Reduced-dimensional quantum approach to tunneling splittings using saddle-point normal coordinates.
We describe multidimensional extensions to a one-dimensional approach to tunneling splittings using a relaxed potential in the imaginary-frequency normal mode of the relevant saddle point (J. Chem. Phys. 2008 , 129 , 121103). Tests of these extensions are given for H(3)O(+) and NH(3) where full dimensional tunneling splittings are available and for the vinyl radical using a new full-dimensional potential energy surface.
Kamarchik
Eugene
E
Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.
Wang
Yimin
Y
Bowman
Joel
J
D000641:Ammonia / Q000737:chemistry*; D004735:Energy Transfer; D005609:Free Radicals / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry*; D008956:Models, Chemical; D011789:Quantum Theory; D014753:Vinyl Compounds / Q000737:chemistry*
D005609:Free Radicals; D014753:Vinyl Compounds; D000641:Ammonia; D006859:Hydrogen