Copyright © 2016 American Scientific Publishers Journal of

All rights reserved Computational and Theoretical Nanoscience

Printed in the United States of America Vol. 13, 1–7, 2016

Identification of the Rydberg Interatomic Potential for

Problems of Nanotechnology
C. R. Kikawa∗ , T. N. Malange, M. Y. Shatalov, and S. V. Joubert
Department of Mathematics and Statistics, Tshwane University of Technology, Republic of South Africa

Methods like the maximum likelihood and Newton’s iterative techniques are usually employed to
estimate the parameters of the classical Rydberg interatomic potential function. However, such
approaches require initial guess values (IGV) to compute the optimal solutions of the unknowns.
In this work, a multiple objective function approach that is used to compute the parameter estimates
via the least-squares method is presented. The new approach does not necessitate the uniqueness
and existence of the initial guess values to compute the required estimates. The classical Rydberg
interactomic potential is firstly considered as a general solution of a second order linear differential
equation with constant coefficients. Secondly, the characteristic equation of the general solution of
the potential function is formulated and it’s constraints derived. Two objective functions are con-
structed from the assumed ordinary differential equation. The first objective function is constrained
and selected parameters are estimated using the least-squares method and the second objective
function is directly minimised by formulating normal equations that can be solved for exact solu-
tions of the unknowns. The new method and the computer algebraic system (CAS) are tested using
experimental datasets of copper, silver ions and silver-copper alloy. Estimates from both approaches
are compared and used to construct potential energy curves of the atoms considered. Three poten-
tial surfaces, that is, for experimental data, new method and the CAS for each atom are plotted on

RESEARCH ARTICLE
the same axis for better comparison. It is observed that estimates from the new method are greater
in absolute terms than those from the CAS. However, all the estimates have the same direction.
The potential curves from the experimental data, the new method and the CAS all have the same
shape and close to each other, especially at the minimum of the potential well and at that point
they are all indistinguishable. Estimates from the new method can be trusted as they produce a
potential curve that is close to that of the experimental data and the CAS. As the present iterative
methods usually converge to the required solutions given “good” IGVs, it is proposed that the new
method be used symbiotically with the present methods to systematically compute the necessary
IGVs. Hence the new method can be used in both theoretical and practical applications to estimate
parameters of the Rydberg potential function since it does not require provision of IGVs to the
unknown parameters.
Keywords: Parameter Estimation, Least-Squares, Interatomic Potentials, Rydberg potential.

1. INTRODUCTION These concepts could be better explained by assuming that

Nuclear motion and the separation of nuclei as well as the
formulation of a successful potential energy surface were
first examined by Born and Oppenheimer.1 Modern theo-
ries seldom take into consideration the method of Born and
Oppenheimer—however these theories are still referred to
as Born-Oppenheimer approximations and potential energy
surfaces.1
The concept of a potential energy surface is fundamental
to both quantum mechanics and the semi classical inter-
pretation of molecular energy states and dynamic systems.
∗
Author to whom correspondence should be addressed.
electronic vibrations are more vigorous than nuclear vibra-
tions. Surfaces consisting of the potential energy against
inter-atomic distance form an appropriate way of exhibit-
ing the energy levels of diatomic molecules.2 Tradition-
ally potential energy surfaces were fitted to data using the
classical Morse or the Lennard-Jones potential functions.
However, due to a poor fit, modifications on the method by
Rydberg were developed. Such methods allow the numer-
ical calculation of more reliable potential surfaces over
the range for which spectroscopic data sets are obtained.
In the past, several researchers have made attempts to
numerically derive series solutions for computing potential

