Nuclear Electromagnetic Shieldings via

Charge and Current Density Functions

PAOLO LAZZERETTI
Dipartimento di Chimica, Università degli Studi di Modena e Reggio Emilia, via G. Campi 183,
41100 Modena, Italy

Received 18 July 2001; accepted 12 December 2001

DOI 10.1002/qua.999

ABSTRACT: The general concept of time-dependent charge and current densities for
the electrons in a molecule responding to electromagnetic fields is considered. It is shown
that nuclear electric and electromagnetic shieldings, related to absorption intensity in
infrared and vibrational circular dichroism spectroscopies, can be expressed in terms of
density functions in real space. Plots of charge and current densities obtained by the
theoretical methods developed in the present study are expected to provide a physical
basis on the absorption process and simple tools for the interpretation of vibrational
spectroscopy parameters. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem 90: 464–471, 2002

Key words: nuclear electromagnetic shieldings; density functions; time derivative of

dipole accelerations

and transition matrix elements between the refer-

Introduction ence and excited states.
To rationalize response, and to develop viable

S tandard quantum mechanical relationships are

customarily used to define intrinsic tensor
properties of the electrons of a molecule in the
presence of electromagnetic field and/or internal
perturbations, e.g., nuclear magnetic dipoles and
electric quadrupoles. Perturbation theory and prop-
agator methods yield expressions for, say, perma-
nent electric dipole, multipole electric polarizabili-
ties, and hyperpolarizabilities, in terms of ground
state eigenfunction, natural transition frequencies,
Correspondence to: P. Lazzeretti; email: lazzeret@unimo.it.
Contract grant sponsor: MOLPROP.
Contract grant number: HPRN-CT-2000-00013.
Contract grant sponsor: MURST.
computational schemes of observable quantities, we
can also avail ourselves of formal tools provided
by classical electromagnetic theory. It is sometimes
advantageous to introduce charge density, ρ, and
current density, Jα , evaluated by quantum mechan-
ical methods, into the deterministic equations that
describe their interaction with perturbing fields and
moments. In fact the Maxwellian theory can be
assumed to provide us with a body of phenom-
enological relationships that are valid also in quan-
tum mechanics, owing to the special character of
the density functions. ρ and Jα , are subobservables,
that is, expectation values of corresponding opera-
tors, according to Hirschfelder [1]. If these functions
are available from quantum methods, they can be

International Journal of Quantum Chemistry, Vol. 90, 464–471 (2002)

© 2002 Wiley Periodicals, Inc.
 NUCLEAR ELECTROMAGNETIC SHIELDINGS

safely used within the context of classical electro- RI , etc. Throughout this section the Einstein conven-
magnetism. tion of implicit summation over two repeated Greek
Charge and current density functions are defined subscripts is retained.
over three-dimensional space, and the economy The general expression for the expectation value,
of thinking achieved with respect to conventional in the electronic state a, of an operator T, character-
formulation in terms of electronic wavefunctions, ized by the perturbation expansion
which depend on 3n coordinates for a molecule
T = T0 + T1 + · · · (1)
with n electrons, is evident. However, the funda-
mental advantage provided by a description relying is given by time-dependent perturbation theory,
on density functions is that of visualizing the inter- within the quadrupole approximation [3],
action process. Plots of ρ(r) and Jα (r) yield models
whereby molecular response can be easily inter- Ta = a|T0 |a + a|T1 |a

preted in a number of cases. For instance, maps 1  2
+ a|T0 |j
of streamlines and modulus of the current density h̄ ω − ω2
2
j = a ja
vector field induced in the electrons of a molecule   
by a stationary, time-independent magnetic field af- × j|µα |a ωja Eα (0, t) + iĖα (0, t)
 
ford significant physical insight on the interacting + j|µαβ |a ωja Eβα (0, t) + iĖβα (0, t)
system and produce successful “ring current mod- 
 
