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Molecular quadrupole moments, magnetizability, nuclear magnetic shielding and spin-rotation tensors of CO2, OCS and CS2
Roger D. Amos & Maurice R. Battaglia
a a a

University Chemical Laboratory, Lensfield Road, Cambridge, CB2 1EW, U.K. Available online: 23 Aug 2006

To cite this article: Roger D. Amos & Maurice R. Battaglia (1978): Molecular quadrupole moments, magnetizability, nuclear magnetic shielding and spin-rotation tensors of CO2, OCS and CS2 , Molecular Physics, 36:5, 1517-1527 To link to this article:

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[10] who M. VOL. 2. 0. nuclear quadrupole moments can be found from the nuclear quadrupole coupling constants (e2 Qq) or vice-versa [5].P. the diamagnetic part of the magnetizability and nuclear shielding tensors. 13C chemical shifts and nuclear quadrupole moments.R. 1517-1527 Molecular quadrupole moments. for the quadrupole moments. OCS and CS 2 by ROGER D. Lensfield Road. Cambridge CB2 1EW. experimental or ab initio. Downloaded by [University of California. AMOS and M A U R I C E R. 1. PREVIOUSab initio STUDIES As might be expected the most studied of these three molecules is carbon dioxide. and the interaction between molecules in condensed systems [l]. a full analysis of the magnetizability and nuclear magnetic shielding tensors has been obtained for these molecules. we have been able to determine Xp. gP. The electronic second moments are comparatively easily evaluated by ab inltio techniques and are simply related to the quadrupole moment and to the diamagnetic part of the magnetizability tensor Xd. U. INTRODUCTION The electric moments of molecules provide valuable information about their ground state charge distribution. which is related to the N. Xa. The paramagnetic component a p can be related to the spin-rotation tensor C [4-]. There have been several calculations of the quadrupole moment of CO 2 [6-10]. there is a paucity of reliable data. magnetizability. B A T T A G L I A University Chemical Laboratory. 36. 3]. of non-dipolar molecules [1.MOLECULARPHYSICS. 5 E . The nuclear magnetic shielding tensor g. By combining these calculated properties with experimental data.K. C and ez Qq for these molecules. We have performed ab initio M C S C F calculations of 0.M. nuclear magnetic shielding and spin-rotation tensors of C02. and electric field gradients in CO2. a a and the electric fieldgradients for CO2. Berkeley] at 23:33 14 December 2011 (Received 20 January 1978) Ab initio calculations have been made of molecular quadrupole moments. the most accurate of which is that by England et al. Using literature values of g. OCS and CS2.1978. The total magnetizability X can be determined by combining Xa with the paramagnetic contribution Xp which may be obtained from the rotational g factors [4]. No. The calculated properties are in good agreement with experimental data. Although the dipole moments of most simple molecules are known with great precision [2]. 5. has a diamagnetic component ga which is readily obtained by ab initio calculation. OCS and CS 2. If the field-gradients produced by the non-spherical electronic charge distribution can be calculated. chemical shift.

. These are augmented with a set of d functions (STO-2G) on each atom. some representative properties of CO 2 are shown. In table 2. Second moments. using an accurate Hartree-Fock wavefunction. and the diamagnetic part of the magnetizability though. rCS=l.u. corresponding to the cr and 7r bonds in each molecule. For carbon disulphide Fischer and Kemmey [9] have calculated the quadrupole moment. as with CO2. On the other hand. 12]. r c ~ rc s = 1 . are correlated. 5 • 10 -26 e. The basis sets used consist of the standard Dunning [15] 5s3p set of contracted gaussians on carbon and oxygen. The accuracy of the present calculations should be greater than all previous [6-12] studies. Amos and Maurice R.u. magnetizabilities and quadrupole moments are calculated relative to the centre of mass for each molecule. McLean and Yoshimine [11. The usefulness of this type of wavefunction for the calculation of molecular properties is demonstrated in a recent study of hydrogen fluoride [14]. OCS and CS 2 calculated with the M C S C F wavefunctions are shown in table 1.s. Berkeley] at 23:33 14 December 2011 3. 