The Dual-Basis Idea
Photochemical Dynamics of Co(CO)3NO:
In collaboration with Karma Sawyer and the experimental spectroscopy group of Charles Harris at Berkeley, the photochemical dynamics of the excited states of Co(CO)3NO were investigated. Their experiment provides time-resolved vibrational spectra, which tracks the changes in the force constant of the nitrosyl bond. Two bent nitrosyl structures were observed in the excited state, and state-to-state dynamics were elucidated. After initial photoexcitation to a high-lying state, fast (sub-ps) conversion to a bent triplet occurs (T2 or T3). Subsequent relaxation to T1—a species with even greater NO bending—occurs with a time constant of 350 ps. Slow conversion to the linear, ground singlet state occurs on a timescale longer than the experiment (>1 ns).
Collaboration with Karma Sawyer and Charles Harris
Owing to its unique σ and π* orbital interactions, the nitrosyl ligand can exist in four distinct configurations when bonded to transition metal centers.
"Direct observation of photoinduced bent nitrosyl excited-state complexes"
K. R. Sawyer, R. P. Steele, E. A. Glascoe, J. F. Cahoon, J. P. Schlegel, M. Head-Gordon, C. B. Harris. J. Phys. Chem. A 112 8505–8514 (2008).