Molecular Orbital Theory of Magnetic Shielding and Magnetic Susceptibility

R. Ditchfield

Citation: J. Chem. Phys. 56, 5688 (1972); doi: 10.1063/1.1677088

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 THE JOURNAL OF CHEMICAL PHYSICS VOLUME 56, NUMBER 11 1 JUNE 1972

Molecular Orbital Theory of Magnetic Shielding and Magnetic Susceptibility

R. DITCHFlELD

Bell Telephone Laboratories, Incorporated, Murray Hill, New Jersey 07974

(Received 22 June 1971)

Hartree-Fock perturbation theory of magnetic susceptibility and magnetic shielding is developed using
a basis set of gauge invariant atomic orbitals. The theory is used to calculate magnetic shielding and spin-
rotation constants associated with the nuclei in LiH and HF giving results in good agreement with experi-
mental values.

INTRODUCTION THEORY
Absolute values of magnetic shielding constants
have been poorly reproduced by ab initio molecular The electronic Hamiltonian describing a closed
orbital theories using minimal basis sets of field- shell molecule in the presence of a uniform magnetic
independent Slater-type atomic orbitals (STO).1 In field H and the field of fixed nuclear moments IlA,
addition the results obtained are dependent on the IlB, .•. at positions R A• R B, •.• is given by
gauge chosen for the vector potential describing the
magnetic field. Within the framework of Hartree--
Fock perturbation theory, there are two ways of ap-
proaching gauge invariance. First, the basis set could Here c is the velocity of light, V is the potential energy
be extended to include a larger number of field-inde- term representing electron-nucleus and electron-
pendent atomic functions since the results will become electron interactions, and the vector potential at elec-
gauge invariant in the limit of a complete set of such tronj is
basis functions. 2 Studies of this kind have been made
A(rj) =!H/\rj+ L: (IlB/\rjB)/rjB3, (2)
by several groups of workers3- 7 and have led to the B
general conclusion that a carefully optimized extended
set of STO's about 3 times the size of the minimal set where rf, R A, R B, •.• are defined with respect to some
is required if results of a few percent accuracy are to arbitrary origin and rjB=rj-R B. (The arbitrary
be obtained. However, even at this level the results in nature of the choice of the origin of rj leads to the
some cases are still markedly dependent on the gauge problems with gauge mentioned above.)
of the vector potentia}.! A second way is to develop We seek a solution \[f(H, IlA, IlB, ... ) to the per-
Hartree--Fock perturbation theory using a basis set of turbed Schrodinger equation,
gauge invariant atomic orbitals (GIAO).8 Such a
theory will give gauge invariant results for magnetic Je(H, IlA, Iln, .•. )\[f(H, IlA, !lB, .•. )
properties even with minimal sets of atomic functions. 9
Use of GIAO in problems of molecular diamagnetism
was first made by Londons in connection with ring
currents in aromatic hydrocarbons and they have since where the wavefunction is calculated as a single de-
been employed in more general studies of magnetic terminant of molecular orbitals ljIj. To ensure gauge
properties by Hameka,9 Pople,1° McWeeny,ll Hall and invariance we further write each molecular orbital ljIj
Hardisson,12 Davies,13 Amos and Roberts,14 and Bley.l. as a linear combination of GIAO tPJl'
Self-consistent perturbation theory of magnetic sus-
(4)
ceptibility and magnetic shielding was first developed
13
by Davies and by Hall and Hardisson.12 These
authors, however, were interested in the ring current where ClSj are the LCAO coefficients and
contributions to X and IT and consequently their de-
velopments reflected the approximations of pi-electron tPJl=exp[ - (i/c)AJl·rJxJl' (5)
methods.
In this work we outline Hartree--Fock perturbation Here AJl = !H/\RJl where RJl is the distance vector from
theory for magnetic properties using GIAO in a general the arbitrary origin to the nucleus on which tPJl is
form, presenting equations for magnetic susceptibility located, and XJl is the atomic orbital in the absence of
and magnetic shielding. The method is used to cal- the magnetic field.
culate magnetic shielding and spin-rotation constants The LCAO coefficients are determined by applying
for the nuclei in LiH and HF and the results compared the variational principle to the energy of Eq. (3)
with the best results obtained by Stevens and Lips- subject to orthogonality constraints between molecular
comb.4.6 orbitals ljIj. For closed shell molecules this leads to the
5688