0 = .48 • 10-26 e. and consist of a relatively small number of configurations obtained by making double excitations from the Hartree-Fock function. No promotions from the core orbitals are included in the wavefunction.4 . CS2. and it is unlikely that the field gradients have been calculated to . and this is true for all components of the C. An indication of the accuracy of the results may be obtained from the variation of the calculated properties with the size of basis set. O and S diamagnetic shielding tensors in CO2. The component of the nuclear magnetic shielding quoted in table 2 shows hardly any variation. calculated using restricted Hartree-Fock wavefunctions instead of MCSCF. are 1. 2. The exponents used for the d functions. PRESENT ab initio RESULTS The wavefunctions used are of the type called ' pair-replacement M C S C F ' [13]. 5 5 8 A .985 debye for OCS (-OCS § and a quadrupole moment.s.0. Downloaded by [University of California. the value quoted for X• a seems to be in error. with the exception of the calculation of the quadrupole moment of CO 2 by England et al. for the equilibrium geometry. using a CI wavefunction. unlike CI calculations.5 for oxygen and 2-1 for sulphur. Battaglia obtained 0 = . calculated a dipole moment of 0.818 • 10-26 e. which have been chosen to minimize the energy. r c ~ OCS. the diamagnetic contributions to the nuclear magnetic shielding tensors have been determined with a high degree of precision. Consequently it seems certain that. OCS and CS 2. with M C S C F wavefunctions. [10]. and a 5s3p contraction of Veillard's [16] basis on sulphur.s.u.1. The results for various properties of CO2.554A. It is apparent from the example in table 2 that this quantity varies significantly. relative to the centre of mass. of . and using a reduced basis set with only 5s3p gaussians on each atom instead of the full 5s3pld basis. The diamagnetic part of the magnetizability of CO 2 has been calculated by Snyder and Basch [7] and Fischer and Kemmey [9]. Only the valence shell molecular orbitals. and type of calculation. it is not necessary to include single excitations tO achieve accurate values of molecular properties [43]. though the value for X• a quoted in [9] seems to be in error.1518 Roger D. No previous ab initio estimates are available for the majority of these properties. The bond lengths used in these calculations are: CO2.8 for carbon. the field gradient at a nucleus (q) is one of the more difficult properties to calculate accurately.

SCF 5s3p (x 2) (z 2) 3'082 26"193 415"34 6"37 M C S C F 5s3p 3"091 26"041 414"89 5"81 Units as in table 1. T h e s e c o n d m o m e n t s ( x 2) a n d ( z 2) s h o w c o m p a r a t i v e l y little v a r i a t i o n w i t h the t y p e of c a l c u l a t i o n .p.m.832"8741 6-607 83"442 77"282 .3"990 -6. for t h e e q u i l i b r i u m g e o m e t r y . second moments in 10 -s~ m s .3"618 4. T h i s i m p l i e s t h a t the c o m p o n e n t s of the d i a m a g n e t i z a b i l i t y e2 (1) and X.57 284"22 439"18 414"67 506"49 --. magnetizabilities in 10 -s9 joule tesla -s .364"03 . are a c c u r a t e to a b o u t 89 per cent.s.510"3498 4"905 46'765 41 "574 .93"09 .u. p a r t i c u l a r l y i n t h e case of ( x 2 ) . Some selected properties of COs showing the variation of the calculated property with size of basis set and type of calculation. b e i n g of larger m a g n i t u d e .u.202'05 -4. This behaviour also a p p l i e s to O C S a n d C S 2 a n d it s e e m s p r o b a b l e t h a t t h e s e c o n d m o m e n t s .Properties of C02. 1519 Ab initio M C S C F properties of COs.994 -- Units : energies in a. c o n s i d e r a b l y g r e a t e r u n c e r t a i n t y associated w i t h the 5E2 ..36 286"69 485 "56 415"09 540"16 1061 "52 1139"90 -4"330 1. h o w e v e r . O C S and C S 2 Table 1.s.307 CSs . OCS and CSs.187"7592 3"077 25"604 21 "574 -43"36 .~ 3"336 x 10 4 C m s) . Berkeley] at 23:33 14 December 2011 Ozz ((rzza)c (axxa)c (~zzd)O (axx a)o (Ozzd)S (axxa)s (q)c (q)o (q)s .~4"35981 x 10-18joule) . reduced field gradients in 103o m -3. or e v e n b e t t e r i n the case of Xz~ d. T h e r e is. b e t t e r t h a n 10 per cent.u. quadrupole moments in 10 -s6 e.u.984 E (x s) (z 2) 3~ZNrN 2 Xzza Xxxd Downloaded by [University of California. (10 -s6 e. has g r e a t e r relative accuracy.1. .634"38 2"10 290"54 533 "41 --1061 "48 1171 "07 .69"14 . (1 a. shieldings in p. except p o s s i b l y for the field g r a d i e n t at the s u l p h u r n u c l e i w h i c h . COs OCS .926 12. Table 2. d = ~za = 82 2m <x2) (2) SCF 5s3pld 3"074 25"697 414"96 5"27 M C S C F 5s3pld 3"077 25'604 414"67 4"99 (ozza)o (q)o will also be d e t e r m i n e d to a b o u t 1 p e r cent.

