1. Specific Optical Rotation Values Measured and Calculated at the Sodium D-Line (589 nm), [α] _D for the Molecules Under Study.

(R)-neopentyl-1d-Cl			(R)-3–1d 1-exocamphor			(S)-1-phenylethane-1-d1
Exp.	Calc.		Exp.	Calc.		Exp.	Calc.
	eq	Vibr.		eq	Vibr.		eq	Vibr.
–0.25	0.00	–0.07	(+)	+43.6	+46.4	+0.81	–0.05	+3.35

(R)-neopentyl-1d-Br			(R)-camphor			(S)-1-phenylethane-1,2,2,2-d4
Exp.	Calc.		Exp.	Calc.		Exp.	Calc.
	eq	Vibr.		eq	Vibr.		eq	Vibr.
–0.124	0.00	–0.15	+44.1	+43.6	+43.6	+0.79	–0.05	+3.30
			+59

			(S)-camphor
			Exp.
			–43

^aAll [α]­D are measured at 25 °C, except for phenylethanes, where they were measured at 20 °C. Experimental values are compared with equilibrium simulated values (eq.) and with the vibrational corrected one (Vibr.) , Vibrational corrected OR values were computed accounting for thermal effect (298 K) and the terms related to the poorly described low-energy vibrations were removed. Data taken from:

^bStephenson et al.;

^cAnderson et al.;

^dSigma-Aldrich catalogue;

^eRosini.;

^fElsenbaumer and Mosher;

^gExpected sign, numerical value not reported in the literature.

^hNumerical value different from zero due to slightly asymmetric optimized geometry.