J. Comput. Theor. Nanosci. 2016, Vol. 13, No. 7 1546-1955/2016/13/001/007 doi:10.1166/jctn.2016.5331 1

 Identification of the Rydberg Interatomic Potential for Problems of Nanotechnology
energy surfaces from the conventional spectroscopic con-
G1
n
stants. However, these calculations were only utilised for
2 i=1
the lowest part of the potential surface because it was sus-
pected that they were inaccurate for “higher portions” of
G1
n
the potential surface.2, 3
 i=1
In this study a simpler analytical method that depends
on the minimisation of two objective functions is derived.
The objective functions are minimised using the ordinary
least squares (OLS) approach to estimate the required
unknown parameters. The estimated Rydberg function is
used to fit potential energy surfaces of known states of
molecular ions of copper and silver. An attempt has been
made to use all information available to fit the curves, not
only to the lower point at the potential well, but to a broad
length of the curve involved. The fit from the proposed
method compares well with those generated by the com-
puter algebraic system (CAS) and the experimental results.
2. THEORY
Several studies that provide information about the vari-
ous parameters of the Rydberg function have been con-
ducted.1, 4–6 However, these methods have all tended to
use spectroscopy, kinetics experiments as well as quantum
mechanical electronic ????electronic???? computations.1, 7
In some cases numerical methods are also employed since
the Rydberg function usually presents equations that are
not easy to solve analytically.
In the present work, one form of the generalised
RESEARCH ARTICLE
Rydberg potential function is considered
E
r = 1 e−r + 2 re−r =
1 + 2 re−r (1)
which is a slight modification of that used by Ref. [8]
where i for i = 1 2;  are the function constants for a
given solid which are to be approximated and r is the inter-
atomic separation. The modified Rydberg function (see
Eq. (1)) is the same as that studied by Ref. [9], although
this fact took several years to be recognised.10
2.1. Present Estimation Approach
To approximate the Rydberg potential function, it is always
assumed that the experimental data-set, say ri  Ei  with
Ei = E
ri  for i = 1     n is obtainable and n consists of
all experimental data points.
Firstly, an objective function from Eq. (1) is con-
structed as
1
n
G1
 =
 e−ri + 2 re−ri − Ei 2 (2)
2 i=1 1
where = 1  2 and  a collection of distinct parameters
in Eq. (1)
Secondly, partial derivatives with respect to the
unknown parameters in Eq. (2) are derived as
G1
n
Kikawa et al.
=
1 e−ri + 2 ri e−ri − Ei ri e−ri = 0 (4)
=
1 e−ri + 2 ri e−ri − Ei 
×
−1 e−ri − 2 ri e−ri  = 0 (5)
Observing Eqs. (3)–(5), it is noticed that they can not be
explicitly solved to obtain exact solutions for the unknown
parameters. At this point the methods presently in use
employ iteration routines which require starting approx-
imations for the unknowns. Hence initial approximation
problems arise. A question arises:
Which are the best approximations that will guarantee
convergence to the required solution?
For those interested in using numerical techniques that
employ iteration routines, the approach presented below
could be used to answer this question.
3. RATIONALE
Majority of the current mathematical software like Math-
cad, MATLAB, Maple, etc. can not carry out direct mini-
mization of objective functions with out the user providing
initial guess values (IGVs). Hence, it is a challenge to both
new and experienced users to always provide logical IGVs
that guarantee convergence to the optimum solution. From
reviewed literature there is no documentation on how to
compute IGVs systematically and algorithmically.
The main aim of this work is to propose a regular
approach for computing IGVs that will always guarantee
convergence to the optimal solution. However, the values
from the proposed method may not be “accurate” solutions
to the transcendental problem as they contain errors that are
due to the numerical differentiation approach used.11 It is
also noted from literature, that Lim 5 used local approxi-
mations to obtain estimates the extended Rydberg. In this
study, we approximate the parameters globally in a broad
range of distances and construct the potential energy curves
not only at the minimum but at a wider domain.
4. PROCEDURE
A knowledge of ordinary differential equations (ODEs)
prompts us to observe that Eq. (1) is the general solution
of a second order ODE of the form
d2E dE
+ 2 + 2 E = 0 (6)
dr 2 dr
which is linear with respect to the unknown coefficient 
and whose characteristic equation is

