Topology of Currents

On the Topology of Total and Diamagnetic Induced Electronic Currents in

Molecules
R. J. F. Berger,1, a) G. Monaco,2, b) and R. Zanasi2, c)
1) Fachbereich für Chemie und Physik der Materialien, Paris-Lodron Universität Salzburg,
Jakob-Harringerstr. 2a, A-5020 Salzburg, Österreich.
2) Dipartimento di Chimica e Biologia “A. Zambelli”, Università degli Studi di Salerno,
via Giovanni Paolo II 132, Fisciano 84084, SA, Italia

(Dated: April 21, 2020)

An application of the continuous transformation of the origin of the current density

(CTOCD) scheme to constrain the diamagnetic induced charge current density (Jd ) to
be divergenceless is introduced. This results in a family of Jd fields perpendicular and
proportional to both the gradient of the electron density and the external magnetic field.
Since, in the limit of a complete basis set calculation, the paramagnetic component J p also
becomes divergenceless, we call this scheme CTOCD-DC (CTOCD for Divergenceless
Components). CTOCD-DC allows for a topological characterization of both Jd and J p
in terms of their stagnation graphs. All stagnation graphs of Jd from CTOCD-DC con-
tain the zero points of the gradient of the unperturbed electron density (∇ρ ). In this way
an intimate topological relation between ∇ρ and the diamagnetic current contribution is
revealed. Numerical experiments exemplified by the case of LiNHF in point group sym-
metry C1 , suggest that the corresponding paramagnetic current contributions J p can show
tendencies to accumulate pseudo-stagnation lines in proximity of some kind of the zero
points of ∇ρ . Common zero points of ∇ρ and the total currents are exactly zero points of
the mechanical momentum density.

a) Electronic mail: raphael.berger@sbg.ac.at.; Formerly at Dipartimento di Chimica e Biologia “A. Zambelli”, Uni-

versità degli Studi di Salerno, via Giovanni Paolo II 132, Fisciano 84084, SA, Italia.
b) Electronic mail: gmonaco@unisa.it
c) Electronic mail: rzanasi@unisa.it

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Topology of Currents

I. INTRODUCTION

Molecular magnetic response properties, such as chemical shieldings and magnetizabilities, are
determined uniquely by the current density J = −ej, with −e being the charge of the electron and
j being the probability current density, which was classified by Hirschfelder as a subobservable,
which means that it can be treated like a classical quantity to obtain derived properties.1 Due
to the interest in measuring and computing magnetic properties of molecules, J has been at the
focus of intense research activities for several decades in theoretical and computational chemical
sciences.2,3 The study of molecular magnetism moreover, is also gaining increasing attention in
chemistry due to emerging evidences of a close connection between the magnetic response and the
nature of the chemical bond.3 A classic heuristical argument for such a connection is to be seen
in the existence of phenomena subsumed under the label “aromaticity”, that connect magnetic
properties with certain delocalized chemical bonds. A series of important review articles from
this field is referred to in ref.4 . From our point of view J (or to be more precise J B B, where
the second-rank tensor J B describes the first-order response for any direction of the inducing
magnetic field B) is the central quantity that links electron delocalization and bonding with the
magnetic response. For that we aim at a deeper understanding of the nature of J and its links
to chemical bonds. In particular we report here on our findings about the relation between the
gradient of the ground state electron density (∇ρ ) and J in terms of their topology. Such a relation
will be explored by the introduction of a new scheme of gauge transformations, which in turn leads
to a new scheme of partitioning J into dia- and paramagnetic components, Jd and J p , respectively.

II. THEORY

A. Definitions and basic expressions

The concept of the (non-relativistic) quantum mechanical current density J was introduced
by Schrödinger in 1926 when he found a continuity equation that connects the time derivative
of the n particle charge density with this quantity.5 In presence of a uniform magnetic field this
current density, which is divergenceless by construction, can be written in modern notation, under
neglection of spin, as (see Appendix section V A for further details and definitions)2,6,7

en
J=− ℜ[Ψ|π̂|Ψ], (1)
me

2
Topology of Currents

where n and me are the number and the mass of the electrons, [·] denotes an integration over the
spin coordinates of all electrons and over the spatial coordinates of all electrons except one (this
set of variables is denoted as τ ′ ), the mechanical (or kinetic) momentum operator in SI units (that
is used in this work unless stated differently) is

π̂ = p̂ + eA· (2)

p̂ = −ih̄∇ and A is the magnetic vector potential giving the magnetic field by ∇ × A = B.
A gauge transformation of A and p (with the scalar field f )8

A → A′ = A + ∇ f (r), (3)

p → p′ = p − e∇ f (r), (4)

with the space coordinate r, results in

n
ie
 
′
Ψ → Ψ = ∏ exp − f (r j ) Ψ(r1 , r2 , . . . , rn ). (5)
j=1 h̄

(with the indices j, 1, 2, n referring to single electrons), and conserves the mechanical momentum
π and the current density J, which are thus gauge-independent.8 A static homogeneous B can be
obtained by definition as the curl of the vector potential
1
A = B × r. (6)
2
Setting
1
f (r) = d × B · r (7)
2
in (3) with a constant and otherwise arbitrary vector d results in8
1
A → A′ = B × (r − d), (8)
2
which is a gauge transformation by construction but can be re-interpreted also as a “shift of the
origin” of the vector potential by d. Vector potentials A and A′ , (6) and (8), are both Coulomb-type
vector potentials as ∇ · A = ∇ · A′ = 0.

