Accepted Manuscript

Effect of fluorine substitution on the core geometry and refractive

indices in biphenyl-cyclohexane liquid crystals: A DFT study

Anant Kumar

PII: S0167-7322(18)31914-7
DOI: doi:10.1016/j.molliq.2018.09.055
Reference: MOLLIQ 9661
To appear in: Journal of Molecular Liquids
Received date: 11 April 2018
Revised date: 9 September 2018
Accepted date: 10 September 2018

Please cite this article as: Anant Kumar , Effect of fluorine substitution on the core
geometry and refractive indices in biphenyl-cyclohexane liquid crystals: A DFT study.
Molliq (2018), doi:10.1016/j.molliq.2018.09.055

This is a PDF file of an unedited manuscript that has been accepted for publication. As
a service to our customers we are providing this early version of the manuscript. The
manuscript will undergo copyediting, typesetting, and review of the resulting proof before
it is published in its final form. Please note that during the production process errors may
be discovered which could affect the content, and all legal disclaimers that apply to the
journal pertain.
 ACCEPTED MANUSCRIPT

Effect of Fluorine Substitution on the Core Geometry and Refractive Indices

in Biphenyl-cyclo-hexane Liquid Crystals: A DFT Study

Anant Kumar*

Center of Physics and Engineering of Advanced Materials, Instituto Superior Técnico,

Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal.

T
akumar@upatras.gr

IP
CR
Abstract

Incorporating fluorine into liquid crystalline molecules has been found to bring about desirable

US
changes to their physicochemical properties to improve the behavior of the parent compound.
This paper attempts to determine the effect of fluorine incorporation on the optical properties
AN
refractive indices in three biphenyl-cyclo-hexane (BCH) liquid crystals. To understand the
mechanisms of the effect, quantum chemistry calculations were carried out. For the
investigated liquid crystals, refractive indices are estimated through the calculated molecular
M

polarizabilities at different optical wavelengths. Through a systematic relationship between the

ED

fluorine substituents and the optical constants, it has been demonstrated that the optical
properties refractive indices of the investigated liquid crystals do not change largely in the
PT

studied wavelength range. However, the fluorine substituents significantly affect the optical
properties refractive indices. The effects of fluorine substitution on the core geometry are also
CE

examined.

Keywords: Biphenyl-cyclo-hexane liquid crystals, Fluorine substitution, Refractive indices,

AC

Quantum chemistry calculation, DFT

1
 ACCEPTED MANUSCRIPT

1 Introduction

Liquid crystals (LCs) are molecular systems in which liquid like-like order is present at
least in one direction of space along with some degree of anisotropy [1]. Synthesis and production
of new LC materials have always been a key to the advancement of LC display technology.
Consequently, by varying the mesogenic rigid core or the terminal polar groups, several types of
LC materials have been synthesized [2], [3]. Various properties of LCs can be strongly influenced

T
by incorporating different polar substituents into the LC molecules. Therefore, many kinds of polar

IP
substituents have been frequently incorporated into different LC structures to change the

CR
conformational preferences, mesophase behavior, phase transition temperature, and other essential
physical properties. Such changes are not only significant to produce new LC materials with

US
improved properties suitable for display applications but also to understand the structure-property
relationship.
AN
To produce novel liquid crystals for many different applications, a common technique is
to substitute fluoro, chloro, bromo, and alkyl groups in the mesogenic units [4]. In these such LCs,
M

the controlled choice of the position and number of the substituents allows tailoring of desirable
properties as compared to their parent compounds [5]. These substituents can be incorporated into
ED

a wide variety of locations within the LC molecule, for example, at any lateral position of the
mesogenic unit; at the terminal of the mesogenic unit or into the linking groups. Among different
PT

polar substituents, fluorine atom has gained a significant importance because it’s incorporation
into the mesogenic unit of an LC molecule provides broader nematic phase range, low viscosity,
CE

high resistivity, and increased stability of the material [2], [4], [6], [7], [8], [9]. Also, due to its
small size (Rvdw=1.35Å), which is only slightly bigger than that of hydrogen atom (Rvdw=1.20Å),
AC

a fluorine atom can be incorporated into an organic molecule as a replacement for hydrogen
without dramatically affecting the overall molecular size. Thus, producing minimum changes to
the molecular shape, the fluorine substitution does not significantly alter the existing LC nature of
the compound. Due to all of these features, specifically fluorinated LCs have become important
materials for their potential application in flat panel displays [10] as several their properties of
these materials can be altered by changing the number and location of fluorine atoms [7], [11],
[12].