so the magnitude of the vibrational correction is less certain for this property.(< z2) -. so the vibrational corrections to Xxx d and X=d are likely to be small.57_+ - 0.s. units of the closely related quantity magnetic susceptibility. small changes in (x 2) and (z 2) can have a relatively large effect upon the quadrupole moment.I. The properties of CO2.1520 Roger D.u.E0 (4) t The magnetizability has (S. reasonable estimates of the error bounds for the quadrupole moments are. which are the c. are cubic force constants. Ozz --.u. Downloaded by [University of California. and ~o are i the harmonic frequencies. Since this quantity is the difference of nearly equal nuclear and electronic terms. + 2"10 + 0"9 • 10-26 e. Battaglia quadrupole moment which. The difference in the value of a property at the equilibrium geometry (Pc) and its value in the ground vibrational state (P0) is given by the expression [17] { where qi are the normal coordinates. since the properties observed are for the ground vibrational state.u. 4.Ie l[ ~ Z N r N 2 -.r i ~ r i ~ ] O ) + f ~ m ~ ~ i k~ 0 E~ . indeed even for diatomic molecules the rigorous inclusion of vibrational averaging is rare. e2 e2 (OlL~[k)(k]Lp]O) - 4m (0[ ~ r i 2 8 ~ p . so the evaluation of the derivatives in this expression would require the calculation of the value of the property at a large number of points on the three-dimensional energy surface of the molecule. (z 2) and the nuclear term will fortuitously cancel in the calculation of the quadrupole moment. Berkeley] at 23:33 14 December 2011 CO 2 OCS CS2 -4.g. This is beyond the scope of the present study.s. It is unlikely that small changes in the geometry will have a great effect on (x 2) and (zZ).36_+ 0. 1.<X2))] .) units joule tesla-2 molecule-1. The conversion factor is : 10 x susceptibility in cmz -+ magnetizability in JT ~2. which being essentially core properties are unlikely to have a strong dependence upon small changes in the molecular geometry. for a linear molecule. OCS and CS~ have been calculated at their equilibrium geometries. Amos and Maurice R. This also applies to the components of the diamagnetic nuclear shielding tensors gd.s. k isJ. F r o m the behaviour of the calculated second moments in table 2. is (3) N where Z N is the atomic number of the N t h nucleus and r N is the distance from the N t h nucleus to the origin (usually the centre of mass). THE MAGNETIZABILITYTENSOR The magnetizabilityt tensor of a closed shell molecule is given by the expression. Strictly.s.6 x 10 -26 e.3 x 10 -26 e. the effect of vibrational averaging should be considered. . x~p= x~pd + x~p. For a triatomic molecule there are three normal coordinates. However there is no guarantee that the changes in (x~). and their omission is unlikely to be serious. Much of the older literature data is quoted in cmz molecule -1.