B. Perturbation theoretic approach

For practicable numerical calculations but also for a theoretical description of the molecular J
field the central task is the determination of the magnetically perturbed electronic ground state Ψ

3
Topology of Currents

in (1). A natural approach to determine Ψ in the presence of B is perturbation theory, since no

relevant magnetic field under terrestrial conditions amounts to more than a small fraction of an
atomic unit (≈ 2.35 × 105 Tesla). The first order perturbing Hamiltonian simplifies by using the
symmetric Coulomb gauge (6) to

ieh̄ e
− (A · ∇ + ∇ · A) = L·B (9)
2me 2me

with the total angular momentum L with respect to an arbitrary (common) origin. Then, using the
conventions of McWeeny,2,9 the first order approximation to the perturbed ground state,

(0) (1)
Ψ0 ≈ Ψ0 + Ψ0 , (10)

is

(1)
Ψ0 = ΨB
0 ·B (11)
(0) (0)
e (0) hΨ j |L · B|Ψ0 i
=
2me h̄ ∑ |Ψ j i
ω j0
, (12)
j6=0

(0) (0)
with the difference of unperturbed state energies E j − E0 = h̄ω j0 .
Furthermore, inserting (10) into (1) and using (6) the conventional partitioning into diamagnetic
(JB B
d ) and paramagnetic (J p ) components for the first order current approximation is obtained

J = JB B
d + Jp (13)
e2 ne
Z
(1)∗ (0) (0)∗ (1)
=− B × r ρ (r) − Ψ0 pΨ0 + Ψ0 pΨ0 d τ ′ , (14)
2me me

where ρ (r) is the probability density.10

By performing a gauge transformation using the gauge transforming scalar function (7) in (1),
which is formally equivalent to a shift of the origin of the vector potential, one obtains the four
terms

J′ = JB d×B
d (r) + Jd (r) + JBp (r) + Jd×B
p (r), (15)

4
Topology of Currents

with

e2
JB
d (r) := − B × r ρ (r) (16)
2me
e2
Jd×B
d (r) := − d × B ρ (r) (17)
2meZ
en (1,L)∗ (0) (0)∗ (1,L)
JBp (r) := − Ψ0 pΨ0 + Ψ0 pΨ0 d τ ′ (18)
me Z
en (1,P)∗ (0) (0)∗ (1,P)
Jd×B
p (r) := − Ψ0 pΨ0 + Ψ0 pΨ0 d τ ′ (19)
me
(0) (0)
(1,L) e (0) hΨ j |L|Ψ0 i
Ψ0 := −
2me h̄ ∑ |Ψ j i
ω j0
·B (20)
j6=0
(0) (0)
(1,P) e (0) hΨ j |P|Ψ0 i
Ψ0 := −
2me h̄ ∑ |Ψ j i
ω j0
·d×B (21)
j6=0
(1) (1,L) (1,P)
Ψ0 = Ψ0 + Ψ0 (22)

and P refering to the total momentum. From the gauge independence of J and (15)

J′ = J = JB B
d (r) + J p (r) (23)

it follows immediately that

Jd×B
d (r) = − Jd×B
p (r), (24)

which holds true for complete basis set calculations, where the off diagonal hypervirial theorem11
for momentum and position (R = ∑i ri ),

ime ω ja h j|R|ai = h j|P|ai , (25)

is fulfilled.

C. Continuous set of gauge transformations

One way to handle the ambiguity of gauge symmetries is to use a specific gauge (i.e. to “fix the
gauge”) to adapt the most convenient algebraic form for a particular computational purpose or for
a physical interpretation.12 For that a high flexibility by gauge symmetry can be desirable. In our
case of the cross product type symmetric Coulomb gauge (vector potential) one is still left with
the choice of the origin (8), that is the free choice of one constant vector d.

