Activation of CO2 by Zr atom. Matrix-isolation FTIR spectroscopy and density functional studies

Combined experimental and theoretical studies have been performed for exami ning the interaction between Zr atom and CO2. Matrix-isolation FTIR spectra reveal that OZrCO is the main reaction product of laser-ablated Zr with CO 2, identified by IR bands at 1837.8 and 878.9 cm(-1), correlating to the C- O and Zr-O stretching modes, respectively. Density functional calculations at the B3LYP level have been used to characterize the formation channel of the insertion product OZrCO. We have found that interaction of ground state Zr atom (4d(2)5s(2)) with CO2 On the triplet energy surface leads eventual ly to the insertion product OZrCO and the process is barrierless, indicatin g that activation of CO2 by Zr atom requires no energy input. The theoretic al results are consistent with the experimental observations. (C) 2000 Else vier Science B.V. All rights reserved.