have been used to determine X2 which in t u r n have been c o m b i n e d with our calculated diamagnetic c o m p o n e n t s to facilitate a complete b r e a k d o w n of the magnetizability tensors for these molecules .02 x 10 -39 J T -~. F o r a linear molecule equation (4) simplifies considerably as there are only two i n d e p e n d e n t c o m p o n e n t s of the diamagnetic part. equations (1) and (2). O C S and CS2.364"03 0 309"65 . and only one i n d e p e n d e n t c o m p o n e n t of the paramagnetic t e r m x• = xx p = y I<OILxlh)l E k ..65"40 541.1 4 . while the positive paramagnetic contribution (X p) requires a s u m m a t i o n over all excited states.14-76 .69"14 .568"98 -. Table 3.15 112"39 . For most closed shell molecules the diamagnetic t e r m dominates.59"30 CS~ .73 206"43 . Berkeley] at 23:33 14 December 2011 T h e paramagnetic c o m p o n e n t (XxP) is closely related to the rotational g factor (gA X.z g J T -2.71 + 0.32 -74"63 AXa AXP AX s s s -43"36 . OCS and CS2. CO2 Xa X• d X .309"65 -.27"69 .9"90 .54"38 294. is of course greater as this quantity is the difference of two t e r m s of nearly equal magnitude.P = 4m [~g• I • e2 ~ ZNrN ~} . F r o m this we obtain an experimental diamagnetic anisotropy AXa =293"9 x 10 -39 J T -2.P X~P X i~ X • OCS .93"09 . Calculated (MCSCF) diamagnetic components. [18]. which are k n o w n accurately f r o m molecular b e a m studies of Cederberg et al.69 168"59 -.265. O C S and C S 2 1521 T h e diamagnetic t e r m (X a) depends only on the g r o u n d state wavefunction. A X = .29 -.95 379. 7 6 x t 0 . Rotational g factors for COs.634"38 0 568"98 . the difference is only 6 per cent. . experimental (from g factors) paramagnetic components. 9 x 1 0 . this is shown in table 3.149.Properties of COs.202"05 0 168"59 -43"36 33"46 158.E0 (5) Downloaded by [University of California. For O C S the magnetic anisotropy (AX) is k n o w n accurately f r o m molecular b e a m studies of de L e e u w and D y m a n u s [19] AX= - 15.2 9 J T -2. and is always negative.35"76 -- Units 10 -29 joule tesla -2.89 -. which is very close to our calculated value A X a = 2 9 4 .93"09 . (6) where I is the m o m e n t of inertia and Mp is the p r o t o n mass. T h e relative error in the calculated total anisotropy.453. Magnetizability tensors of CO2.69"14 . b u t the agreement is still good .

It can be seen from table 3 that our calculated values of AX and AXa for CO~ and CS 2 are also in good agreement with experimental data.2. we note that OCS often contains traces of oxygen [25] and that the presence of as little as 0. The diamagnetic contribution to the magnetic anisotropy AXa is proportional to ((z ~ ) . Berkeley] at 23:33 14 December 2011 .288 )k2 and 2-724 A 2 respectively. From these values the experimental diamagnetic anisotropies are CO2 and CS2 AXa = 541 + 2 • 10-29 JT -2. The general trends within this series of molecules. We see from table 1 that f z 2) . are easily explained. and a rigorous explanation of the increase in X• p would require a detailed examination of the transition angular momentum matrix elements for these molecules. However. 30]. MOLECULARQUADRUPOLEMOMENTS For a linear molecule there is only one independent component of the quadrupole moment.5 • 10 -29 JT -2 Downloaded by [University of California.( x 2) ~ ~ ZNrN 2. 1. in terms of the relative energies of low lying unoccupied rr orbitals.(x2)).043 A. O and S atoms to be 1. (x ~) = ( y 2 ) = (z 2) for each atom. Most experimental determinations AXd = 158-2 + 0. and CS2.2 7 + 3 • -2 respectively [22. For a dipolar molecule 0 is dependent upon the choice of origin. To explain the increase in X. Using Hartree-Fock wavefunctions Malli and Froese [26] have calculated (89 2) for isolated C. then simply adding the atomic second moments as appropriate produces values for (x 2) and (z 2) in the molecules which are in error by only a few per cent. to the resulting increase in the bond lengths.2 4 + 2 and A X = .4 • 10-~9 JT -2 [20] from the gas phase Cotton-Mouton effect. a and X:_ from CO s to CS 2 is due almost entirely to the greater size of the sulphur a atom.2 per cent paramagnetic oxygen could explain this discrepancy. in the case of X• a. and. this approach is known to be dubious in some cases [27].) Thus the increase in X. Battaglia Buckingham et al. i. The 10 per cent difference in 2 for OCS is surprisingly large. i.p (and hence AX) it is tempting to interpret equation (5) qualitatively.a[ and the threefold increase in I xl l. Pure liquid and dilute solution Cotton-Mouton effect measurements yield A X = .e. 21].e. The experimental mean magnetizabilities 2 are [24] -34-0 (CO2). -28-5 + 0. have measured AX for CO 2. and also that the atoms are spherical.1 0 . Amos and Maurice R. that is. 5 [20. 23] for CS2. 4 + 0 . 5. -53-8 (OCS) and -70. which is given by equation (3). (This is of course the basis of various semi-empirical schemes [29.1 • 10-29 JT -2 (CS2). N SO that the threefold increase in AXa is also simply explained in terms of the increase in bond lengths and increased number of electrons on going from COs to CS~. Ozz. Considering the level of agreement between calculated and observed AX and AXd we would expect that our calculated (table 3) mean susceptibilities are accurate to about 1-2 per cent. However. If the crude assumption is made that the electron density of the molecule is just the sum of the electron densities of the constituent atoms. the twofold increase in IX. .1522 Roger D.