5
Topology of Currents

However, more flexibility can be re-introduced by a scheme proposed by Keith and Bader13 which
makes use of the notion that the d independence of J is a local property that holds in every point r
in space separately. This scheme was originally called “continuous set of gauge transformations”.
Any calculation of J by (15) requires a choice of d such that we can write the evaluation of J in a
particular point r as
J = J(r; d(r)) (26)

with a sufficiently well behaved function

d(r) : R3 → R3 (27)

Hereby, the right hand side of (26) has to be interpreted as a family of functions that is indexed
by r via d(r) such that for every point r in space for which J should be evaluated, a different
expression is used. Though this scheme is quite general, there are only few specific realizations
published in the literature. The most important one is probably, the one that is called “continuous
transformation of the origin of the current density - diamagnetic current set to zero” (CTOCD-
DZ)14,15 where, according to Keith and Bader,13 d is set to equal r in every point r, such that the
total current J reduces to the two “paramagnetic” terms

J(r; d = r) =JBp (r) + Jd×B

p (r) (28)
en
Z h i
(1,L) (1,P)
∗ (0)
=− Ψ0 + Ψ0 pΨ0 + c.c. d τ ′ (29)
me
(1,L) (1,P)
with Ψ0 and Ψ0 given by (20) and (21). The importance of this scheme is twofold, for the
one it is for molecular computations with finite basis sets, it is numerically considerably more accu-
rate than a common origin approach, which was the main motivation when it was first introduced,13
but most notably from a purely theoretical perspective it gives rise to symmetry based selection
rules (Steiner-Fowler rules) for the occurrence of dia- an paramagnetic current contributions.16
The second scheme which has been introduced by Lazzeretti and coworkers,17,18 is the “continu-
ous transformation of the origin of the current density - paramagnetic current set to zero” (CTOCD-
PZ) where d(r) is sought such that only the components of the paramagnetic current perpendicular
to the inducing magnetic field vanish and, consequently, replaced by two diamagnetic terms.19 For
the hydrogen atom an analytical solution (in a.u.) is given by d(r) = r − 14 ln(πρ )∇ ln ρ . For
the general n-electron molecular case numerical solutions for d(r) can be found.17 It is worth of
notice that for non-radially symmetric systems one has to expect (paramagnetic) parallel current

6
Topology of Currents

component (w.r.t. the magnetic field), leading to a contradiction in the CTOCD-PZ Ansatz, which
is usually accounted for by restricting it to the remaining two dimensions.
Modifications of the above schemes to shift the origin towards closest nuclei have also been
proposed and are needed to achieve better results for computed nuclear shieldings; they have been
variously called as CSDGT,13 CTOCD-DZ2 and CTOCD-PZ2.20 An evolution of one of these
schemes led to what is now commonly referred to as CSGT.21 To the best of our knowledge a part
from an unrelated very recent refinement of the last method,22 no other schemes for gauge origin
distributions have been suggested in the literature, as yet.

D. Divergenceless dia- and paramagnetic current contributions

The central focus and main idea underlying this work is the introduction of a scheme for con-
tinuous origin shifts (gauge transformations) leading to a divergenceless diamagnetic current con-
tribution. This is in our point of view of utmost importance for two reasons. Firstly, previous
methods of continuous translation of the origin of the current density have been worked out im-
posing analytical conditions either on the dia- or the paramagnetic component, separately. Now,
the most important property – actually the defining property – of the current density is its zero
divergence, and, as it has never been attempted before, it seemed us of fundamental interest to see
which computational scheme satisfies such a property. Secondly, since, as we have lined out in
the introduction, we are interested in the relation between the topologies of the current density and
of the electron density, and the conventional topological characterization in terms of stagnation
graphs is only applicable for divergenceless vector fields, the importance of the Ansatz of a zero
divergence for the diamagnetic current component appears obvious.
In more generality, imposing physical/analytical constraints, separately, on the dia- and param-
agnetic current contributions is a common strategy that leads to a gauge fixing or a partial gauge
fixing and at the same time it can lead by physical interpretation to a particular definition of dia-
and paramagnetic terms.
We were interested in a origin-shifting function d(r) that leads to divergenceless diamagnetic cur-
d×B
rent contributions Jd = JB
d + Jd (see (15))

∇ · [JB d×B
d (r) + Jd (r)] = 0. (30)

Such a choice would imply in the “analytic” (= complete basis set limit) case also divergenceless

7
Topology of Currents

paramagnetic current contributions (∇ · J p = ∇ · JBp + Jd×B

p = 0) due to the linearity of the
divergence operator and since the full currents are divergenceless (∇ · J = ∇ · Jd + ∇ · J p = 0),
as well. With (16) and (17) this leads to a system of equations with the general field-independent
solution (see Appendix section VI A for further details)

d(r) = r − f (ρ )∇ ln ρ (31)

with a sufficiently well behaved and otherwise arbitrary scalar function

f :R→R (32)

that maps the electron density to a real valued function. In particular this means the complete
diamagnetic current density contribution Jd (and noting that ρ > 0) becomes by (31)

