ClPO






 








 









Chlorine


Nuclear Quadrupole Coupling Constants

in Phosphenous Chloride

 








 








 








Chlorine nqcc's in phosphenous chloride, as well as ro, rs, and rdel(I/P) structures, have been determined by Brupbacher-Gatehouse and Brupbacher [1].  Calculation of the nqcc tensors was made here on these structures, and on an ab initio (CBS+CV+SR) estimate of the equilibrium structure by Puzzarini [2].

 








Calculated nqcc's are compared with the experimental results in Tables 1 - 4.  Structure parameters are given in Table 5.

 








In Tables 1 - 4, 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 plane.  Ø (degrees) is the angle between its subscripted parameters.  ETA = (Xxx - Xyy)/Xzz.

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.

 








 








   







Table 1.  35Cl nqcc's in ClPO (MHz).  Calculation was made on the ro and rs structures [1].
   









Calc. / ro
Calc. / rs
Expt. [1]
   







Xaa - 28.93 - 28.85 - 28.91910(46)

Xbb
22.88
22.84
21.55643(61)

Xcc
  6.05
  6.01
  7.36267(79)

|Xab|
16.85
16.88
15.97(62)

 







RMS
1.08 (5.6 %) 1.08 (5.6 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
27.88
27.87



Xyy
  6.05
  6.01



Xzz - 33.93 - 33.88



ETA - 0.644 - 0.645



Øz,a
16.52
16.57



Øa,PCl
17.92
17.92



Øz,PCl
  1.40
  1.34



 








 








 







 
   







Table 2.  37Cl nqcc's in ClPO (MHz).  Calculation was made on the ro and rs structures [1].
   









Calc. / ro
Calc. / rs
Expt. [1]
   







Xaa - 22.89 - 22.83 - 22.88350(97)

Xbb
18.13
18.10
17.08399(80)

Xcc
  4.76
  4.74
  5.79951(128)

|Xab|
13.14
13.16
11.68(171)

 







RMS
0.85 (5.6 %) 0.85 (5.5 %)



RSD
0.44 (1.1 %)
0.44 (1.1 %)



 








 








 








   







Table 3.  35Cl nqcc's in ClP18O (MHz).  Calculation was made on the ro and rs structures [1].
   









Calc. / ro
Calc. / rs
Expt. [1]
   







Xaa - 28.23 - 28.16 - 28.2310(55)

Xbb
22.19
22.14
20.8532(228)

Xcc
  6.05
  6.01
  7.3778(227)

|Xab|
17.88
17.90



 







RMS
1.09 (5.8 %) 1.08 (5.8 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 








 








 








   







Table 4.  35Cl nqcc's in ClPO (MHz).  Calculation was made on the  rdel(I/P) [1] and estimated re [2] structures.
   









Calc / rdel(I/P)
Calc / est. re
 Expt. [1]
   







Xaa - 28.85 - 28.59 - 28.91910(46)

Xbb
22.85
22.72
21.55643(61)

Xcc
  6.01
  5.87
  7.36267(79)

|Xab|
16.86
16.93
15.97(62)

 







RMS
1.08 (5.6 %) 1.11 (5.8 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 








 








 



Table 5.  ClPO.  Molecular structure parameters (Å and degrees).
 




   ro [1]    rs [1]  rdel(I/P) [1]  est. re [2]





ClP 2.0586(44) 2.0576(1) 2.0576(8) 2.0527(20)
PO 1.4620(105) 1.4609(5) 1.4604(28) 1.4581(11)
ClPO 110.04(43) 109.98(3) 110.00(17) 109.85(8)


 








 








[1] B.Brupbacher-Gatehouse and T.Brupbacher, J.Chem.Phys. 111,6300(1999).

[2] C.Puzzarini, J.Mol.Struct. 780-781,238(2006).

 








"The Diode-Laser Spectrum of Phosphoryl Chloride" I.S.Bell, P.A.Hamiltom, and P.B.Davies, J.Mol.Spectrosc. 200,287(2000)  rs(ClP) = 2.0603(2) Å, rs(PO) = 1.4614(34) Å, rs(ClPO) = 109.89(13)o

 








ClPO2 PCl3 OPCl3 SPCl3

ClNO H2C=PCl





 








 








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Last Modified 10 May 2006