 + 2 = 0 (7)
Equation (6) is re-parameterised in order to have linear
coefficients, hence
d2E dE
=
1 e−ri + 2 ri e−ri − Ei e−ri = 0 (3) + 1 + 2 E = 0 (8)

1 i=1 dr 2 dr
2 J. Comput. Theor. Nanosci. 13, 1–7, 2016
Kikawa et al. Identification of the Rydberg Interatomic Potential for Problems of Nanotechnology

where i for i = 1 2 are parameters determined by . The parameter  is unknown and, for simplicity, i
Hence for i = 1 2 can be written as functions of  since the
1 = 2 and 2 = 2 (9) design matrix in Eq. (15) is assumed to be invertible.12
Hence,
The constraint, characterised by the coefficients in Eq. (8),
⎡ n     ⎤−1
is constructed as
⎡ ⎤
dEi 2
n
dEi


1  2  = 21 − 42 = 0 1
 ⎢ 2 + dri
Ei
dri ⎥
⎦=⎢ ⎥
(10)
⎣ ⎢ n
i=1
 
i=1
⎥
2
 ⎣
dEi
n ⎦
4.1. Objective Functions Ei
Ei 2
i=1 dri i=1
As mentioned in Section 1, the estimation process involves
⎡ n  2  ⎤
the construction of two objective functions that are
dEi d Ei
employed to approximate the unknown parameters using ⎢− dri2 ⎥
⎢ i=1 dri ⎥
the OLS approach. The first objective function is con- ×⎢   ⎥ (16)
⎣
n
d 2 Ei ⎦
structed in order to approximate 1  2   and  and the
second is to approximate the Rydberg constants 1 and 2 .
4.2. First Objective Function
In this case, a data set such as that mentioned in
Section 2.1 is assumed to be obtainable. The OLS
approach is used to minimise Eq. (8) and hence the con-
strained Rydberg function is constructed as
n  2 2
4 − Ei
i=1 dri2
In order to apply methods that use the linearity con-
cept to identify the unknowns in given functions, we firstly
decrease the dimensional space of the unknown parameters
from three to one, see Eq. (17). Therefore, the constraint
see Eq. (10) can be formulated as
1
d Ei dEi
1
2 − 42
 = 0 (17)
G1
1  2   = +  1 +  E
2 i
2 i=1 dri2 dri
+ 
21 − 42  (11) which is used to estimate the value of . Using
the OLS approach, Eq. (15) is employed to compute
where, Ei = E
r = ri , dEi /dri = dE/drr=ri and 1 and 2 .

RESEARCH ARTICLE
d 2 Ei /dri2 = d 2 E/dr 2 r=ri . Deriving the partial derivatives
of the constrained Rydberg function (see Eq. (11)) with
respect to 1  2 and , we obtain 5. ANALYSIS
n  2  In this section some numerical computations are performed

G1
d Ei dEi using experimental data-sets obtained from Ref. [13]. The
= +  1 +  E
2 i

1 i=1 dri2 dri CAS Mathematica is applied to perform all computations
dEi in this study. The pair interactions of copper, silver and
× + 21 = 0 (12) a copper–silver alloy are considered for numerical eval-
dri
uation. It should be noted that, parameters containing a
n  2 

G1
d Ei dEi “hat” indicate that their respective values are not exact, but
= + 1 + 2 Ei Ei − 4 = 0 (13) simply estimated values.