Jd =JB d×B
d (r) + Jd (r) (33)
e2
=− (B × ∇ ln ρ ) f (ρ ) ρ (34)
2me
e2
=− (B × ∇ρ ) f (ρ ) (35)
2me
e2
=−∇× F(ρ )B (36)
2me
=∇ × Mind
d (37)

with f = F ′ . These expressions give rise to a series of important interpretative arguments:

• Since the condition (30) is too general for a complete gauge fixing (i. e. a unique definition
of the vector potential distribution), we are left with a considerable freedom of variation
in being able to choose f in (31). A choice of particular significance is f = 0 (or F =
const.) which leads to vanishing Jd in all points in space. This is obviously equivalent to the
CTOCD-DZ Ansatz, that also gives a trivially divergence free Jd

∇ · Jd = ∇ · [JB d×B
d (r) + Jd (r)] = ∇ · 0 = 0 (38)

and consequentially in the analytic case ∇ · J p = ∇ · [JBp + Jd×B

p ] = 0 as well. Hence

CTOCD-DZ is a special case of general gauge origin distributions with divergenceless dia-
and paramagnetic current components. We want to abbreviate these schemes for consistency
with previously established acronyms as CTOCD-DC (=Continuous Transformation of the
Origin of the Current Density for Divergenceless Components).

8
Topology of Currents

• Geometrically (35) means that a divergenceless vector field Jd has to be tangential to elec-
tron density isosurfaces while being at the same time perpendicular to the external magnetic
field B (like any diamagnetic current). While the modulus (= absolute length mod (Jd ) of
Jd ) can be set via f in general to any, sufficiently well behaved, function of the electron
density times the modulus of the electron density gradient ( mod (∇ρ )).

• Constraining Jd and thus J p (in the analytic case) to be divergenceless implies that both
resulting fields will be equipped with the topology of a divergenceless vector field. That
in particular means that the (B direction independent) set of zero points of Jd , which is
also called set of “stagnation points” or “stagnation graph”23 , and which is a fundamental
characteristic of its topology, is, in the generic case of a function f that does not intro-
duce additional zero points, determined only by the condition ∇ρ = 0.24 Such points in a
molecule in turn are the so called bond critical points (BCPs) in Bader’s AIM theory25–27 ,
where they constitute the most important characteristics of the topology of the electron den-
sity. In this way a natural correspondence between the topology of the unperturbed electron
density and the topology of the magnetically induced current density, namely in its diamag-
netic component, is unveiled.

From a physical perspective the result is intriguing: by constraining Jd to be equipped with

the topology of a divergenceless vector field, a direct connection with the topology of the
unperturbed electron density via ∇ρ is obtained.

• Expression (37) gives the physical relation between a magnetic response field Mind
d and the
corresponding magnetically induced current28,29 (Jd ). (36) implies that the divergenceless
diamagnetic currents Jd give rise to a “diamagnetic” magnetisation contribution Mind
d which
is of the form − 2me e F(ρ )B, such that − 2me e F(ρ ) can be interpreted as a (dia)magnetic sus-
ceptibility component that only depends on the unperturbed ground state electron density.

We have undertaken a numerical study for two instances of f . In one case we took the arguably
next simplest choice: f everywhere equal to the constant value α , leading to

e2
Jd = − α (B × ∇ρ ). (39)
2me

We foresee that α would be lower than zero, because, close to any nucleus at RN , ∇ρ is antipar-
allel to (r − RN ) and such a negative value would keep the tropicity of the diamagnetic vortex for

9
Topology of Currents

an isolated closed-shell atom unchanged. This leads to a method which we call CTOCD-GRRO
(after the GRadient of RhO).
The second method is obtained by dimensional analysis, imposing the correct choice of a power
law for f (ρ ) = β ρ n , where β is an adimensional constant, such that [ f (ρ )∇ ln ρ ] = [L]. This leads
2
to f = β ρ − 3 , and

e2 2
Jd = − β (B × ∇ρ )ρ − 3 , (40)
2me

which we call CTOCD-GPRO (after the Gradient and a Power of RhO). The above Jd current co-
incides with the current density approximation obtained by Harris and Cina30 in the framework of
2
a Thomas-Fermi based current density functional theory, if one sets β = −1/6(3π 2 ) 3 = −0.0174.

III. A CASE STUDY

We have studied the current density of a simple asymmetric sample molecule, the ammonia
derivative
We have studied the current density of a simple fully asymmetric sample molecule, the ammo-
nia derivative LiNHF. This unusual un-synthesized molecule qualifies as a convenient test for this
theoretical-oriented paper, because:

1. any coincidence of BCPs and SPs will not be caused by symmetry (a case that we wanted
to exclude in this first investigation);

2. its smallness will simplify the analysis, also in terms of computational efficiency;

3. it contains an interesting spectrum of chemical bonds, both ionic (Li–N and Li–F) and polar
covalent (N–H and N–F).

