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Accurate quantum mechanical calculations on deuterated vinylidene isomerization
Jia Luo1, Jianwei Cao1, Hao Liu1
1Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Abstract:
We present accurate quantum dynamics calculations on vinylidene-d2 (fully deuterated vinylidene) isomerization. This is achieved by large-scale parallel computations with an efficient theoretical scheme developed by us in which basis functions are customized for the deuterium migration process. Mode-specific permutation tunneling splittings of vinylidene-d2 states are reported here for the first time, and evident isotope effects are revealed. The A1 ', B2 ', A1 ″, and B2 ″ symmetric vinylidene-d2 states are calculated, and the peaks recently observed in the cryo-SEVI spectra are analyzed, with very good agreement between theory and experiment achieved for the energy levels. In addition, a few vinylidene-d2 states beyond the experimental energy region are reported. Our studies are helpful for acquiring a better understanding of isotope effects in the double-hydrogen migration processes.
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