Chemistry Research

Faculty, graduate students, and undergraduates are actively engaged in chemical research.  Basic research is done in all the general areas of chemistry: analytical chemistry, biochemistry, inorganic chemistry, organic chemistry, and physical chemistry including  both experimental and computational research areas.  The research activity is supported by the major instrument centers in the department: Magnetic Resonance Center, Mass Spectrometry Center, Center for Laser Spectroscopy, the X-ray Crystallography Center, as well as High Performance Computing resources (ARCC HPC cluster) provided by the University. You can read about the faculty research areas by following the links below.  In addition, synopses of selected graduate and undergraduate research projects are highlighted.

[Pt@Sn₁₇]⁴⁻: An Exception from Group 14 Endohedral Clusters

Graduate Student: Chad Studvick

Mentor: Dr. Ivan Popov

Group 14 endohedral clusters containing a metal center inside usually possess a single cage topological structure. A recently reported [Pt@Sn₁₇]⁴⁻ is found to exhibit an unexpected single-metal-filled double-cage framework, representing the largest group 14 intermetalloid cluster encapsulating a single transition metal atom. DFT calculations show that the capsule-like architecture of [Sn₁₇]⁴⁻, similar to that found in the previously reported [Pt₂@Sn₁₇]⁴⁻, is unstable if filled with a single Pt atom and collapses to the title cluster upon geometry optimization. Deviation of the central Sn atom occurs due to the vibronic coupling as a consequence of pseudo-Jahn-Teller distortion leading to the bent C_s-symmetrical structure, in contrast to the more symmetrical D_2d cage previously reported in [Ni₂@Sn₁₇]⁴⁻.

This research was published in Chemistry - A European Journal receiving the highest recognition from the reviewers and was selected as a VIP paper by the journal. In addition, it was chosen to be featured on the journal's inside cover.

Divergent Stabilities of Tetravalent Cerium, Uranium, and Neptunium Imidophosphorane Complexes

 Graduate student: Chad Studvick

Mentor:  Dr. Ivan A. Popov

DFT studies on the experimentally synthesized imidophosphorane complexes of Ce, U, and Np show that the cathodically shifted M^4+/3+ redox potentials afforded by the strongly donating NPC ligands (NPC = [N=P^tBu(pyrr)₂]⁻; pyrr = pyrrolidinyl)) can be rationalized by their relative LUMO energy values, which can therefore be instrumental in guiding the synthesis of similar f-element complexes. The metal f-dominant LUMO of the U⁴⁺ species (+0.02 eV) resides appreciably higher in energy, i.e., by +1.10 eV and +0.56 eV from that of Ce⁴⁺ and Np⁴⁺ complexes. This indicates the following order in the capacity of these species to be reduced: Ce⁴⁺>Np⁴⁺>U⁴⁺, making trivalent [U³⁺(NPC)₄]⁻ complexes inaccessible.

The article describing collaborative work of Prof. Popov and Prof. La-Pierre (Georgia Tech) groups is published in Angewandte Chemie International Edition.