1. Geometry optimization

To warrant the virial relation between potential and kinetic energy25 we have used a Hartree-
Fock wave function but with a rather large Dunning type aug-cc-pVQZ basis set. Geometry opti-
mization was carried out at this level of approximation obtaining a structure, see Fig. 1, with all
real harmonic vibration frequencies.

10
Topology of Currents

Li

F
N z
y
H
x

Figure 1. Ball-and-stick model of LiNHF showing the orientation of the molecule with respect to the
Cartesian axes after geometry optimization. The point of view is the same as in Figs. 2 and 3. Sticks are
drawn whenever a bond path is found in the gradient of the electron density, as defined within AIM theory.

2. Optimization of α and β parameters

After geometry optimization, we have determined the α and β constants in (39) and (40),
searching for the value which gives simultaneously the best possible calculated 6 Li, 15 N, 1 H, and
19 F magnetic shielding constants with respect to some accurate forecasts.
Shielding constants, i.e., nuclear magnetic shielding tensor average values, have been calcu-
lated as (Einstein implicit sum over repeated Greek indices)
1 I 1
Z
rβ − R I β
σαα = − εαβ γ dV JγBα (r; d(r)), (41)
3 3c |r − RI |3
where RI is the position vector of the Ith nucleus and the components of the second-rank current
density tensor JγBα (r; d(r)) have been determined using, for each spatial point r, the origin dis-
tribution function d(r) which provides the GRRO and GPRO methods. The volumetric integral in
(41) has been computed using the adaptive deterministic method of the NAG library.31
Accurate forecasts for the optimization have been chosen to be the magnetic shielding con-
stants calculated at the same level of theory using the Bragg-Slater atomic size adjusted CSGT-BS
method.22 Owing to the good quality of the basis set, they differ in average only by less than
0.5 ppm with respect to CTOCD-DZ220 results and are almost the same as the standard CSGT21
estimates, see Table I for details and for nuclear shielding constants calculated varying α and β .
When α and β are both vanishing, shielding constants coincide with the CTOCD-DZ values by
definition. For ever larger α and β values the common origin results are obtained.
As can be readily verified, nuclear shielding constants change in strict linear way varying α

11
Topology of Currents

Table I. Nuclear magnetic shielding constants calculated for different values of the α and β constants of
the GPRO and GRRO methods in comparison with CTOCD-DZ2, CSGT, and CSGT-BS results. The mean
absolute error (MAE) is the average over all nuclei of the absolute deviation with respect to the Bragg-Slater
atomic size adjusted CSGT-BS method.
Method α N H F Li MAE

-0.1000 -438.88 4.43 700.97 107.26 23.67

-0.0800 -465.02 4.21 665.04 96.53 5.41
GPRO -0.0748 -471.88 4.15 655.59 93.71 1.44
-0.0700 -478.11 4.10 646.66 91.15 3.99
-0.0600 -491.16 3.98 629.02 85.78 12.98
-0.0400 -517.33 3.76 593.00 75.02 31.16
0.0000 -569.64 3.29 520.71 53.49 67.81

β
-0.0100 -338.11 3.34 1049.38 69.36 137.47
-0.0050 -453.88 3.31 785.06 61.43 44.44
-0.0030 -500.19 3.30 679.39 58.26 20.66
GRRO -0.0026 -509.44 3.30 658.23 57.62 17.84
-0.0020 -523.33 3.30 626.52 56.66 28.99
-0.0010 -546.57 3.29 573.65 55.08 48.41
0.0000 -569.64 3.29 520.71 53.49 67.81

CTOCD-DZ2 -473.26 3.75 657.17 89.90 0.43

CSGT -473.34 3.77 657.14 91.43 0.03
CSGT-BS -473.35 3.76 657.23 91.45 0.00

and β for both GRRO and GPRO methods. Then, the determination of the optimum constants α
and β can be done straight away looking on the regression line for the values which minimize the
mean absolute error (MAE) defined as the average over all nuclei of the absolute deviation with
respect to the CSGT-BS results. Best values turns out to be α = −0.0026a0 and β = −0.0748, for
which the MAE is 17.8 ppm and 1.4 ppm for GRRO and GPRO methods, respectively, reveling
a clear superiority of the GPRO method with respect to the GRRO method, as also confirmed by
the agreement of the individual nuclear shielding constants. Incidentally, we observe that the best

12
Topology of Currents

β value we have found is about 4.3 larger than the Harris and Cina factor30 . The optimum values
found for α and β have been used to obtain the results discussed here in the following.