2 i=1 dri2 dri

G1
= 21 − 42 = 0 (14) 5.1. The Copper Atom Parameters

 The data obtained by observing the motion of copper
The matrix representation for Eqs. (12) and (13) is atoms is analysed here. Applying Eq. (16) to the experi-
⎡ n    ⎤ mental data recorded in Ref. [13] and making the neces-

dEi 2
n
dEi
⎢ 2 + Ei ⎥
 sary algebraic simplifications we obtain
⎢ dri dri ⎥ 1
⎢ i=1
 
i=1
⎥ ⎡ ⎤
⎢

⎥ 1

⎣
n n
dEi ⎦ 2
Ei
Ei 2 ⎣ ⎦
i=1 dri i=1
 2  ⎤ 2

⎡
n
dEi d Ei ⎡ 96305312+76151
−274925+4 ⎤
−
⎢ dri2 ⎥
⎢ i=1 dri ⎥ ⎢ 13309156+42390 ⎥
=⎢  2 ⎥ (15) =⎢ ⎥ (18)
⎣
n
d Ei ⎦ ⎣ 346008618+
90153+2
−274925+4 ⎦
4 − Ei
i=1 dri2 13309156+42390
J. Comput. Theor. Nanosci. 13, 1–7, 2016 3
 Identification of the Rydberg Interatomic Potential for Problems of Nanotechnology Kikawa et al.

It is clear that Eq. (18) represents solutions for 1 and 5.3. Copper–Silver Alloy Parameters
2 in terms of . Substituting these solutions into Eq. (17) For copper–silver alloy parameters, applying Eq. (16) to
yields the experimental data recorded in Ref. [13] and making
 2 the necessary algebraic simplifications we obtain
96305312+76151
−274925+4 ⎡ ⎤
13309156+42390 1

  ⎣ ⎦
346008618+
90153+2
−274925+4 2

−4
13309156+42390 ⎡ ⎤
92944606+855338
−395526+4
=0 (19) ⎢ ⎥
10023287+40265
=⎢ ⎥
⎣ 394882260+
861267+2
−395526+4 ⎦
with the real solution
10023287+40265
 = 3339 (25)

To obtain estimates for 1 and 2 , substitute the real solu- The real solution for
tion of  into Eq. (18). Hence
 = 15564



ˆ1 5679
= (20) and the estimated values for 1 and 2 which satisfy the
ˆ2 8063 constraint in Eq. (10) are



The values of 1 and 2 clearly satisfy the constraint ˆ1 6051
in Eq. (10). Now  in Eq. (6) can be estimated using the = (26)
ˆ2 9152
representations given in Eq. (9) as follows
The value for  is thus estimated as
1 
ˆ = = 2 = 2840 (21)  
2 ˆ = 1 = 2 = 3025 (27)
2
5.2. Silver Atom Parameters
RESEARCH ARTICLE

In this section the pair interactions of silver atom data are 6. SECOND OBJECTIVE FUNCTION
considered. Applying Eq. (16) to the experimental data The aim of this formulation is to estimate the the Rydberg
recorded in Ref. [13] and making the necessary algebraic constants, that is, 1 and 2
simplifications we obtain
⎡ ⎤ 1
n

⎡ ⎤
1268314+1469
50987+4 G2
1 2  =
 e−r
ˆ i
+2 re−r
ˆ i
−Ei 2 (28)
1
 2 i=1 1
⎢ 195580+18019 ⎥
⎣ ⎦=⎢ ⎥
2
 ⎣ 206835+
21948+2
50987+4 ⎦ The partial derivatives of Eq. (28) with respect to the
195580+18019 constants are
(22)
G2
n
=
1 e−r
ˆ i
+2 ri e−r
ˆ i
−Ei e−r
ˆ i
=0 (29)

1 i=1
The solutions of  from Eq. (22) are substituted into

G2
n
Eq. (17). The real solution is =
1 e−r
ˆ i
+2 ri e−r
ˆ i
−Ei ri e−r
ˆ i
=0 (30)

2 i=1
 = 268367
Equations (29) and (30) are presented in matrix form
The value of  is then substituted into Eq. (22) to obtain as done earlier in Section 4.2, see Eqs. (15) and
(16). Further applying experimental data,13 the parame-