OCS and CSz 1523 are referred to the centre of mass. T h e small differences between the hypothetical spherical atom moments and the true second moments are treated as semi-empirical parameters in some schemes [30]. 5 7 . 3 6 and + 2 . T h e small differences between the M C S C F moments and those obtained from a spherical atom model are shown in table 4. Berkeley] at 23:33 14 December 2011 0=co~< 0=ocs< 0=cs. This illustrates the high degree of accuracy required in (x 2) and (z 2) if good values of 0 are to be obtained.s.(xZ)). . and the anisotropy in the electronic second moments.374 25"604 24"948 21"574 -0"297 0"656 It was mentioned in w4 that (x z) and (z 2) for the molecule can be predicted to within a few per cent from atomic data using a simple additive spherical atom model.Properties of C02. We note that in order to obtain good values for the quadrupole moment the differences ( ( z e ) . It is interesting to note that the differences in the axial moments ( ( z z ) . it would of course predict a zero quadrupole moment for all molecules. this simple model would predict the wrong sign for CS2. though for some experiments a different choice of origin is required [39]. All nuclear and electronic moments quoted here are relative to the centre of mass.905 5.u.(x2) sA) both have to be considered. respectively.(z2) sA) are oppositely signed for CO 2 and CS 2. E ZNrN 2. Comparison of the MCSCF second moments and those obtained from a spherical atom (SA) model (see text). The interpretation of this is not straightforward since these molecules are not formed from initially spherical species as would be the case in an ionically bonded molecule.1 .( z 2 ) sA) and ((xe) . ((z 2 ) . While such a model is useful for the discussion of qualitative trends in the magnetizability. An analysis of the type given in table 4. may be of use in the refinement of such semi-empirical schemes. OCS and CS 2 give . CO2 OCS 4. in units of 10-2o m ~. T h e M C S C F calculations of the quadrupole moments of CO 2. Table 4.054 46"765 46"624 41"574 -0"149 0"141 CS2 6.. From field . derived from accurate calculations on small molecules. However since oxygen and sulphur are in fact negatively charged in all three molecules.077 3.4 .<z2) sA 3. It might be predicted from electronegativity arguments (based on an opposing dipole model for 0) that the quadrupole moments of these molecules become more positiye in the direction Downloaded by [University of California. the nuclear contribution.734 83"442 84"014 77"282 -0"127 -0"572 <xz) (x2>sA (z ~> <z2>sA EZNrN 2 <x2>-(x2) sA <z~) . Because the quadrupole moment is the difference between terms of nearly equal magnitude. 1 0 x 1 0 -26 e.607 6. rather than assuming that only the second moment along the bond direction changes. N this property is difficult to calculate accurately and care is required even to determine the sign of 0 [9].

