instead of eight to each metal atom.
Alexander I. Boldyrev was a Russian-American computational chemist and R. Gaurth Hansen Professor at Utah State University. Professor Boldyrev is known for his pioneering works on superhalogens, superalkalis, tetracoordinated planar carbon, inorganic double helix, boron and aluminum clusters, and chemical bonding theory, especially aromaticity/antiaromaticity in all-metal structures, and development of the Adaptive Natural Density Partitioning (AdNDP) method.