2
 ACCEPTED MANUSCRIPT

Inspired by such background, in this paper, we report the effect of fluorine substitution on
the core geometry and optical properties refractive indices in LC molecules of biphenyl-cyclo-
hexane (BCH) series by using a quantum chemistry approach. In contrast to the conventional liquid
crystal molecule (such as n-CB) which have been extensively studied both experimentally and
theoretically (ab initio and DFT calculations), BCH liquid crystals have been restricted to a limited
number of investigations. Concerning the fluorinated BCH LCs, the number of these investigations
is even less. Experimentally, the fluorinated BCH LCs have been the subject of some XRD [13],

T
[14], optical [14], [15], [16], [17], and dielectric [15] investigations. On the other hand, concerning

IP
the DFT analysis of molecular polarizabilities and refractive indices in BCH LCs, we could find

CR
only a few studies [17], [18], in which, these molecules have been studied in nematic hosts. In ref
[17], the temperature-dependent refractive indices in BCH5-F3 has been investigated. However,

US
no systematic wavelength-dependent could be found for any of the fluorinated BCH molecules.
Hence, due to the lack of systematic studies investigating the effect of fluorine substitution on
AN
molecular polarizabilities and associated properties, we believe that the present study will provide
new and valuable insights into how the fluorine substitution affects the molecular structure,
M

molecular polarizabilities, and refractive indices in fluorinated BCH LCs.

Over the years, there have been several experimental attempts to obtain the molecular
ED

polarizabilities through refractive indices in several classes of semi-flexible LC materials [19],

[20], [21]. However, the results obtained through different experiments often exhibit discrepancies
PT

[22]. Additionally, the experimental investigations do not provide enough information about
molecular structure and molecular polarizabilities. Hence, it becomes difficult to establish a
CE

reliable relationship between the molecular structure and the physical properties. The accurate
determination of LC molecular polarizabilities has been recognized as a prerequisite to
AC

understanding the structure-property relationship [22]. In such a case, the quantum chemistry
serves as a complementary approach to the experimental determination of molecular
polarizabilities and other related properties. Also, it has been found that the quantum chemistry
methods can accurately describe the molecular structure, torsional potentials, dipole moments, and
several other microscopic properties [22]. Motivated by this, we believe that if molecular
polarizabilities are known through any standard quantum chemistry method, the optical parameters
can be calculated by one of the appropriate expressions relating polarizabilities to refractive
indices. The molecular structures of these LC molecules (I to III) are shown in Figure 1 along with

3
 ACCEPTED MANUSCRIPT

their phase transition temperatures [2]. For comparison, we also investigate a non-fluorinated LC
compound (IV) in which, instead of fluorine, a cyano group is longitudinally attached at the
terminal. They have similar structures, the only difference within the molecular structure is the
number and position of fluorine atoms at the terminal. All four LCs exhibit nematic phase over a
wide range of temperature.
The bulk properties such as birefringence have a microscopic origin, and therefore the basic
need is to find a suitable expression connecting refractive indices (macroscopic properties) to

T
molecular polarizabilities (microscopic properties). Different internal field models have been

IP
proposed to produce analytical expressions relating molecular polarizabilities to refractive indices

CR
including those of Vuks [23], Neugebauer [24], Maier and Meier [25] etc. Accurate determination
of LC molecular polarizabilities has also been recognized as a prerequisite for the understanding

US
of structure-property relationship [16]. Over the years, there have been several experimental
attempts to obtain the molecular polarizabilities through refractive indices data in several classes
AN
of LC material [17], [18], [19]. Motivated by this, we believe that if the molecular polarizabilities
are known through any standard quantum chemistry method, the optical parameters can be
M

calculated by one of the appropriate expressions relating polarizabilities to refractive indices. This
approach can also be complementary to the experimental determination of polarizabilities and
ED

other related properties. The density functional theory (DFT) is a general-purpose quantum
chemistry method, and therefore can be applied to most systems including atoms, molecules, and
PT

solids. On the cost of the computer resources, the DFT methods are more frequent than the ab-
initio methods, and therefore the DFT approach has been successfully applied to predict various
CE

properties of liquid crystalline materials [22], [26], [27], [28]. The molecular structures of the
investigated LC molecules (I to IV) are shown in Figure 1 along with their phase transition
AC

temperatures [2],[16]. For comparison, we also investigate a non-fluorinated LC compound (IV).