ˆ1 5571 ter estimates for the studied atoms are as presented in
= (23) Sections (6.1, 6.2, and 6.3).
ˆ2 7759
6.1. The Copper Potential
The solutions in Eq. (23) satisfy the constraint in Eq. (10)
The Rydberg function constants for the copper atom are,
and  can be calculated using Eq. (9), as



ˆ1 2058427
1  = (31)
ˆ = = 2 = 2786 (24)
2 ˆ2 −903918

4 J. Comput. Theor. Nanosci. 13, 1–7, 2016

Kikawa et al. Identification of the Rydberg Interatomic Potential for Problems of Nanotechnology

When the results of Eqs. (21) and (31) are substituted Substituting estimates from Eq. (37) into Eq. (1), the
into Eq. (1), the potential for the copper atom is then con- estimated Copper potential function is
structed explicitly as
E
r = 1 e−r +2 re−r
E
r = 1 e−r +2 re−r
=
1513835−663335re−2719r (38)
=
2058440−903918re−2480r (32)
7.2. Silver Atom Parameters and Potential Function
6.2. The Silver Potential
The silver atom parameter estimates computed using the
The constants due to the silver atom are,


 CAS are ⎡ ⎤ ⎡ ⎤
ˆ1 4991876 ˆ1 777002
= (33) ⎢ ⎥ ⎢ ⎥
ˆ2 −1886726 ⎢ ˆ ⎥ = ⎢ −302134 ⎥ (39)
⎣ ⎦ ⎣2 ⎦
On substitution of the results from Eqs. (24) and (33) ˆ 2268
into Eq. (1), the potential for silver is explicitly Substituting estimates from Eq. (39) into Eq. (1), the
E
r = 1 e−r +2 re−r estimated Silver potential function is
=
1336924−506422re−2786r (34) E
r = 1 e−r +2 re−r

6.3. Copper–Silver Potential =
2326580−885148re−2557r (40)

The constants of the Rydberg function due to the copper–
silver alloy are, 7.3. Copper–Silver Alloy Parameters and


 Potential Function
ˆ1 5257618
= (35) Parameter estimates of the Copper–Silver alloy calculated
ˆ2 −2122751 by CAS ⎡ ⎤ ⎡ ⎤
ˆ1 1050418
Substituting the results of Eqs. (27) and (35) into ⎢ ⎥ ⎢ ⎥
⎢ ˆ ⎥ = ⎢ −419046 ⎥ (41)
Eq. (1), the potential for the copper–silver alloy is ⎣ 2⎦ ⎣ ⎦
explicitly ˆ 2426

RESEARCH ARTICLE
E
r = 1 e−r +2 re−r
Substituting estimates from Eq. (41) into Eq. (1), the
=
5257618−2122750re−3025r (36) estimated Copper–Silver alloy potential function is

E
r = 1 e−r +2 re−r

7. COMPUTER ALGEBRAIC
SYSTEM (CAS) RESULTS =
1050418−419046re−2426r (42)
The commercial program Mathematica was used as the
computer algebraic system (CAS) to compute the optimal 8. GRAPHICAL REPRESENTATION OF
values of the unknowns in the non-linear Rydberg poten- THE ESTIMATED POTENTIALS
tial model, using the experimental data-set by provided In this section, schematic illustrations of potential energy
by Ref. [13] for the respective metal atoms considered. curves of the diatomic molecules of Copper and Silver are
In this section, the Rydberg constants as computed using presented. It must be well understood that the region of
the CAS are presented. Models of the interactions of the
atoms involved are studied and constructed.
U(r), UU[r], UUU[r]

7.1. Copper Atom Parameters and Potential Function 0.2

The Copper atom parameters as computed from the CAS.