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 MAGNETIC SHIELDING AND SUSCEPTIBILITY 5689

Roothaan16 equations, We also note from Eq. (10) that

L: (F),.-E;S),.)e.;=O. (6) ap),' -_ 2 ~
L.J
(ac*"i Cva C*'" .ac. i ) • .+
(17)
aHt i aHt aHt
The Fock matrix elements Fl" are given by
Using Eqs. (6), (16), and (17) in Eq. (14) leads to
(7)
[aE(H, ll)jaHtJ
where
= L: e*";(2[ajaH t«cp,, I Hcore I CP.»]
HI'.COf6= (cp)' \ Hcore \ CP.) i,lJ,v

= (cp" \ [t[ -iV+e-1A(r) J2- L: ZBjrBJ I CP.), (8)

B
-2(aSI'.jaH t)Ei)C.;. (18)
An important point to note about Eq. (18) is that eval-
(9) uation of the first derivative of the energy does not
require the first derivative of either the LeAO coef-
occ
ficients C)'i or the orbital energies Ej. Thus the second
P).a = 2 L: e)./e a;. (10) order properties Xtu and UBt .. require only the first
; derivatives of e"j and Ej. The equation for the magnetic
The energy associated with molecular orbital Vt; is Ej, susceptibility tensor is
rB is the distance from the electron to nucleus B of Xtu= -t L: «ac*I'JlaH,,) {2ajaH t(H,,:ore)
charge ZB, and S". and (IlIJ \ AU) are the usual overlap i./J,v

and two-electron integrals, respectively. The energy

corresponding to the self-consistent wavefunction
'!r(H, !LA, !LB, ••• ) is +c*l'j{2[a2jaH"aH t (H,,:ore)]+ L: [aP).a(Hu)jaH,,]
). ..
E(H, !LA, !LB, ••• ) = L: P),.H".oore +t L: pp"c".. (11) x [ajaHt(GI'.Aa) ] + L: P).a(O) [a 2jaH"aH t(G".).a) ]
p.
).0'

The magnetic susceptibility tensor Xt .. and the magnetic -2(a2sl'.jaH"aHt)Ej-2(aS)'./aHt) (aEjjaH.. ) }e.i
shielding tensor at nucleus B, UBtu may be formally de-
fined by +e*,,;[2ajaH t(H,,:ore) + L: P).a(O) [ajaHt(G".).a)]
).0'

(12) -2 (aSI'.jaHt)E;](ae.JlaH,,,) ), (19)

where P).a(O) is the density matrix in the absence of the
magnetic field H. A similar equation may be obtained
Thus determination of these magnetic properties for UBt" by differentiating Eq. (18) with respect to
requires derivatives of Eq. (11) with respect to com- IlB". In this case terms involving derivatives of GIAO
ponents of the magnetic field and the nuclear moment. with respect to !LB are zero since the atomic orbitals
Differentiating Eq. (11) with respect to H t we ob- depend only on the external magnetic field H. How-
tain ever, an alternative, simpler form for the shielding
tensor may be obtained by differentiating Eq. (11)
first with respect to IlBu and then with respect to H t,
+pp.[ajaHt«cp" I Hoore I CP.»J+ (ap".jaHt)G". [aE(H, !LB)jaIlB,,]= L: P".(H)
+tP". L: P).a{ajaHt[(IlIJ I AU) -t(IlU I AIJ)J}). (14) x [(cp" I aHcorejallB" I CP.)], (20)
From the orthogonality conditions between molecular and the shielding tensor is given by
orbitals, we may write UBt .. = L P".(O) [ajaHte (cp" \ aHoorejallBu \ cf>.»]
(15)
".
+[(ap".(Ht)jaHt)(X" \ aHoorejall Bu \ x.»J (21)
Differentiating Eq. (15) with respect to field com- = (1/2c2) L {P".(O) (x" \ (rB·r.o tu -rBtr... )/rB3 \ x.)
ponent H t gives
+P".(o)[«acf>,,/aHt) \ LB"jrB 3 \ x.)
L: (ae*,,;jaH t) e.jS".+c*,,;(ac.jjaH t) S".
". + (x" \ LB,,/rB I (acf>./aH t»]
3

+[aPI'.(Ht)/aHtJ(xl' I LB../rB3 \ x.)}, (22)

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5690 R. DITCHFIELD

TABLE 1. Calculated and experimental magnetic shielding' and spin-rotation b constants.