They have similar structures, the only difference within the molecular structure is the number and
position of fluorine atoms at the terminal. All four LCs exhibit nematic phase over a wide range
of temperature. This paper is organized in the following manner: at first, we apply the standard
DFT approach to calculate the frequency/wavelength-dependent molecular polarizabilities of
investigated molecules in the optical range. Then, we extract the wavelength-dependent refractive
indices using Vuks’ approximation approach. Afterwards, optical properties refractive indices of

4
 ACCEPTED MANUSCRIPT

BCH compounds are compared. Meanwhile, the effect of fluorine substitution on the core
geometry of the investigated molecules is also discussed.

T
IP
CR
US
AN
M

Figure 1. Molecular structures of investigated compounds (I) 4-fluoro-4ʹ-(4-pentyl-cyclohexyl)-

ED

biphenyl (BCH5-F1) (II) 3,4-difluoro-4ʹ-(4-pentyl-cyclohexyl)-biphenyl (BCH5-F2) and (III)

3,4,5-trifluoro-4ʹ-(4-pentyl-cyclohexyl)-biphenyl (BCH5-F3) (IV) 4-(4-Pentyl-cyclohexyl)-
biphenyl (BCH5). The phase transition temperatures of these molecules are as follows: (I) C 120
PT

N 153.9 I (oC) (II) C 55.0 N 105.4 I (oC) (III) C 25.0 N 54.8 I (oC) (IV) C 57.9 Sm 81.6 N 97.9 I
(oC).
CE

2 Theoretical Background
2.1 Calculation of Optical Properties Refractive Indices
AC

Calculations of refractive indices from molecular polarizabilities are complicated because

of the local field effect. And, in the case of anisotropic LC molecules, this has been difficult to
estimate [29]. Among various internal field models, Vuks’ isotropic internal field model is the
simplest and most commonly used model relating molecular polarizabilities to refractive indices
of nematic LCs. The isotropic refractive index, in relation to density and polarizability, is described
by the Lorentz-Lorentz equation:
n2 1 4
 N , (1)
n2  2 3
5
 ACCEPTED MANUSCRIPT

where n and α are isotropic values of refractive index and polarizability, respectively and
N   NA Mw is the molecular packing density or number of molecules per unit volume, in which
ρ is LC density, Mw is the molecular weight, and NA is the Avogadro number. Using polarizability
of an isolated molecule, this equation enables the prediction of refractive index. However, for an
anisotropic liquid crystal, there are two principal refractive indices (ne, no) and two corresponding
molecular polarizabilities (αe, αo). Hence, the Vuks’ formula, relating the principal polarizabilities

T
and refractive indices, takes the following form:

IP
ne2,o 1 4
 Ne,o , (2)
n2  2 3

CR
where n2  (ne2  2no2 ) / 3 and ne and no are the extraordinary and ordinary refractive index,

US
respectively.
Based on these equations, one can drive separate expressions to calculate ne and no [30] as:
AN
4 Ne
ne  1 , and (3.1)
4
1 N
M

3
4 No
ED

no  1 , (3.2)
4
1 N
3
PT

where   is average polarizability defined as   (e  2o ) / 3 and polarizability anisotropy is

expressed as   (e o ) .

CE

Through the available DFT programs, the calculation of the polarizability tensor is easy
AC

and straightforward. The frequency dependent polarizabilities can be calculated by specifying the
input frequencies to which the calculation is requested. Each polarizability tensor produced by
DFT calculations is a 3×3 square matrix, which has six independent elements. To obtain the
polarizabilities along each principal component axis of the molecule, the polarizability tensor was
diagonalized, Hence, the polarizability tensor acquires a simple diagonal form:
xx 

   yy 

 zz 
. (4)

6
 ACCEPTED MANUSCRIPT

The frequency-dependent polarizability calculations are performed at default temperature, 298.15

K. And, for the calculation of refractive indices from the polarizability data, using Eq. 3.1 and 3.2,
the density ρ is assumed as 1.0 g/cc which is a classical value for calamitic liquid crystals [31].
Although this a coarse assumption and does not provide an accurate variation of refractive indices,
this value has provided satisfactory estimations of refractive indices in various BCH [15], [17] and
nCB [27], [29] liquid crystals.

T
2.2 Extended Cauchy Model

IP
The three-parameter Cauchy equation fits well the wavelength-dependent refractive

CR
indices in isotropic media. For the anisotropic LCs, the extended Cauchy model [32] is used to
describe the wavelength effect on refractive indices. The three-parameter extended Cauchy model

US
has the following form:

Be Ce
ne  Ae  
AN
, and (5.1)
 2
4

Bo Co
no  Ao   4,
M

(5.2)
2

ED

in which  Ae , Be , Ce  and  Ao , Bo , Co  are the fitting parameters and their values are obtained by

the calculated values of ne and no at three different wavelengths.