Amos and Maurice R.Eo 8~rm2 ~ 0 ~ where tiN is the vector from nucleus N to electron i and other symbols have their usual meanings.Lix (9) (10) a 4~ _ tzoe2 • and <o[ ~r-~N lk)<klGlO>+c. The quadrupole moment can be related to other molecular properties. Downloaded by [University of California. from the data discussed in w4. -.1~ . N--~ E k . ) <ol E ..1524 Roger D. + (%pP)N. [40] have determined 0zz=-4. Diamagnetic shieldings do not vary dramatically with chemical environment.3+0.2• -2. XiN~+ZiN2 [0). 9].c. . NUCLEARMAGNETICSHIELDINGTENSORS The discussion of the nuclear magnetic shielding tensors ~ for these molecules parallels that of the magnetizability tensors. This corresponds to a quadrupole moment 0==2..0 . = .5 _+ 1.N=4--m <01X I~oe2 XiN------2 IO). -/~~ 8 fl'm (0[ V riN~ 3~ -ri~r~ ~i tiN 3 10) (8) ' /Loe2 L.s.u. 0 ~ . Battaglia gradient birefringence studies of CO2.u. The quadrupole moment of OCS is known accurately. For CS 2 the quadrupole moment is much less accurately known. there are only three independent non-vanishing components of a N for a closed shell linear molecule. 0=-[e[g•177 4m AX.0 • 10-29 J T -2.c. 7 9 + 0.8 + 0"7 x 10 -26 e. from molecular beam studies [19]. A reasonable estimate of AX for CS2.~ [k)<klL~[O +c.81r kZ:o 2~n *~ r gk-Eo (11) The diamagnetic terms a d have the effect of shielding the nucleus from the magnetic flux while the negative paramagnetic term adds to the flux.28. and considering the difficulties in calculating a moment as small as this our value is in reasonable agreement with the experimental result. is . e. 6..u. Buckingham et al. The calculated M C S C F values for alrd and a• are given in table 1. and literature values.s. the principal uncertainty (neglecting vibrational effects) in the quadrupole moment arises from the error in AX. cannot agree on either the sign or the magnitude of 0. The shielding tensors may be divided into diamagnetic and paramagnetic components [4] (%AN = ( ~ % .01 • 10-26 e. .s. Berkeley] at 23:33 14 December 2011 (7) Mp }el Since g• and I• are known accurately. ~ (aft)N=. both ab initio and experimental [3. (~ . As with X.

f r o m N . in p. F r o m t e m p e r a t u r e and field dependence studies of the spin-lattice relaxation in liquid CS 2 Spiess et al. and we see f r o m table 1 that oa at the sulphur nucleus is closest to that for the isolated atom.155"0 334"9 5"30 + 0"04 .388"1 286"7 485"6 0 CS~ .m. O and S atoms to be 260. Table 5. M .p.m. p .Properties of COs. and r K i is the distance f r o m the K t h nucleus to the shielded nucleus.p.8"4 452"4 . OCS and CS~. R . T h e absolute shielding at the laC nucleus in CO can be determined [31-33] f r o m a combination of experimental and ab initio data to be + 3 . and C • ( T h e value quoted by . and C .5 326"6 284"2 439"2 0 OCS 31 "2 419"3 . [37].m. O C S and CS2 1525 Downloaded by [University of California. Using lsC chemical shift data for COs [33]. m . oi Ao~ Aoa Ao C• (kHz) -489"9 284"2 . relative to some reference molecule whose absolute shielding is known. [36] have calculated A a = 4 2 5 + _ 1 6 p . the anisotropy (aFla--a• d) is least for sulphur and greatest for carbon which has the most distorted chemical e n v i r o n m e n t in these molecules. table 5. C02 60"9 387. CS~ [34] and OCS [35] together with our M C S C F values of ~ H and ~• d we have been able to produce a full analysis of the shielding tensors in these molecules.198"9 383"3 3'16 + 0"03 .50"7 489"9 -. T h i s is to be expected since the major contribution to 6a comes f r o m the core electrons at that nucleus. R .8 290"5 533"4 0 oa ~P - aa o• ct o i~P alp o.691 "2 290"5 .7.1 and 1050.460.p. m . = 3. ~. respectively. calculated A a = 4 3 8 _ _ 4 4 p . p .1 __ 0. of the N t h nucleus.157"8 691 "2 -. Analysis of nuclear magnetic shielding tensors and spin-rotation constants for the carbon nucleus in CO2. Berkeley] at 23:33 14 December 2011 particularly in the case of ~ E~a. M . using the point charge a p p r o x i m a t i o n [29] for a d.5 p.582"2 286"7 -96"6 582"2 -. A m o r e complete analysis of the nuclear magnetic shielding tensors at the carbon nuclei could be m a d e if iaC N . isotropic shifts were measured. 6 ) p.p. Pines et al. Also. studies of solid CS2. T h e more tightly b o u n d the core the less will be the effect of chemical e n v i r o n m e n t on the diamagnetic shielding. Malli and Froese [28] have calculated ~ for the isolated C.m. MpC•177 ~~ Y ZK mgNh2 8rrm K~N rKN' (12) where gN is the nuclear g-factor. obtained using MCSCF values for 6a and experimental isotropic shielding.2 kHz. 395. Also shown in this table is the spin-rotation constant C• which is simply related to e l p. cf.242"9 448"3 2"01 + 0"02 F r o m molecular b e a m studies of O C S de L e e u w and D y m a n u s [19] have measured A a = 372_+ 42 p. 1 ( + 1 .