3. Stagnation graph of the induced current density vector

Since our interest here is manly on the topological features of the magnetically induced cur-
rent density and their connection with the gradient of the electron density, we have calculated
the stagnation graphs of the current density for all three perpendicular principal space directions
(B k x, B k y, B k z, see Fig. 1) using the SYSMOIC package.32 These are shown in Fig. 2 and 3 for
the GRRO and GPRO methods, respectively, reporting from top to bottom the diamagnetic, para-
magnetic and total components for the three directions of the inducing magnetic field by columns.
Stagnation graphs provide a compact representation of the magnetically induced current regimes,
which are, especially in this case lacking of symmetry, very complex to represent using conven-
tional ways. In general, a stagnation graph is formed by a set of stagnation lines and isolated
critical points33,34 which are represented in green/red for diatropic/paratropic vortexes and blue
for saddles, the latter separating homotropic vortexes. This same convention is used in 2 and 3.
Critical points of the density gradient have been calculated and are shown in Fig. 2 and 3 by
magenta crosses over the interatomic curves (in black) of the molecular graph;26 they are four
BCPs (three between the central nitrogen and the three substituents, and one between Li and F),
and a ring critical point (RCP) amidst Li, N and F.

4. Discussion

As a first observation we note that, of the 6 stagnation graphs (SGs) of the total current com-
puted for this molecule, three orientations of the magnetic field for each of the two schemes, not
even a single critical point is found. This might in part be ascribed to the existence of a non-
zero parallel component of the induced current (also called “non-classical component”), which is
generally found to vanish only for symmetry reasons or at infinity. On the other hand, the pseudo-
stagnation graphs (pseudo-SG), which neglect that component, turns out rather rich in centre and
saddle lines, and can be profitably used to model the main features of the current density field.34–36
In the following, we will examine the SGs or pseudo-SGs obtained for the diamagnetc, paramag-
netic and total current, for the methods of calculation CTOCD-GRRO and CTOCD-GPRO, given

13
Topology of Currents

Figure 2. Pseudo stagnation graphs of LiNHF at HF/aug-cc-pVQZ level of theory for the GRRO method,
superposed to the molecular graph. Each column corresponds to a different orientation of the magnetic
field, from left to right B is parallel, respectively, to x, y, and z Cartesian axes as shown with atom positions
in Fig. 1. From top to bottom DIA, PARA, and TOTAL, respectively. Magenta crosses mark bond critical
points and the ring critical point (∇ρ = 0) over the black curves of the molecular graph. Green/red lines
are for diatropic/paratropic stagnation lines, whilst blue lines are for saddle stagnation lines of the current
field.

14
Topology of Currents

Figure 3. Stagnation graphs of LiNHF for the GPRO method. See Fig.2 caption for details.

in Figs. 2 and 3, respectively.

Starting from the pseudo-SG of Jd (which coincides with the SG since the parallel component is
zero by definition) we can observe that, in agreement with Eqs. 39 and 40, it is the same for the
two methods and has stagnation lines passing through all critical points of ∇ρ : the BCPs and
the RCP. An intersection of the three stagnation graphs of Jd for the three orientations of B, thus
yields exactly the BCPs and the RCP (as well as the atoms). The stagnation lines passing through

15
Topology of Currents

BCPs are either of saddles (blue) or of diatropic vortex type (green), while those passing through
the RCP are either of saddle or of paratropic vortex type (red).

Table II. Distances in au of the four bond critical points and the ring critical point from the nearest stagnation
line of the pseudo-current density, computed for three orthogonal directions of the perturbing magnetic field.
Stagnation lines formed by saddles, diatropic centres, and paratropic centers are indicated as (s), (d) and
(p).
CP GPRO GRRO

x y z x y z
N–F 1.17 (p) 0.20 (d) 1.14 (s) 1.17 (p) 0.20 (d) 1.14 (s)
N–Li 0.74 (s) 0.49 (s) 0.85 (s) 0.71 (s) 0.45 (s) 0.83 (s)
Li–F 0.27 (s) 0.23 (s) 0.22 (s) 0.49 (s) 0.35 (s) 0.40 (s)
N–H 0.21 (p) 0.72 (d) 0.30 (d) 0.21 (p) 0.72 (d) 0.29 (d)
RCP 0.44 (s) 0.43 (p) 0.62 (s) 0.39 (s) 0.29 (p) 0.43 (s)