els” [2]. + j|mα |a ωja Bα (0, t) + iḂα (0, t) . (2)
The present study is aimed at extending the ap-
proach to time-dependent properties, in particular In this relationship Eα (0, t), Bα (0, t), and Eαβ (0, t)
to nuclear electric and electromagnetic shieldings, are electric field, magnetic field, and electric field
i.e., second-rank molecular tensors that are used gradient (at the origin of the coordinate system)
to interpret absorption intensities in infrared (IR) of a monochromatic external radiation, with fre-
and vibrational circular dichroism (VCD) spec- quency ω. Their partial time derivatives are indi-
troscopy [3]. The article is organized as follows. cated by a dot, e.g., Ėα (0, t). These time derivatives
First we report quantum mechanical expressions correspond to out-of-phase fields. The electronic
for charge density, current density, and expectation operators for electric dipole, magnetic dipole, and
value of the electric field at a nucleus of a molecule electric quadrupole are denoted by µα , mα , and µαβ ,
(0)
in the presence of electromagnetic field. An equa- respectively [3]. The reference state |a ≡ |a 
tion connecting charge density to current density (0)
and the excited states |j ≡ |j  are eigenfunc-
formalism is obtained in the next section by classical tions to the unperturbed time-independent Hamil-
methods, showing the equivalence of the two rep- tonian H(0) , and the natural transition frequencies
resentations in the time-dependent case. Then we are indicated by ωja .
introduce the formalism of time-derivative of dipole The first-order charge polarization density in-
acceleration. This is needed to prove the equiva- duced by the electromagnetic perturbation within
lence of charge and current density descriptions of the electron distribution is given by the relation-
electromagnetic shieldings in quantum mechanics. ship [4]
The explicit definitions of these properties in terms
of ρ(r) and Jα (r) induced by the perturbation are 2en  2 −1
ρ (1) (r, t) = ωja − ω2
given in the last two sections. h̄
j=a

 
× a H(1) j ωja − i a Ḣ(1) j
The Expectation Value of the
(0)∗
Electric Field at a Nucleus × dx2 · · · dxn j (r, x2 · · · xn )

(0)
For a molecule with n electrons and N nuclei, ×a (r, x2 · · · xn ) , (3)
charge, mass, position with respect to an arbitrary
origin, and canonical and angular momentum of the where H(1) is the first-order time-dependent Hamil-
ith electron are denoted by −e,
me , ri , pi , li =

ri × pi , tonian, with Ḣ(1) its partial time derivative. The
i = 1, 2, . . . , n, whereas R = ni= 1 ri , L = ni= 1 li , space-spin coordinate of the ith electron is denoted
etc. Analogous quantities for nucleus I are ZI e, MI , by xi .

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 465

LAZZERETTI

The induced electronic current density to first or- relates the nuclear electric shielding tensor to the
der in Bα (0, t) contains a Larmor-type term, geometrical derivatives of the molecular electric
dipole moment M, i.e., the ∇Iα Mβ APT. The IR in-
e2 tegrated absorption intensities are proportional to
JBL (r) = − B × rγ (0) (r), (4)
2me c squares of M derivatives with respect to normal
coordinates, which are related to the APT via a sim-
related to the probability density of the unper-
ilarity transformation.
turbed molecule, γ (0) (r). The JBL (r) field is transver-
Equation (10) provides a reinterpretation of IR
sal; i.e., the electron flow is fully contained in planes
absorption along the following lines: the IR radia-
perpendicular to B. A non-Larmor contribution is
tion is a dynamic electric field which causes oscilla-
given by [4]
tions in the electronic density ρ and induces current
(1) en  2 −1
densities Jα . The perturbed electrons, in turn, induce
JNL (r, t) = ωja − ω2
me h̄ an additional dynamic electric field at the nuclei via
j=a
 a feedback mechanism. The latter are hence acted
 
× a H(1) j ωja − i a Ḣ(1) j upon by the effective electric field
 
× dx2 · · · dxn j
(0)∗
(r, x2 · · · xn ) Eeff (RI ; ω) = 1 − γ I (ω) · E, (11)

