. Author manuscript; available in PMC: 2011 May 11.

Published in final edited form as: Biochemistry. 2010 May 11;49(18):3868–3878. doi: 10.1021/bi901458x

Table 1.

Comparison of experimental and theoretical isotope effects and geometric and electronic changes in representative models of the reactant and the transition state for the hydrolysis reaction calculated using B3LYP/6-31G**

Isotope Effects			Bond Properties
			Bond Type	Bond Length		Bond order change^a Δ(σ^-σ*)	RS hybrid^b	Carbon cont. (%)^c	TS hybrid^b	Carbon cont. (%)^c
Position	Experimental	Calculated	Bond Type	RS	TS	Bond order change^a Δ(σ^-σ*)	RS hybrid^b	Carbon cont. (%)^c	TS hybrid^b	Carbon cont. (%)^c
Carbonyl carbon	1.045 ± 0.003	1.045	C-OH	-	1.61	-	-	-	sp^4.81	29.5
Carbonyl oxygen	1.040 ± 0.005	1.040	C-O	1.21	1.39	−0.896	sp^1.99	33.9	sp^2.49	36.8
3′-oxygen	1.006 ± 0.003	1.006	C-O3′	1.35	1.43	−0.036	sp^2.56	30.5	sp^3.45	29.0
α- hydrogen	0.959 ± 0.002	0.959	C-H	1.10	1.10	0.075	sp^3.10	64.3	sp^3.95	60.1

Calculated by subtracting the number of electrons occupying the σ* orbital from the number occupying the σ orbital and listed as change between the reactant state (RS) and transition state (TS). For the carbonyl bond in the RS electrons in both σ and π bonds were added.

Hybridization of the carbon atom.

Contribution of the carbon atom to the bond in percent.