In contrast to the pseudo-SG of Jd , the pseudo-SG of the paramagnetic currents J p is not ex-
pected to be identical for different CTOCD-DC methods. This is confirmed by the comparison
of the three subfigures in the second row of Fig. 2 and Fig. 3, for the CTOCD-GRRO and the
CTOCD-GPRO method, respectively. In both cases, the stagnation lines pass the BCPs in some
non-zero distance.
The pseudo-SGs of the total current obtained with the two methods have strong similarities close
to atoms, but disagree far from them, which is a residual effect of the finiteness of the basis set
(bottom lines of Fig. 2 and 3).
As could be expected from previous studies,33,35 the center stagnation lines pass through atoms,
and this implies the occurrence of saddle stagnation lines passing between atoms. However, in
most cases the saddle line remains in a finite distance from the BCP; this is particularly true for
the ring critical point which is generally not located on a stagnation line. To have a quantitative
indication, we have computed the shortest distances from the pseudo-stagnation lines to BCPs and
RCP, see Table II. The shortest average distance is found for Li-F bond. This has some mean-
ing considering that, according to the AIM theory, both ionic bond and the previously studied
H-bonds36 are closed-shell interactions. Cases where stagnation lines pass close to a BCP are: a

16
Topology of Currents

center diatropic vortex line near by the BCP on the F-N bond-path and a paratropic vortex line
close to the BCP of the N-H bond. However, these values are found only for a specific direction
of the perturbing field.
Summarizing our computational results, BCPs of the electron density belong only to the stagna-
tion graph of the diamagnetic component of the current density vector for any orientation of the
inducing magnetic field. In other words, varying the orientation of the inducing magnetic field the
stagnation points forming the stagnation graph of the diamagnetic component change except those
points which coincide with a BCP (and the nuclei). This is not true for any point of the pseudo
stagnation graph of the paramagnetic component in this sample case. The paratropic stagnation
graphs are intentionally visualized to show the lack of any coincidence in a case with no symme-
try elements at all. Moreover, it is remarkable that CTOCD-GRRO and CTOCD-GPRO provide
two different diamagnetic current density vector fields having the same identical stagnation graph,
which, when added to the two fully nonequivalent CTOCD-GRRO and CTOCD-GPRO paramag-
netic fields, provide exactly the same total current density vector field in the limit of a complete
basis set calculation, irrespective of the approximation used to obtain the wavefunction. In gen-
eral, the occurrence of a BCP on the SG of the total current density implies a zero point of the
mechanical momentum density
π = [Ψ|π̂|Ψ] (42)

(see eq. (1) for definitions) since the real part of π is proportional to the current density,6 while its
imaginary part
e
ℑ(π) = − ∇ρ (43)
2me
is proportional to the gradient of the electron density. This special condition can occur for symme-
try determined positions, e.g., a position in the centre of symmetry in higher point group symmetry
that constrains both the gradient of the electron density and the current density to be equal zero at
the same time.
The partitioning of the current density described in this paper can help understanding the occur-
rence of less stringent conditions, i.e. BCPs close to critical points, such as those found in unpolar
covalent bonds, ionic contacts or hydrogen bonded systems.36 A close position of the critical
points of the two fields ∇ρ and J can be understood assuming the existence of a function f (ρ )
that yields Jd ≃ J, i.e. such that the paramagnetic contribution is just a small term, at least in a
small region around the BCP. In such instances it would then be possible to write approximations

17
Topology of Currents

of the current density solely in terms of the electron density, as are indeed those proposed within
the Thomas-Fermi current density functional theory.37

IV. CONCLUSION

We have developed a family of schemes for continuously distributing the origin of the mag-
netically induced current density (i. e. the gauge origin) such that the dia- and (in the complete
basis set limit) the paramagnetic part (Jd and J p ) of the current density become independently
divergenceless. We call this family of schemes CTOCD-DC, andthe CTOCD-DZ method is a
special case thereof. In addition, the Thomas-Fermi based current density functional theoretic ap-
proximation to the current densities is of the same form as Jd in the CTOCD-DC variant which
we call the CTOCD-GPRO method. The divergence free vector fields Jd and J p in general are
consistently accessible to a topological analysis in terms of their stagnation graphs. While the
stagnation graphs of Jd for all three principal directions of the magnetic field are strictly intersect-
ing at the positions of atoms or zero gradient of the electron density independently of the particular
CTOCD-DC scheme, the stagnation graphs of J p are method dependent. The zero points of ∇ρ
and J, which correspond to the imaginary and real part of the mechanical momentum density, do
not have to coincide, apart for symmetry reasons. However, here and elsewhere36 cases have been
found where they approach each other. No general quantitative relation between the two could be
established as yet38 , but it seems a worthy goal for further investigations.

DATA AVAILABILITY

The data that supports the findings of this study are available within the article.

ACKNOWLEDGMENTS

RB acknowledges Prof. Dr. Paolo Lazzeretti (Modena), Richard Bader† , and Prof. Dr. Andrzej
Herczyński (Boston) for fruitful discussions, the University of Salerno for hosting RB and Prof.
Dr. Nicola Hüsing (both from the University of Salzburg) and the University of Salzburg for
generously supporting his research activities.