(0)
×pa (r, x2 · · · xn ) i.e., by a frequency dependent Lorentz force,
ZI Eeff (RI ; ω), which is responsible for changes of nu-
(0)∗
+ dx2 · · · dxn a (r, x2 · · · xn ) clear vibrational motion. Accordingly, the electron
(0)
distribution of a molecule plays a fundamental role
× pj (r, x2 · · · xn ) in determining the general features of nuclear vibra-

  tions and the magnitude of IR parameters.
× jH (1)
a ωja + i j Ḣ (1)
a . (5) VCD is the differential absorption of left- and
right-circularly polarized infrared light. In this spec-
(1)
The JNL (r, t) vector has a component parallel to the troscopy it is the magnetic field of the monochro-
external perturbing field. For matic wave which induces the dynamic electric
Lorentz force causing a change of dynamic state of

n
ri − RI
T0 ≡ EnI = e , (6) the nuclei. The theoretical connection is given by the
|ri − RI |3 Stephens integral [5]
i=1

the operator for electric field induced at nucleus I by iZI e I

I
Iαβ =− ξ̂ (0). (12)
the perturbed electrons, it obtains from Eq. (2) 2h̄ αβ

EnIα = −γαβ
I
Eβ (0, t) + ξ̂αβ
I
Ḃβ (0, t) + · · · . (7)

The physical meaning of the response tensors ap- Moments of the Density Functions
pearing in formula (7) is immediately grasped. The in the Lagrangian Formalism
dynamic dipole properties are
The classical Lagrangian of one electron with
e  2ωja  
γ I (ω) = a EnI j  j|R|a , (8) mass me , charge −e, position r, and velocity ṙ, within
h̄ ω −ω
2
j = a ja
2
an electromagnetic field, is a sum of “particle” and
I e  2   “interaction” terms,
ξ̂ (ω) =  a EnI j  j|L|a . (9)
2cmh̄ ωja − ω
2
j=a
2 L = Le + LI , Le = 12 me ṙ2 ,
e
Equations (8) and (9) define the electric and the LI = eφ(r, t) − ṙα Aα (r, t). (13)
c
electromagnetic shielding at nucleus I, respectively.
These quantities are related to the intensities of IR The Euler–Lagrange equations of motion are
and VCD vibrational spectroscopies [3] via their d ∂L ∂L
connection with the atomic polar tensor (APT) and − = 0, (14)
dt ∂ ṙα ∂rα
the atomic axial tensor; e.g.,
  where φ(r, t) and Aα (r, t) are the scalar and vector
∇Iα Mβ = ZI e δαβ − γαβ
I
(0) (10) potential. They are defined to within a gauge trans-

466 VOL. 90, NO. 1

 NUCLEAR ELECTROMAGNETIC SHIELDINGS

formation, which does not affect the fields and the In a gauge transformation (15) where f = f (R, t), the
Maxwell equations, new Lagrangian density is given by
Aα → Aα = Aα + ∇α f , 
1 ∂f
1 ∂f (15) LI → LI = LI + ρ + Jα ∇α f
φ → φ = φ − , c ∂t
c ∂t 
1 ∂
where f = f (r, t) is an arbitrary continuous scalar = LI + (ρf ) + ∇α ( Jα f )
c ∂t
function. If the field potentials are required to satisfy 
the Lorentz condition ∂ρ
−f + ∇α Jα , (26)
1 ∂φ ∂t
∇·A+ = 0, (16)
c ∂t where the last contribution vanishes if the conti-
then a restricted class of f is chosen, obeying the nuity equation (23) is fulfilled. Integrating over all
D’Alembert equation space, the second contribution within the brackets,
 owing to the Gauss theorem, gives a surface inte-
1 ∂2