.. Nuclear Quadrupole Coupling Constants (Academic Press). Note added in p r o o f .E. H. Battaglia Spiess et al. J. = Q . but is radioactive and an unsuitable candidate for experiments. A. the 11C nucleus has a quadrupole moment. has been divided by 27r to facilitate comparison with our results. (b) FLYGARE.. 1956. OCS and CS 2 are given in table 1. Molecular Beams (Oxford University Press) .068 b. 1970..m. Phys. 1974. and helpful discussions with Professor A..5 M H respectively. chem.. W. Molecular Wavefunctions and Properties (WileyInterscience). Financial support for this research from the Science Research Council. 1966. 1969. 371..m. SNYDER.1526 Roger D.. the nuclear quadrupole coupling constants in CO 2 and CS 2 are predicted to be 4. 74. Using this data to determine CrxV( . experiments [5]. Amos and Maurice R. Unfortunately there is no stable isotope of carbon with 1/> 1. Jost (Academic Press). 1972. E. D./ N.031 b. edited by H.N. Phys.W e would like to thank Professor W.m.M. Physical Chemistry : An Advanced Treatise. Tables of Experimental Dipole Moments (Rahara).. 1974.. Flygare for drawing our attention to a microwave Zeeman study of OCS and OCSe [44] in which similar conclusions are drawn concerning the failure of the pointcharge model for the quadrupole moments in these molecules.L. This result is probably slightly more accurate than a previous estimate. 1347. Buckingham are gratefully acknowledged. P. 653. + 0. STOGRYN.A. A. IV.0. Molec. Berkeley] at 23:33 14 December 2011 A nucleus with spin I >i 1 will have a quadrupole moment which can interact with the electric field gradient at that nucleus. 1963. 5 = 842 + 12 p. McCLELLAN. [1] [2] [3] [4] [5] [6] [7] REFERENCES BUCKINGHAM.R. which was derived by a similar method [42] but using a Hartree-Fock calculation of the field gradient. NUCLEARQUADRUPOLECOUPLINGCONSTANTS Downloaded by [University of California... and BASCH. F.0263 b (b = barn = 10-2s mS). producing effects which can be seen in the hyperfine structure of the microwave spectrum..p.H. By combining the experimental value for the a3S nuclear quadrupole coupling constant in OCS [38] with our calculated value of the field gradient.D. H. 7.) we calculate.6 MHz and 16. For the 170 nucleus the quadrupole moment is known accurately [41].. MCLEAN. D.Q. Henderson and W.p. LUCKEN. Vol. and STOGRYN.p. Reinartz and Dymanus [38] have measured C• for the (quadrupolar) aaS nucleus in OCS. Ae=329 + 18 p.. the quadrupole moment of a3S is deduced to be -0.R. by adding our M C S C F values of a d. These field gradients may be used to calculate the nuclear quadrupole coupling constants (eeOq) provided values are available for the nuclear quadrupole moment Q. D. L. Eyring. . The calculated values of the reduced electric field gradients (q) at the C. (a) RAMSEY. 11.A.063 b. or in N.A.) Our calculated results are in good agreement with these experimental values. Chem. Rev. C. Using our value for the asS quadrupole moment. 38. -0.4 0 8 p. and the value of -0-0263 for 170. O and S nuclei in CO2. D. C.

