Sequential capture of o(3p) and hcn by helium nanodroplets: infrared spectroscopy of the van der waals complex supplemented by ab initio computations of the potential energy surface and bound states
Franke, Peter R.
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https://hdl.handle.net/2142/107591
Description
Title
Sequential capture of o(3p) and hcn by helium nanodroplets: infrared spectroscopy of the van der waals complex supplemented by ab initio computations of the potential energy surface and bound states
Author(s)
Franke, Peter R.
Contributor(s)
Douberly, Gary E.
Issue Date
2020-06-24
Keyword(s)
Comparing theory and experiment
Abstract
Catalytic thermal cracking of O$_{2}$ is employed to dope helium droplets with O($^{3}$P) atoms. Sequential capture of O($^{3}$P) and HCN leads to the production of a hydrogen-bound O-HCN complex in a $^{3}$$\Sigma$ electronic state, as determined via comparisons of experimental and theoretical rovibrational Stark spectroscopy. Ab initio computations of the three lowest lying intermolecular potential energy surfaces reveal two isomers, the hydrogen-bound ($^{3}$$\Sigma$) O-HCN complex and a nitrogen-bound ($^{3}$$\Pi$) HCN-O complex, lying 300 cm$^{-1}$ higher in energy. The non-relativistic HCN-O to O-HCN interconversion barrier is predicted to be only about 40 \wn. Moreover, the barrier is reduced upon explicit consideration of spin-orbit coupling. Consistent with the prediction of a relatively small interconversion barrier, there is no experimental evidence for the production of the nitrogen-bound species upon sequential capture of O($^{3}$P) and HCN. Rigorous atom-molecule bound-state computations are also performed, considering the couplings of various angular momenta, providing support for the lack of existence of HCN-O.
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