2 f ≡ ∇ 2 − 2 2 f = 0, (17) gral that vanishes for the boundary conditions (the
c ∂t products f ρ and f Jα tend to 0 sufficiently quickly at
so that, for the transformed potentials, infinity). One is left with a time derivative, i.e., with
1 ∂φ  an equivalent Lagrangian (19) and the same Euler–
∇ · A + =
2 f = 0. (18) Lagrange equations of motion (14).
c ∂t
Let us now consider the Lagrangian density of
In a change of gauge the primitive Lagrangian is the electron distribution, rewriting Eq. (24) in the
transformed into an equivalent one, form
dg 1
L → L = L + , (19) LI = −ρ(r, t)φ(r, t) + Jα (r, t)Aα (r, t). (27)
dt c
where From Eq. (26), describing the variation of the La-
dg ∂g e grangian density in a gauge transformation, and
= ṙα ∇α g + , g = − f. (20) from Eq. (19) for the corresponding change of the
dt ∂t c
Lagrangian, it is found that
Only LI is modified, whereas the particle La-
grangian stays the same. In order to deal with dg 1 ∂ 1 d
= d3 r (ρf ) = d3 r (ρf ), (28)
continuous systems, it is useful to introduce the con- dt c ∂t c dt
cept of Lagrangian density. Although the classical so that the function
electron is a particle localized at the point r(t), it can
1
be can formally assumed that its charge is spread g= d3 r (ρf ) (29)
out with density ρ(R, t) at point R and flows with c
current density Jα , given by can be chosen to yield a transformed Lagrangian
  according to Eq. (19). Allowing again for Eq. (26),
ρ(R, t) = −eδ R − r(t) , (21) the relationship
 
Jα (R, t) = −eṙα (t)δ R − r(t) , (22)  
dg d 1
= d3 r (ρf )
and satisfying the continuity constraint dt dt c

∂ 1 ∂f
∇ ·J+ ρ = 0. (23) = d3 r ρ + J · ∇f (30)
∂t c ∂t
Accordingly, an interaction Lagrangian density is
is arrived at. Since f is any continuous function of
defined,
position and time, by choosing f ≡ rα , the compo-
1 nents of the position vector, it is obtained that
LI = −ρ(R, t)φ(R, t) + Jα (R, t)Aα (R, t), (24)
c d
d3 r ρrα = d 3 r Jα . (31)
such that the Lagrangian is obtained from it by inte- dt
grating over spatial coordinates, If the function f = rα rβ is alternatively chosen, then
d
LI = LI d3 R. (25) d3 r ρrα rβ = d3 r ( Jα rβ + Jβ rα ). (32)
dt

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 467

LAZZERETTI

N
Therefore a general series of moments of the density Unα potential is
function is connected to corresponding moments of
e2  
N n
the current density via equations like (31) and (32), N
Unα = ZI ∇iα ∇iβ |ri − RI |−3 piβ
the next of which is me
I=1 i=1
2 N n 
d e 4
d3 r ρrα rβ rγ = d3 r ( Jα rβ rγ − ZI πδ(ri − RI )δαβ
dt me 3
I=1 i=1
+ Jβ rα rγ + Jγ rα rβ ). (33) 
− |ri − RI |−5 3(riα − RIα )(riβ − RIβ )

These identities have been obtained allowing for 
− |ri − RI |2 δαβ piβ . (34)
Lagrangian formalism, i.e., within the context of
classical electrodynamics. In fact, Eqs. (31)–(33), etc.,
Such a potential is not used in classical mechanics.
provide useful computational recipes for the calcu-
However, it can be adopted in quantum mechani-
lation of response properties [4], e.g., electric dipole
cal radiation theory [7 – 10]. The Hermitian operator
polarizabilities and optical rotatory power, and sum
corresponding to the classical expression (34) is
rules related to force and velocity theorems [6]. written
However, the two sides of the moment equations do
e2   4 
N n
not necessarily provide the same numerical quan- 
N
Unα =− ZI π δ(ri − RI ), piα +
tities in approximate quantum mechanical calcu- 2me 3
I=1 i=1
lations, unless the electronic densities and current  
densities appearing in these relationships satisfy − |ri − RI |−5 3(riα − RIα )(riβ − RIβ )

some special constraints.  
− |ri − RI | δαβ , piβ + ,
2
(35)