Calculated results

Stevens and
Molecule Magnetic property This work Lipscomb Observed results

LiH e O"Li d 100.4

O'Li P -10.6
O'Li 89.8 9O.2d
CLi 9.8 9.6d 9.92±0.04e
(wi ~ rLi;-ll w) 107.9

O"H d 25.0
O"H" 1.3
O"H 26.3 26.5 d
CH -9.2 -9.6 d -1O.1±1.0e
(wi ~ rHr! Iw) 39.5

HFf O"F d 468.5

O"F" -51.7
ITF 416.8 413.9-
CF 294.9 312.4- .105±2 h
(wi ~ rF;-l i w) 481.7

ITHd 25.5
O"H" 8.7
O"H 34.2 30.5·
CH -90.2 -84.2- 71±3 h
(w I ~ ' H rl Iw) 110.7

& Magnetic shielding constant units are parts per million.

b Spin-rotation constant units are kilohertz.
e All calculations are at R=3.015 a.u.
d Reference 4 .
• Reference 14.
fAll calculations'are at R= 1.733 a.u.
I Reference 5.

h Reference 15.

where cule can be obtained from three (t = x, y, z) perturbed

r.=r-R., (23) wavefunction calculations.
The first derivative (ap,../aH t ) may be calculated
Ln .. = -i(rn/\ V)", (24) numericallyl7 or by separating orders of perturbation
and all derivatives are taken in the limit of H= ILB=O. and solving the first order perturbation equations. ls
In Eq. (22) the first term is the diamagnetic contribu- In either case only terms containing up to linear powers
tion (UBt"d) to the magnetic shielding constant and of H t need to be included in the expressions for the
depends solely on the unperturbed wavefunction. Fock matrix elements F,. •. Thus in all the integrals over
The second and third terms are the paramagnetic GIAO in Eqs. (6)-(10) we can expand the gauge
contribution UBI,," and are determined by the per- factors and retain only the first and second terms. For
turbed wavefunction. It is clear from Eq. (22) that example,
only those parts of X of Eq. (1) which describe the
unperturbed problem and the effect of the external J<PI'*<p.dr = Jx,.x.dr - (i/ 2c) (H"R.· R,.J x,.x.dr
magnetic field need to be included in the Hamiltonian -H"R,..· Jx,.r,.x.dr). (25)
used to calculate the perturbed wavefunction. Thus the
magnetic shielding tensors for all the nuclei in a mole- If the zero field basis set contains only sand p atomic

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 MAGNETIC SHIELDING AND SUSCEPTIBILITY 5691

