CH2ClHC=CH2						PDF
		Chlorine
	Nuclear Quadrupole Coupling Constants
		in cis-3-Chloropropene
	Calculation of the chlorine nqcc's in c-3-chloropropene was made on a molecular structure derived ab initio, as described below.  These are compared with the experimental nqcc's of Hirota [1] in Table 1.  Structure parameters are given in Z-matrix format in Table 2.  Rotational constants are given in Table 3.
	In Table 1, RMS is the root mean square difference between calculated and experimental diagonal nqcc's (percentage of the average of the magnitudes of the experimental nqcc's).  RSD is the calibration residual standard deviation for the B1LYP/TZV(3df,2p) model for calculation of the chlorine nqcc's.
	Subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  The nqcc y-axis is chosen coincident with the inertia c-axis, these are perpendicular to the molecular symmetry plane.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.
	Table 1. Chlorine nqcc's in c-3-Chloropropene (MHz).     Calc. Expt. [1]     35Cl Xaa - 18.19 - 18.19 Xbb - 16.84 - 17.80 Xcc 35.02 35.99 |Xab| 51.64   RMS 0.79 (3.3 %) RSD 0.49 (1.1 %)   Xxx 34.13 Xyy 35.02 Xzz - 69.16 ETA 0.013 Øz,a 44.62 Øa,CCl 45.17 Øz,CCl   0.54     37Cl Xaa - 15.71 Xbb - 13.42 Xcc 29.12 |Xab| 42.92   RSD 0.44 (1.1 %)
	Molecular Structure
	The molecular structure was optimized at the MP2/6-311+G(d,p) level of theory assuming Cs symmetry.  The optimized CC bond lengths, single and double,  were corrected using equations obtained from linear regression analysis of the data given in Table IX of Ref.[2].  For the CCl bond, the structure was optimized at the MP2/6-311+G(2d,p) level and corrected by linear regression analysis of the data given in Table 4 of Ref.[3].  The CH bond lengths were corrected using r = 1.001 ropt, where ropt is obtained by MP2/6-31G(d,p) optimization [4].  Interatomic angles used in the calculation are those given by MP2/6-311+G(d,p) optimization.
	Table 2.  Z-Matrix (Å and degrees).   H C 1 R1 C 2 R2 1 A3 C 2 R3 1 A4 3 180. H 4 R4 2 A5 3 180. H 4 R5 2 A6 3     0. Cl 3 R6 2 A7 6     0. H 3 R7 2 A8 6 -D H 3 R7 2 A8 6 D   R1 = 1.086 A3 = 113.45 R2 = 1.494 A4 = 119.56 R3 = 1.330 A5 = 120.26 R4 = 1.081 A6 = 121.68 R5 = 1.080 A7 = 114.49 R6 = 1.777 A8 = 109.90 R7 = 1.090 D = 120.60
	Table 3.  Rotational Constants (MHz).  35Cl species.   Calc. ropt      Expt. [1] A 13 721.7 13 580.58(44) B   3 827.0   3 816.71(38) C   3 049.1   3 035.15(38)
	[1] E.Hirota, J.Mol.Spectrosc. 35,9(1970).
	[2] J.Demaison, J.Cosléou, R.Bocquet, and A.G.Lesarri, J.Mol.Spectrosc. 167,400(1994).
	[3] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996).
	[4] J.Demaison and G.Wlodarczak, Structural Chem. 5,57(1994).
	H2C=CHCl			H2C=CFCl			c-ClHC=CHCl
	c-FHC=CHCl			t-FHC=CHCl			H2C=CCl2
	H2C=CClCN			F2C=CHCl			F2C=CCl2
	(CH3)2C=CHCl			Cl2C=CHCl			F2C=CFCl
	c-CH3HC=CHCl			t-CH3HC=CHCl			CH3ClC=CH2
	c-CH3FC=CHCl
	Table of Contents
	Molecules/Chlorine
						3ClPropene.html
						Last Modified 22 June 2004