where {A, B}+ is the anticommutator of operators A

and B.
N
A more compact expression for the Unα potential
Hypervirial Relations for is obtained introducing the electronic current den-
Time Derivative of Force sity operator,

e 
n

Newtonian equations involving the operators for Ĵα (r) = − δ(r − ri ), piα + , (36)
position Rα and linear momentum Pα of the elec- 2me
i=1
trons in a molecule can be written in the form and the “experimental” field gradient operator,
dRα 1 
= Pα , EiIαβ = e|ri − RI |−5 3(riα − RIα )(riβ − RIβ )
dt me 
− |ri − RI |2 δαβ . (37)
dPα   riα − RIα
N n
= FN
nα = −e
2
ZI , Then the operator for time derivative of force on
dt |ri − RI |3
I=1 i=1 electrons becomes
4  e   i
N N n
where the vector FN nα is the total force exerted by

N
Unα = πe ZI Ĵα (RI ) + ZI EIαβ , piβ + .
the nuclei on the electrons in the absence of ex- 3 2me
I=1 I=1 i=1
ternal perturbation. The time derivative of force is (38)
obtained from
A series of off-diagonal hypervirial relationships [6]
dFN 
N 
n can now be written as
nα
≡ Unα
N
= I
Uiα , i −1 1
dt
I=1i=1 a|Rα |j = ω a|Pα |j = − ωja−2 a FNnα j
me ja me
dFI ∂FI driβ 1 I
e −2 
N
I
Uiα = iα = iα ≡ F piβ .
dt ∂riβ dt me iβα = ωja ZI a EnIα j ,
me
I=1
The FIiβα second-rank tensor is obtained from the i
Poisson’s equation, so that, in classical terms, the = − ωja−3 a Unα
N
j, (39)
me

468 VOL. 90, NO. 1

 NUCLEAR ELECTROMAGNETIC SHIELDINGS

connecting transition matrix elements in dipole Allowing for Eq. (44), and using the quantum me-
length, velocity, acceleration, and time derivative of chanical expression, Eq. (5), for the current density
acceleration. These identities are satisfied by opti- induced by the electric field derivative [3, 4],
mum variational functions obeying corresponding 
hypervirial theorems [6]. en  2 
2 −1
Jα = −
Ė
ωja − ω  a|µβ |j dx2 · · · dxn
me h̄
j=a
(0)∗ (0)
×j (r, x2 · · · xn )pα a (r, x2 · · · xn )
Electric Shielding at Nucleus I
(0)∗
− dx2 · · · dxn a (r, x2 · · · xn )
The polarization density induced within the

electron cloud by the electric field of an imping- (0)
ing monochromatic wave is obtained via time- ×pα j (r, x2 · · · xn ) j|µβ |a Ėβ (0, t), (45)
dependent perturbation theory [see Eq. (3)] in the
a non-Hermitean expression for the electric shield-
form [3, 4]
 ing is arrived at. It is therefore convenient to replace
2en  ωja the classical relationship (44) by introducing the
ρ (r, t) = −
(E)
a|µβ |j dx2 · · · dxn
h̄ ω2 − ω2
j = a ja
symmetrized definition for the electric shielding in-
 duced by the time derivative of the electric field,
(0)∗ (0)
×j (r, x2 · · · xn )a (r, x2 · · · xn ) Eβ (0, t). (40)
1  Ė Ė 
I
γαβ = d3 r Jγ β ∇γ EIα + (∇γ EIα )Jγ β . (46)
From Eq. (30), using the generating function 2e

rα − RIα 1 Multiplying by ZI and summing over I the alterna-

f ≡ = EIα , (41) tive definitions for nuclear electric shielding from
|r − RI |3 e
Eqs. (42) and (46), it is verified that Eq. (30) is ful-
it obtains filled only if the hypervirial theorem for the position
operator, Eq. (39), is satisfied. In such a case the def-
d rα − RIα
d3 r ρ (E) = γαβ
I
(ω)Ėβ (0, t), (42) initions for the electric shielding from polarization
dt |r − RI |3 density and current density could be regarded as
where γαβ I
(ω) is the dynamic nuclear electric shield- equivalent.
ing tensor in dipole length picture defined by
Eq. (8). This integral expression can be used to cal-
I
culate γαβ (ω) by formally putting the components
Electromagnetic Shielding at Nucleus I
Ėβ (0, t) = 1 in a given system of units.
Let us now calculate the integral on the right From eq. (3), the polarization density induced by
hand side of Eq. (30) via the expression for the quan- the time derivative of the magnetic field is [3, 4]
tum mechanical current density induced by the time