18
Topology of Currents

V. DEFINITIONS AND EXPRESSIONS FOR J

A. Conventional definition

For convenience we use atomic units in this section. The current density is usually defined as
the real part of the mechanical momentum density, this can be written (for the spin free case) like

J =ℜ{π̃ } (44)

with the mechanical momentum density

Z
π̃ = Ψ∗ (r, r2 . . . , rn )π̂ Ψ(r, r2 , . . . , rn )dr2 . . . drn (45)

where we have used the mechanical momentum operator π̂ defined in (2). This can be rewritten
by using d τ ′ := dr2 . . . drn as integration variable like
Z
π̃ = Ψ∗ (r, r2 . . . , rn )π̂ Ψ(r, r2 , . . . , rn )d τ ′ (46)

or even shorter by abbreviating ·d τ ′ = [·] as

R

π̃ =[Ψ∗ π̂ Ψ] (47)

=:[Ψ|π̂ |Ψ] (48)

which was used in the Introduction section.

B. Reduced density matrix formalism

Another possibility for formulating the current density arises from using the one-particle re-
duced density matrix (1-RDM) formalism. The 1-RDM can be defined, by using the above intro-
duced [·] convention as

ρ (r, r′ ) :=[Ψ∗ (r, r2 . . . , rn )Ψ(r′ , r2 . . . , rn )]. (49)

Then the current density is given by

J(r) =ℜ{π̂ρ (r, r′ )}r′ =r (50)

19
Topology of Currents

C. Operator formalism

The current density in a specific point r0 can be expressed as the expectation value of the
anticommutator1,2

J̃ =π̂δ (r − r0 ) + δ (r − r0 )π̂ (51)

={π̂ , δ (r − r0 )}+ , (52)

yielding

J(r0 ) = hΨ|J̃|Ψi (53)

= hΨ|{π̂ , δ (r − r0 )}+ |Ψi (54)

This gives according the Hirschfelder1 rise to the interpretation of J as a "subobservable".

VI. SOLVING EQUATION (30)

A. The general solution

Eq. (30) in explicit form is given by

e2
 
∇· − (B × (r − d)) ρ =0 (55)
2me
which evaluates to

[ρ (∇ × (r − d)) + ∇ρ × (r − d)] · B =0 (56)

If this should hold for any possible choice of the magnetic field B, obviously

ρ (∇ × (r − d)) + ∇ρ × (r − d) =0 (57)

has to hold. In attempting to solve (57) for

v := r − d, (58)

we observe that

• if v1 is solution and v2 is a solution, a linear combination of v1 and v2 is a solution as well

• v = ∇ρ is a special solution

20
Topology of Currents

• v = ∇(ρ n ) for all n > 0 are solutions

• thus any (converging and sufficiently well behaved) power series in ρ is a solution

We conclude that v = ∇G(ρ ) with all (sufficiently well behaved, e.g. differentiable) G(ρ ) with

G:R→R (59)

are solutions for (57). In addition it can be easily seen, that if v contains non-zero components
perpendicular to ∇ρ , eq. (57) cannot be fulfilled in the general case and of a general non-zero
magnetic field (thus the "field direction independent case") B and for a general density function ρ .
Thus we have shown that all (sufficiently well behaved) solutions v of eq. (57) are exactly of the
∂G
form ∇(G(ρ )), with G : R → R. Then using f (ρ ) := G′ (ρ )ρ = ∂ρ ρ in (58) yields

d = r − f (ρ )∇ ln ρ , (60)

which is (31) introduced in subsection II D.

B. Exemplary cases for f (ρ )

1. f (ρ ) = 0 yields Jd = 0. This is the known CTOCD-DZ scheme,2 that formally as well

yields a zero, thus divergenceless Jd .

2. f (ρ ) = 1 yields

e2
Jd = − (B × ∇ρ ) (61)
2me

We note that in order to obtain physically correct units a constant (α ) of the dimension of
e 2
m2 has to be introduced, leading to Jd = −α 2m e
(B × ∇ρ ). This scheme is called in the
discussion section CTOCD-GRRO.

3. f (ρ ) = ρ yields
e2
Jd = − (B × ∇ρ ) ρ (62)
2me
We note that in order to obtain physically correct units a constant (β ) of the dimension of
e 2
m5 has to be introduced, leading to Jd = −β 2m e
(B × ∇ρ ).

21
Topology of Currents

2
4. f (ρ ) = ρ − 3 yields
e2 5
Jd = − (B × ∇ρ ) ρ − 3 (63)
2me

In this scheme already the correct physical units are obtained, it is called CTOCD-GPRO.
The general CTOCD-DC Ansatz however, still allows for the scaling with a dimensionless
constant. This constant is called β in the discussion section. One can choose as we have
done a constant such that any magnetic property of choice is numerically optimally de-
scribed by only the diamagnetic current contribution. We have chosen in this case chemical
shieldings for the LiNHF example. This results in β = −0.0748 (using atomic units for Jd ).

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