Alexander I. Boldyrev
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
Our group pursues the development of chemical bonding models for sub-nanoparticles that could have a significant impact on rational design of nanocatalysts, nanomaterials with tailored properties, nano-scale electronic devices, etc. We have collaboration with Prof. Lai-Sheng Wang and co-workers (PNNL and WSU), which is very successful due to the fact that we strengthen our projects by combining complementary theoretical and experimental results.
Working on this idea we made interesting discoveries:
We reported experimental and theoretical evidence of aromaticity and antiaromaticity in all-metal systems, thus, showing that characteristics believed to apply only to organic compounds can be extended to metallic compounds such as Al42- and Al44- in Li3Al4- anion.

Picture 1. Geometrical structure and seven valence molecular orbitals of all-metal aromatic Al42-.
Observation of All-Metal Aromatic Molecules. X. Li, A.E. Kuznetsov, H.-F. Zhang, A.I. Boldyrev, L. S. Wang. Science, 291, 859- 861 (2001).
All-Metal Antiaromatic Molecule: Rectangular Al44- in the Li3Al4- Anion. A.E. Kuznetsov, K.A. Birch, A.I. Boldyrev, X. Li, H.-J. Zhai, L. S. Wang Science, 300, 622 (2003).

We elucidated the striking feature of chemical bonding in transition-metal systems, that is the possibility of the multi-fold nature of aromaticity, antiaromaticity and conflicting aromaticity.
Ta3O3- in 1A1' D3h state was shown to be the first example of δ-aromatic compound and Hf3 in 1A1' D3h state to be the first example of triply (σ, π, δ)-aromatic system.
Picture 2. Geometrical structure and δ-HOMO-1 of Ta3O3- anion.
Aromaticity and Antiaromaticity in Transition-Metal Systems. D. Yu. Zubarev, B. B. Averkiev, H.-J. Zhai, L. S. Wang, A. I. Boldyrev Phys. Chem. Chem. Phys. 2008, 10, 257-267 (perspective article, cover page)
δ-Aromaticity in [Ta3O3]-. H.-J. Zhai, B. B. Averkiev, D. Yu. Zubarev, L. S. Wang, A. I. Boldyrev Angew. Chem. Int. Ed. 2007, 46, 4277-4280
We performed a comprehensive analysis of chemical bonding in pure boron clusters. It's now established in joint experimental and theoretical studies that pure boron clusters are planar or quasi-planar at least up to twenty atoms. Moreover, we showed the analogy between aromatic hydrocarbon species and pure boron clusters.

A Photoelectron Spectroscopic and Theoretical Study of B16- and B162-: An All-Boron Naphthalene A. P. Sergeeva, D. Yu. Zubarev, H.-J. Zhai, A. I. Boldyrev, L. S. Wang J. Am. Chem. Soc. 2008, 130, 7244-7246 (communication)
Comprehensive Analysis of Chemical Bonding in Boron Clusters. D. Yu. Zubarev, A. I. Boldyrev J. Comput. Chem. 2007, 28, 251-268 (cover page, issues 2-16)
All-Boron Aromatic Clusters as Potential New Inorganic Ligands and Building Blocks in Chemistry. A. N. Alexandrova, A. I. Boldyrev, H.-J. Zhai, L. S. Wang Coord. Chem. Rev, 2006, 250, 2811-2866 (review)
We developed novel efficient methods designed for searching of global minimum-energy chemical system, namely: Gradient Embedded Genetic Algorithm and approaches utilizing Simulated Annealing and Particle Swarm Optimization.

Search for the Lin0/+1/-1 (n=5-7) Lowest-Energy Structures Using the ab initio Gradient Embedded Genetic Algorithm (GEGA). A. N. Alexandrova, A. I. Boldyrev. J. Chem. Theory and Comput. 2005, 1, 566-580
Global Minimum Structure Searchers via Particle Swarm Optimization. S. T. Call, D. Yu. Zubarev, A. I. Boldyrev J. Comput. Chem. 2007, 28, 1177-1186
Currently there is no simple chemical bonding model allowing us to use the "paper and pencil" approach for predicting global minima and low-lying isomers of homoatomic and heteroatomic clusters. In order to facilitate this process we recently developed a new theoretical tool for analysis of wave functions – Adaptive Natural Density Partitioning analysis (AdNDP).
Developing paradigms of chemical bonding: adaptive natural density partitioning D. Yu. Zubarev, A. I. Boldyrev Phys. Chem. Chem. Phys. 2008, 10, 5207-5217
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