Rl. Bell et Tn. Truong, PRIMARY AND SOLVENT KINETIC ISOTOPE EFFECTS IN THE WATER-ASSISTED TAUTOMERIZATION OF FORMAMIDINE - AN AB-INITIO DIRECT DYNAMICS STUDY, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 101(42), 1997, pp. 7802-7808
We present an ab initio direct dynamics study of the primary and solve
nt kinetic isotopes effects (KIEs) for the water-assisted tautomerizat
ion in the formamidine-water complex. These calculations are based on
a variational transition state theory plus multidimensional semiclassi
cal tunneling corrections with potential energy information calculated
at the MP2 level of theory using the 6-31G(d,p) basis set. We found t
har both the primary and solvent KIEs are large at low temperatures an
d are due not only to tunneling but also to quantum effects in vibrati
onal motions. The primary KIEs were larger than the solvent KIEs. This
results from differences due to the effect of deuteration on vibratio
nal modes. Bending modes show significant inverse KIEs, while those of
the reactive OH and NH vibrations show both inverse and normal effect
s. Such effects can be explained by examining changes in the zero-poin
t energies of these modes. The adherence of the HH/HD/DD rates to the
rule of the geometric mean is also examined.