HNSO			PDF
	Deuterium and Nitrogen
	Nuclear Quadrupole Coupling Constants
		in Thionylimide
	Deuterium and nitrogen nqcc's have been reported for thionylimide [1-3].  A substitution structure was published by Kirchhoff in 1969 [3], and later modified with respect to the NH bond length by Dal Borgo et al. [4].  An equilibrium structure was derived by Demaison et al. [5].
	Calculation of the nqcc's was made here on the modified molecular structure of Kirchhoff, and on the equilibrium structure of Demaison et al.  These nqcc's are compared with the experimental values in Tables 1-3.  The structure parameters are shown in Table 4.
	In Tables 1 - 3, 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 model for calculation of the nqcc's, B3LYP/6-31G(df,3p) for deuterium and B3PW91/6-311+G(df,pd) for nitrogen.
	Subscripts a,b,c refer to the principal axes of the inertia tensor, subscripts 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 plane of the molecule.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.
	Table 1.  Deuterium nqcc's in DNSO (kHz).  Calculation was made on the re and rs structures.     Calc / re Calc / rs Expt. [1]     Xaa - 117.4 - 111.8 - 114.9(31) Xbb 233.8 222.9 225.4 Xcc - 116.5 - 111.0 - 110.6 |Xab|   14.0   12.7   RMS 6.1 (8.0 %) 2.3 (1.6 %) RSD 1.1 (0.9 %) 1.1 (0.9 %)   Xxx - 117.9 - 112.3 - 115.4 * Xyy - 116.5 - 111.0 - 110.6 Xzz 234.4 223.4 225.9 ETA - 0.006 - 0.006 - 0.021 Øz,a 92.29 92.2 92.1 Øa,ND 91.00 90.8 90.8 Øz,ND   1.28   1.3   1.3
	* Calculated here from the experimental diagonal nqcc's and the calculated off-diagonal |Xab| = 12.7 kHz.
	Table 2.  14N nqcc's in DNSO (MHz).  Calculation was made on the re and rs structures.     Calc / re Calc / rs Expt. [1]     Xaa - 1.294 - 1.309 - 1.4211(19) Xbb - 0.258 - 0.224 - 0.1863 Xcc 1.552 1.533 1.6074 |Xab| 2.112 2.109    RMS 0.090 (8.4 %) 0.080 (7.5 %) RSD 0.030 (1.3 %) 0.030 (1.3 %)   Xxx 1.398 1.411 1.394 * Xyy 1.552 1.533 1.6074 Xzz - 2.950 - 2.944 - 3.001 ETA 0.052 0.041 0.071 Øz,a 38.11 37.8 36.8 Øa,bi 33.03 32.9 32.9 Øz,bi **   5.08   4.8   3.9
	* Calculated here from the experimental diagonal nqcc's and the calculated off-diagonal |Xab| = 2.109 MHz.
	** Angle between the z-principal axis of the nqcc tensor and the bisector ('bi') of the DNS angle.
	Table 3.  14N nqcc's in HNSO (MHz).  Calculation was made on the re and rs structures.     Calc / re Calc / rs Expt. [1]     Xaa - 1.471 - 1.487 - 1.5756(29) Xbb - 0.081 - 0.046 - 0.0254 Xcc 1.552 1.533 1.6010 |Xab| 2.060 2.055   RMS 0.074 (6.9 %) 0.066 (6.2 %) RSD 0.030 (1.3 %) 0.030 (1.3 %)   Xxx 1.398 1.411 1.18(3) Xyy 1.552 1.533 1.604(3) Xzz - 2.950 - 2.944 - 2.78(3) ETA 0.052 0.041 Øz,a 35.68 35.3 33.49(8) Øa,bi 30.60 30.5 Øz,bi *   5.08   4.8   3.0
	* Angle between the z-principal axis of the nqcc tensor and the bisector ('bi') of the DNS angle.
	Table 4.  Molecular structure parameters, re [5] and rs [3,4] (Å and degrees).       re     rs HN 1.020(1) 1.0272 NS 1.510(2) 1.5123 SO 1.448(1) 1.4513 HNS 115.94(39) 114.8 NSO 120.44(10) 120.41
	[1] N.Heineking and M.C.L.Gerry, J.Mol.Spectrosc. 158,62(1993).
	[2] P.Cassoux, A.Serafini, G.Fong, and R.L.Kuczkowski, Inorg.Chem. 17,1204(1978).
	[3] W.H.Kirchhoff, J.Am.Chem.Soc. 91,2437(1969).
	[4] A.DalBorgo, G.DiLonardo, F.Scappini, and A.Trombetti, Chem. Phys.Lett. 63,115(1979).
	[5] J.Demaison, L.Margulès, J.E.Boggs, and H.D.Rudolph, Struct.Chem. 12,1(2001).
	HNCO		ClNCO		HNCSe		HNCS
	Table of Contents
	Molecules/Deuterium
	Molecules/Nitrogen
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						Last Modified 31 Jan 2009