Driving Energies of Hydrogen Scrambling Motions in CH5+.
A comprehensive quantum chemistry study with natural bond orbital analysis is performed to reveal the intrinsic properties of the floppy potential energy surface of the smallest methonium ion CH5+. In contrast to the low-energy barriers of Cs(I)-->Cs(II)-->Cs(I) and Cs(I)-->C2v-->Cs(I) that correspond to the H2 rotation and H-flip motions, the remarkably larger intramolecular interaction energies are the driving power to mimic the hydrogen scrambling in CH5+. As for the H2 rotation and H-flip motions, the hyperconjugative and electrostatic interactions compete strongly. They together with other interactions compensate for each other and lead to the floppy potential energy surface.
Tian
Shan Xi
SX
Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026, China. sxtian@ustc.edu.cn
Yang
Jinlong
J