H.. Soc. Molec. S. 32. PATTERSON. and WHIFFEN. Vol. H. D. 94. P. (b) SCHAEFER.A. 1094.A. H. 1968.. 1978. D. W.J..C. 1976. 1967.. Soc. 7277. 1972. A. Int.. Tables de Constantes et Donndes Numeriques. 1968.T. Phys. Chem. [22] BATTAGLIA. D. 3243. 90. R. . 33. $9... DISCH. K. Phys. chem. and LAUTERBUR.. [14] AMOS. 427. 3104. Soc.. B. chem. H. chem. D. F. Chem. and DUNMUR.U. F. 1133. Faraday Trans.W.. H. R.. 55. 576. 5. R. Reson. [45].C. Phys..... ANDERSON. [38] REINARTZ. 49. Int.V. PRICHARD. magn. A. Phys. 1970. Phys. A. BLUME. Trans. Modern Theoretical Chemistry.. S.K. D. 288 . [27] BATTAGLIA. Phys. Non-linear Behaviour of Molecules. J. P... Atoms and Ions in Electric. chem. J. IS..M. 54.. 1970.. Lett.. SCHWEITZER. [24] (a) FOEX. and FROESE. R. 1968.. J.. L. J. H.. 197t. (b) Handbook of Physics and Chemistry. and RITCHIE. J.. Int. chem. 1967. M. 92. 53... and WAHL.W. Phys... 73. C. [45] BATTAGLIA. Lett. J. and KARPLUS. J.. The correct treatment of local field effects leads to Ag = -. 1971.. A. Berkeley] at 23:33 14 December 2011 [8] VECULIC. and YOSHIMINE. chem..A. and DAS. molec. Phys. 1977.M. and RAYNES. 1971. 5438. L.. W. [33] JACKOWSKI. F. [42] (a) ROTHENBERG. J. [39] BUCKINGHAM. 209. [15] DUNNING. Phys.. Vol. J. D..M. W... [19] DE LEEUW. Phys. R. KLEMM. 1977. 1970. 3122. D..A. quant. Phys.N. chem.. Lett. and MADDEN. and HARRIS..W. 1974. Phys. 1597. 49. 1765. F. A.. J.D.. H. [37] SPIESS. C.. (unpublished data). 65. 1966. 1967.. chem.. Schaefer (Plenum Press). Theor. J. (b) ROTHENBERG. chem.. A. T.. H. H. 1977. Y. [21] BUCKINGHAM. see also ref. T.M..W. J. Am. Atlas Symposium No. R. 1970.J. and MATCHA. 55. [13] SAUNDERS. D.A.. 176. 49. and DYMANUS. R. D....M. G. chem. y. Phys. I.. [28] MALLI.. I. OHRN. J...A. and DYMANUS. E. C. G. 346. Phys. Chem. [40] BUCKINGHAM. and RAIVlSEY. P. M. 1968.. chem. [17] KERN.J. 54. Rev. 1973.B. SCHAEFER. 1968. chim.. [41] (a) KELLY. 22.28"5 + 1"0 for CS2. Phys. 3003. Phys. chem. A. Phys. and McLEAN. J. 63... IS. 1057. CRAPO.K. P. and GUEST. lS. chem. quant... and RAMSEY. J.. 2081. Molec.N. C. G. M. [32] STEVENS. 7. [29] FLYGARE.W.. and BOGAARD. J... see also a footnote in J.. 14.. [9] FISCHER. 3015. 4th edition (Matheson Company). 124. P. and SCHAEFER.. H. 1976.. J... 12. [18] CEDERBERG. 95. i964. L. 2314. Chem.R. Soc. H.. [35] BATTAGLIA.R... [31] OZIER.A. C.M... Phys. 46. R. [44] SHOEMAKER. [11] YOSHIMINE. 63.. C.. 1968. P. 35. 1960.M. 1481.. 1968. HAEBERLEN. 3.. 1968. D. F. Faraday Soc. Am. J. OCS and CS2 1527 Downloaded by [University of California. [43] WAHL. [20] BUCKINGHAM. Molec. 1969. D.H. F. J. Chem.. 48. [36] PINES. J. T. 49..S. F. DISCH. 3682. F. 58th edition (Chemical Rubber Company Press).J. L. and RITCHIE. Phys.. 6. H.. K. [34] ETTINGER. A. H. R. Phys. A960... W... M. 465. chem. W.. 49. C. 1978.. YOUNG. Lett. 1957. 1974. and KEMMEY. A. 405. L. Am.Properties of C02.. 1977. [16] VEILLARD. [25] Matheson Gas Data Book. and HAUSSER.. 24. chem.. and SABIN.. Phys. 1971.. 101. Rev.. R. Molec. 716. G. Acta. J. R.R. 313. RHIM. Rev. [30] GIERKE. 1978.... and WAUGH.. H. L. 684.. and FLYGARE.. quant. 7 (Masson). Chem. edited by H. 99.}-I. G. R. 136. [12] McLEAN. and GOODISMAN. 34.. FORTUNE... Spectrose.M.M. F. J. Magnetic or Electromagnetic Fields (Elsevier)...P. 1967.M.. and FROESE. and LONGUET-HIGGINS. 1967. Phys. [10] ENGLAND..J. 119.. 180.. M. Molec. COX.R. and FLYGARE... Phys. (to be published). Chem.. ROSENBERG. L. [26] MALLI. [23] BATTAGLIA. 4. G.... D.

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