Alexander I. BoldyrevAlexander I. Boldyrev

Associate Professor
Physical Chemistry
B. S., 1974, Novosibirsk University, USSR
PhD., 1978, Institute of New Chemical Problems, USSR
Academy of Sciences, Chernogolovka, Moscow, USSR
Dr. Sci., 1984, Institute of Chemical Physics, USSR
Academy of Sciences, Moscow, USSR
435-797-1630 boldyrev@cc.usu.edu
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If you like chemistry and computers, if you like to design and explore new molecules, new types of chemical bonds, new species with peculiar structures, I urge you to consider joining our group. In our laboratory, we are investigating hyperstoichiometric and nonstoichiometric molecules and clusters, superhalogens and superalkalies, new diatomic molecules, high-spin molecules, floppy molecules, quantum molecular structures, and much more using modern ab initio quantum chemistry. We also plan to have research projects on the computational design of new material.

Aromaticity in metal systems and other chemical species. Aromaticity is a concept invented to account for the unusual stability for an important class of organic molecules, the aromatic compounds. We have recently reported experimental and theoretical evidence of aromaticity in an all-metal system, the Al42- dianion in a series of bimetallic and ionic clusters MAl4- (M=Li, Na, or Cu). The Al42- dianion, both as an isolated species and in the bimetallic molecules (MAl4- ) was found to be square-planar and possess £m- and £k- aromaticity. We have found that the Hg46- unit in Na2Hg3 amalgam is isoelectronic with the Al42- dianion, , suggesting that the former is aromatic as well, thus explaining its unique stability and structure. The current finding of aromaticity in the Hg46- establishes a solid bridge between our gas-phase studies of aromatic clusters and bulk materials containing such species. We continue to search for aromaticity in alkali metal, alkaline earth, boron and other clusters. This work is a joint project with Prof. L.-S. Wang with co-workks (PNNL and WSU).

Hyperstoichiometric and nonstoichiometric molecules and clusters. The octet rule dictates that atoms of the first and second rows are most stable when they are surrounded by eight valence electrons. Based on this rule, one can predict the maximum stoichiometry of hydrides to be: CH4, NH3, H2O and HF. However, when electropositive ligands such as alkali metal atoms, alkaline earth atoms, aluminum, or transition metals are present, thermodynamically stable hyperstoichiometric molecules such as Li6O, Mg2O, Mg3C, Al4O with the number of ligands larger than the octet rule dictates have been predicted computationally and some of them have been recently experimentally observed. We are working on development of new chemical bonding models capable to explain bonding in these new species.

Tetracoordinated planar carbon. In 1874 independently J. H. vanít Hoff and J. A. LeBel recognized that the tetracoordinated tetravalent carbon atom prefers a tetrahedral arrangement of its substituents. This contribution marks a milestone in understanding the structure of carbon compounds. We were able not only to predict computationally pentaatomic molecules with tetracoordinated planar carbon, but also helped to prove the planarity of the first gas-phase made of two pentaatomic tetracoordinate planar carbon molecules, CAl3Si and CAl3Ge which were investigated by a combination of ab initio calculations (by us) and anion photoelectron spectroscopy by (L.-S. Wang with co-workers, PNNL and WSU).

Superhalogens. Halogen atoms possess the highest EAs (3.0-3.6 eV) among all the atoms, however, molecules may exceed the 3.6 eV limit due to collective effects. In 1981 we proposed a simple formula for one class of superhalogens, MXk+1, where M is a main group or transition metal atom, X is a halogen atom, and k is the maximal formal valence of the atom M. Molecules with high electron affinities (EAs) play a very important role in chemistry. For example, in 1962, Bartlett synthesized the first chemically bound xenon in Xe+[PtF6]. We plan to work in close collaborations with L.-S. Wang in further search for superhalogens with record high EDE, which will be exceptionally strong oxidizers.

Selected Publications

Averkiev, B.B.; Boldyrev, A.I.; Li, X.; Wang, L.S., “Planar Nitrogen-Doped Aluminum Clusters AlxN- (x=3-5,” J. Chem. Phys. 2006, 125, 124305-1-12.

Alexandrova, A.N.; Boldyrev, A.I; Zhai, H.J.; Wang, L.S., “All-Boron Aromatic Clusters as Potential New Inorganic Ligands and Building Blocks in Chemistry,” Coord. Chem.Rev.  2006 (review), 250, 2811-2866.

Alexandrova, A.N.; Koyle, E.; Boldyrev, A.I.,  “Theoretical Study of Hydrogenation of the Doubly Aromatic B7- Cluster,” J. Mol. Model. 2006, 12, 569-576.

Zubarev, D.Y.; Li, J.; Wang, L.S.; Boldyrev, A.I., “Theoretical Probing of Deltahedral closo-AuroBoranes BxAux2- (x=5-12),” Inorg. Chem. 2006 (communication), 45, 5269-5271.

Cui, L.F.; Huang,X.; Wang,L.M.; Zubarev,D.Y.; Boldyrev,A.I.; Li,J.; Wang, L.S., “Sn122-: Stannasherene,” J. Am. Chem. Soc. 2006 (communication), 128, 8390-8391.