Unlike other mathematical software that require IGVs to 0.1
solve transcendental problems, the mathematica program
did not require IGVs to minimise the objection function r
2.5 3.0 3.5 4.0 4.5 5.0
is Section 2.1 see, Eq. (2). This could be attributed to the
programming differences in the different software. –0.1
⎡ ⎤ ⎡ ⎤
ˆ1 1513835
⎢ ⎥ ⎢ ⎥
⎢ ˆ ⎥ = ⎢ −663335 ⎥ (37)
–0.2
⎣ 2⎦ ⎣ ⎦
Fig. 1. Potential energy curves from the experimental data (blue), least-
ˆ 2719 squares (orange) and CAS (green) estimation methods for copper atom.

J. Comput. Theor. Nanosci. 13, 1–7, 2016 5

 Identification of the Rydberg Interatomic Potential for Problems of Nanotechnology Kikawa et al.

U(r), UU[r], UUU[r] Table I. Rydberg constants estimated using two approaches, least-
squares (LS) and the computer algebraic system (CAS-mathematica)
methods.
0.2
LS method estimates CAS method estimates
0.1 Atoms ˆ1 ˆ2 ˆ ˆ1 ˆ2 ˆ


Cu–Cu 2058.427 −903918 2.840 1513840 −663.335 2.719

r
3.0 3.5 4.0 4.5 5.0 Ag–Ag 4991.876 −1886726 2.786 777002 −302.134 2.268
Cu–Ag 5257.618 −2122751 3.025 1050418 −419.046 2.426
– 0.1

compare well with those constructed using both experi-

Fig. 2. Potential energy curves from the experimental data (blue),
least-squares (orange) and CAS (green) estimation methods for
silver atom.
attractive potential energy surfaces is usually the region
at the minimum or at the potential well,14 and several
approximation methods aim at obtaining accuracy of their
estimates at the minimum. In the present least-Sqaures
approach, accuracy is attained over the entire domain of
the potential surface, see Figures 1–3. It should be noted
that in all the figures, U
rUU rUUU r = E
r.
From the potential energy curves illustrated in
Figures 1–3, the height of the potential well forms
the equilibrium bond energy of the ground state of
the atoms.
9. RESULTS AND DISCUSSION
RESEARCH ARTICLE
mental and CAS methods. It can be noted that, the esti-
mated Rydberg constants in Table I are not exactly equal;
in future work we hope to investigate the errors due to
the proposed method and other commonly used estimation
methods. From the presented results, the proposed method
can be applied in real world problems to construct con-
stants of the Rydberg potential function in nanotechnology
applications.
10. CONCLUSION
In the present work, the idea is to decrease the dimen-
sional space of the unknown parameters in the potential
function. This enables the application of the well known
least-sqaure method used to estimate the unknown param-
eters in the function. In principle, we can use this approach
to approximate any potential with several unknown param-
eters. In the first stage, the multiple objective functions are

In Table I, the estimates of the Rydberg constants are pre-
sented. These were computed using two approaches, the
least-squares and the built in computer algebraic system
(CAS-Mathematica). Methods for solving nonlinear prob-
lems do exist,15 however, these use iteration approaches
that require initial approximations to compute the opti-
mal solutions of the unknown parameters in the nonlin-
ear functions.15 In the present work, a multiple objective
function (least-squares) method is proposed and used to
compute estimates of the Rydberg function without requir-
ing initial approximations. From Figures 1–3 it is observed
that the proposed method provides potential curves that
formulated, these objective functions are used to solve for
the unknown parameters by constant minimisation. Hence,
the proposed method could be adopted for use in the cur-
rent computer algebraic systems to solve both practical and
theoretical problems.
Acknowledgment: The authors would like to thank
Tshwane University of Technology for the Scholarship of
Ms. T. N. Malange and the Directorate of Research and
Innovation of Tshwane University of Technology for the
Postdoctoral funds that facilitated this research.

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Received: 25 November 2015. Accepted: 30 November 2015.

RESEARCH ARTICLE

J. Comput. Theor. Nanosci. 13, 1–7, 2016 7