derivative of the electric field. It is expedient to in- 2en  2 
2 −1
Ė ρ (r, t) = −
(Ḃ)
ωja − ω  a|mβ |j
troduce a second-rank current density tensor Jα β to h̄
j=a
factor out the Ėβ (0, t) term,
(0)∗
× dx2 · · · dxn j (r, x2 · · · xn )
Ė
JαĖ = Jα β Ėβ (0, t). (43) 
(0)
×a (r, x2 · · · xn ) Ḃβ (0, t). (47)
According to Eq. (30), a classical definition of the
electric shielding at nucleus I in terms of current The paramagnetic contribution to the current den-
density can be proposed in the form sity induced by the magnetic field is determined
 from Eq. (5) in the form
4 Ė
I
γαβ = d 3
πδ(r − RI )δαγ
r Jγ β 
3
 en  ωja
− |r − RI |−5 3(rα − RIα )(rγ − RIγ )
B
Jpα (r, t) = − a|mβ | j dx2 · · · dxn

me h̄ ω2 − ω2
j = a ja

− |r − RI | δαγ .
2
(44) ×j
(0)∗ (0)
(r, x2 · · · xn )pα a (r, x2 · · · xn )

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 469

LAZZERETTI

+
(0)∗
dx2 · · · dxn a (r, x2 · · · xn ) is obtained. Allowing for the commutator relation-
 ship
(0)
×pα j (r, x2 · · · xn ) j|mβ |a Bβ (0, t), n 
(48) i n  4
EIα , Lβ = −eβγ δ riγ πδ(ri − RI )δαδ
h̄ 3
and the diamagnetic contribution from Eq. (4) is i=1

− |ri − RI |−5 3(riα − RIα )(riδ − RIδ )
e2 n 
B
Jdα (r, t) = − αβγ Bβ (0, t) dx2 · · · dxn 
2me c − |ri − RI |2 δαδ , (55)
(0) (0)∗
× rγ a (r, x2 · · · xn )a (r, x2 · · · xn ). (49)
for the obvious identity
Analogously to the electric case [see Eq. (43)]
a second-rank current density tensor is defined via ωja2 ω2
=1+ ,
B ωja2 − ω2 ωja2 − ω2
JαB = Jα β Bβ (0, t). (50)
and using the expressions for paramagnetic and
With ρ (Ḃ) from Eq. (47), the left hand side (l.h.s.) of
diamagnetic contributions to the current density,
Eq. (30) gives (1)
Eqs. (48) and (49), it is found that Ip = −Id with
d rα − RIα
d3 r ρ (Ḃ) = −ξ̂αβI
(ω)B̈β (0, t)
dt |r − RI |3 e2 N
d3 r Jdα
B
=− βγ δ Bβ (0, t) ZI
= ξ̂αβ
I
(ω)ω2 Bβ (0, t), (51) 2me c I=1
 n
as, owing to the wave equation for the electro-  4
magnetic field, B̈(0, t) = −ω2 B(0, t). The dynamic × a riγ πδ(ri − RI )δαδ
3
I i=1
electromagnetic shielding tensor ξ̂αβ (ω) is defined 
via Eq. (9). − |ri − RI |−5 3(riα − RIα )(riδ − RIδ )
In analogy to the electric shielding [see Eq. (44)],  

a non-Hermitean definition of the electromagnetic − |ri − RI |2 δαδ a ≡ Id . (56)
shielding at nucleus I could be given in terms of
current density induced by the external magnetic (2)
The term Ip equals the corresponding expression
field, Eqs. (48), (49), and (50),
from definition (51) on the l.h.s. of Eq. (30). There-

