Experimental and ab initio determination of the bending potential of HCP

The emission properties of HCP excited to the A, B, and d electronic states have been studied. Lifetimes and quenching rates have been measured. By spectrally resolving the emission spectrum, the energy of 94 vibrational levels of the ground electronic state have been measured to an accuracy of ≈5 cm−1. These energy levels were fit to experimental accuracy by a rigid bender Hamiltonian thereby determining the bending potential over a range of bending angle from 0 to 100° (0–17 500 cm−1). An ab initio bending potential has been computed for HCP and found to be in excellent agreement with the experimentally fitted one over the range that the experimental data span. This potential predicts that HPC has an energy maximum with respect to the bending coordinate. The bending potential decreases monotonically by about 30 000 cm−1 in going from HPC to HCP.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/69992/2/JCPSA6-82-10-4460-1.pd