orbitals, then additional integrals involving p and d cluded in the table represent the best available cal-
atomic functions are required. culated values using that type of approach. It is clear
that the minimal b?-sis GIAO method gives results for
RESULTS AND DISCUSSION magnetic shielding constants which compare favorably
with those obtained by the SL method and has the
The above theoretical method has been used to following advantages:
calculate the diamagnetic and paramagnetic contribu-
tions to the magnetic shielding at the nuclei in LiH (1) The GIAO method gives results which are inde-
and HF and the results are reported in Table 1. In pendent of the choice of the origin of the vector po-
addition we present results for spin-rotation constants tential describing the magnetic field.
(CB ), which are related to the magnetic shielding con- (2) The method is computationally more economic
stants by,19 than the SL method and thus can be more easily ap-
plied to a study of magnetic shielding in larger mole-
UB= (1/3c2) [('1'(0) I L rBrl1 '1'(0) cules.
ACKNOWLEDGMENTS
- L ZA/RAB+IICBI/IoIN"YBM], (26)
A;oo<B It is a pleasure to acknowledge useful discussions
where M is the proton mass, loiN is the nuclear magneton, with Dr. J. W. McIver, Dr. D. P. Miller, Professor
"YB is the gyromagnetic ratio of nucleus B, and I is the
J. A. Pople, and Dr. L. C. Snyder.
moment of inertia. Spin-rotation constants have been 1W. N. Lipscomb, Advan. Magnetic Resonance 2,137 (1966).
measured for the nuclei in LiH by Klemperer et al.20 2S. T. Epstein, J. Chern. Phys. 42, 2897 (1965).
3 R. M. Stevens, R. M. Pitzer, and W. N. Lipscomb, J. Chern.
and for the nuclei in HF by Baker et alP Phys. 38, 550 (1963).
The results for LiH were calculated using the STO 'R. M. Stevens and W. N. Lipscomb, J. Chern. Phys. 40,
basis set given by Ransil22 as the zero field atomic 2238 (1964).
6 R. M. Stevens and W. N. Lipscomb, J. Chern. Phys. 41, 184
functions X", except that each STO was replaced by a (1964).
least squares fitted sum of five Gaussians (STO- 8 G. P. Arrighini, M. Maestro, and R. Moccia, Chern. Phys.
5 G) .23 Previous work24 leads us to expect that the Letters 1, 242 (1967); J. Chern. Phys. 49, 882 (1968).
7 G. P. Arrighini, J. Tomasi, and C. Petrongolo, Theoret. Chirn.
STO-SG results will be very close to those that would Acta 18, 341 (1970).
be obtained if STO functions were used directly. The 8 F. London, J. Phys. Radium 8,397 (1937).
& H. F. Harneka, Rev. Mod. Phys. 34, 87 (1962) and references
results for HF were obtained using an STO-5 G repre- therein.
sentation of a minimal basis set of STO's as the zero 10 J. A. Pople, J. Chern; Phys. 37, 53 (1962).
field atomic orbitals X" with scaling factors taken from 11 R. McWeeny, Mol. Phys. 1, 311 (1958).
12 G. G. Hall and A. Hardisson, Proc. Roy. Soc. (London)
the standard set presented by Hehre, Stewart, and A268,328 (1962).
Pople. 23 13 D. W. Davies, Trans. Faraday Soc. 57, 2081 (1961).

As shown in the table calculated results for the l' A. T. Amos and H. G. Ff. Roberts, J. Chern. Phys. SO, 2375
(1969) .
spin-rotation constants are in good agreement with 16 W. R. Bley, Mol. Phys. 16,303 (1969); 20, 491 (1971).
experiment, particularly for the first row atoms. This 16 C. C. J. Roothaan, Rev. Mod. Phys. 23, 69 (1951).
17 J. A. Pople, J. W. McIver, Jr., and N. S. Ostlund, J. Chern.
suggests that the paramagnetic contribution to mag- Phys. 49,2960 (1968).
netic shielding is described adequately at the minimal 18 R. Moccia, Chern. Phys. Letters 5, 260 (1970).

basis GIAO level. Since the diamagnetic contribution is 1& N. F. Ramsey, Molecular Beams (Oxford U. P., New York,
1956).
somewhat easier to calculate, the calculated total 20 W. Klernperer, L. P. Gold, and L. Wharton, J. Chern. Phys.
magnetic shielding constants are also likely to be re- 37, 2149 (1962).
21 M. R. Baker, H. M. Nelson, J. A. Leavitt, and N. F. Ramsey,
liable. This conclusion is supported by comparing our
Phys. Rev. 121,807 (1961).
calculated results with those obtained by Stevens and 22 B. J. Ransil, Rev. Mod. Phys. 32, 239 (1960).
Lipscomb (SL). These workers used extended basis 23 W. J. Hehre, R. F. Stewart, and J. A. Pople, J. Chern. Phys.

sets of field-independent STO's in an attempt to ob- 51,2657 (1969).

2' R. Ditchfield, D. P. Miller, and J. A. Pople, J. Chern. Phys.
tain gauge invariant properties, and their values in- 53, 613 (1970).

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