B 4 fore a cancellation of terms occurs, so that expres-
I
ξ̂αβ = ω−2 d3 rJγ β πδ(r − RI )δαγ
3 sions (51) and (53) become equivalent in the limit of
−5
 exact eigenfunctions to a model Hamiltonian.
− |r − RI | 3(rα − RIα )(rγ − RIγ )


− |r − RI | δαγ .
2
(52)
Conclusions
At any rate, a symmetrized definition, analogous to
that introduced via Eq. (46) is more convenient, i.e., It has been shown that molecular dynamical
 B properties can be described in terms of charge
B 
−2
ω
I
ξ̂αβ = d3 r Jγ β ∇γ EIα + (∇γ EIα )Jγ β . (53) and current densities induced in the electrons by a
2e
perturbing electromagnetic field. The equations of
It can be shown that the two definitions for nuclear classical electromagnetic theory can be used to de-
electromagnetic shielding from Eq. (30), Eqs. (51) fine response properties like the electric shielding
and (53), are equivalent if the hypervirial theorem and the electromagnetic shielding at the nuclei if
for the position operator, Eq. (39), is obeyed. In fact, the density functions have been obtained via quan-
multiplying by ZI ω2 and summing over I on both tum mechanical methods. This approach appears to
sides the definition for electromagnetic shielding, have promise in rationalizing spectroscopical para-
Eq. (53), meters, e.g., atomic polar and axial tensors related to
absorption intensities in vibrational spectroscopies,

N
ω2 I
ZI ξ̂αβ
(1)
(ω)Bβ (0, t) = Ip + Ip + Id
(2)
(54) by means of plots of three-dimensional density
I=1
functions which permit a direct physical picture of

470 VOL. 90, NO. 1


the interaction process taking place in the perturbed
electron cloud.
In the time-dependent case both charge and cur-
rent density fields can be taken into account to
calculate tensor properties, as the corresponding
descriptions are related by simple classical relation-
ships; see Eqs. (31)–(33). However, the numerical re-
sponse obtained within the algebraic approximation
to molecular electronic wavefunctions corresponds
to different formalisms (dipole length, velocity, ac-
celeration, etc.) of radiation theory. Therefore, nu-
clear shieldings calculated in charge or current den-
sity representations would become the same in the
limit of eigenfunctions to a model Hamiltonian, sat-
isfying hypervirial theorems.
ACKNOWLEDGMENTS
Financial support to the present research from the
European research and training network “Molecu-
lar Properties and Materials” (MOLPROP), Contract
HPRN-CT-2000-00013, and from the Italian MURST
(Ministero dell’Università e della Ricerca Scientifica
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
NUCLEAR ELECTROMAGNETIC SHIELDINGS
e Tecnologica), via 60% and 40% funds, is gratefully
acknowledged.
References
1. Hirschfelder, J. O. J Chem Phys 1978, 68, 5151.
2. Lazzeretti, P. Ring Currents; In Prog. Nucl. Magn. Res.
Spectr.; Elsevier: New York, 2000; pp. 1–88.
3. Lazzeretti, P. Adv Chem Phys 1987, 75, 507.
4. Lazzeretti, P. Electric and magnetic properties of molecules;
In Handbook of Molecular Physics and Quantum Chem-
istry; Wilson, S., Ed.; Wiley: Chichester, to be published.
5. Lazzeretti, P.; Zanasi, R.; Stephens, P. J. J Phys Chem 1986,
90, 6761.
6. Epstein, S. T. The Variation Method in Quantum Chemistry;
Academic: New York, 1974.
7. Hansen, A. E. Theor Chim Acta 1970, 16, 217.
8. Hansen, A. E.; Nørby Svendsen, E. Chem Phys Lett 1970, 5,
483.
9. Hansen, A. E. Int J Quantum Chem 1971, 4, 473.
10. Hansen, A. E.; Nørby Svendsen, E. Theor Chim Acta 1971,
20, 303.
471