PT

3 Computational Details
CE

The polarizability tensors, for obtaining the principal polarizability components  xx ,  yy ,

and zz , were calculated using the DFT theory as implemented in GAMESS [33] software package.
AC

Here, zz is the molecular polarizability parallel to the molecular long principal axis, and  xx and

 yy are the molecular polarizabilities perpendicular to the molecular long principal axis. The
values of e and o are estimated from zz and (xx   yy ) / 2 , respectively. Average

polarizabilities (  ) and polarizability anisotropies (  ) are calculated as

 av  (xx   yy  zz ) / 3 and   zz  (xx   yy ) / 2 , respectively. Calculations proceed in
an analogous way to the conventional quantum mechanical calculations. Before each polarizability

7
 ACCEPTED MANUSCRIPT

calculation, with all-trans conformation as starting geometry, full geometry optimization was
carried out without imposing any constraints. Although, for the better estimation of polarizabilities
in such semi-flexible molecules, all conformations arising due to the flexible chain must be
considered. However, Demus and Inukai [34], while studying the 5CB molecule, reported that the
calculated properties do not vary significantly for different conformations and therefore it is time-
saving and sufficient to use the polarizability data of the all-trans conformations only. For
optimizations and polarizability calculations, the hybrid functional B3LYP which employs the

T
Becke exchange and Lee-Yang-Pass correlation functionals was used in conjunction with 6-31G**

IP
basis set (containing both polarization and diffuse functions). Arguments for this specific choice

CR
are given in the next section by comparing the influence of different basis sets on molecular
polarizability. is also compared These basis sets include 6-21G, 6-21G*, 6-21G**,6-31G, 6-31G*,

US
6-31G**, 6-311G, 6-311G*, and 6-311G** basis sets at B3LYP level.

4 Results and Discussion

AN
4.1 Comparison of Basis Sets for BCH5-F1
M

First, polarizability calculations were performed for the BCH5-F1 molecule as a reference
to determine the optimal level of theory and basis set for the quantitative estimation of
ED

polarizabilities in all investigated molecules. These molecular polarizabilities were calculated

using basis sets of varying size under the B3LYP level of theory. The calculated values of the
PT

molecular polarizability anisotropy of BCH5-F1, at 589.0 nm wavelength, are plotted in Figure 2.

The comparison shown in Figure 2 helps in deciding the accuracy of the basis sets and their
CE

computational costs. On average, the polarizability anisotropy slightly increases as the size of the
basis set becomes larger. This significantly improves the accuracy, but the computational time
AC

becomes enormous. As the size of the basis set is increased, the accuracy of the calculated
polarizability anisotropy also increases but, at the same time, the computational cost becomes
enormous. On detailed comparison, it turns out that the value of the calculated polarizability
predicted by substantially larger basis set 6-311G** is close to the one given by 6-31G** basis
set, but the computation time was about 40% less. Therefore, taking a reasonable compromise
between the accuracy and the computer resources, the 6-31G** basis set was chosen for all
polarizability calculations. Another reason for this choice was that the B3LYP functional with
standard 6-31G** basis set has already been successfully applied for the calculation of

8
 ACCEPTED MANUSCRIPT

polarizabilities (refractive indices) and various other properties in similar liquid crystal molecules
[35], [17].

T
IP
CR
US
AN
M
ED

Figure 2. Molecular polarizability anisotropy of BCH5-F1 (at 589.0 nm) calculated against the
basis sets of varying size under the B3LYP level of theory.

4.2 Effect of Fluorine Substitution on the Core Geometry

PT

Substituting hydrogen atom by one or more fluorine atoms may lead to a change in the
CE

preferred molecular conformation. This effect can be explained by the size and electronegativity
of fluorine. Therefore, dihedral angles in the mesogenic cores of the investigated BCHs would also
AC

be modified by the insertion of fluorine atom(s), with influence on their physicochemical

properties. Here, we have explored the distribution of two dihedral angles of the mesogenic units
of investigated molecules through the potential energy surface (PES) scan at the B3LYP/6-31G**
level. These dihedral angles are depicted in Figure 3. The potential energy scans for the two
dihedral angles of the mesogenic core of BCH5-F1 are shown in Figure 4 and 5. For the rotation
of dihedral angle 1 , there are two equivalent energy minima in the 0 to180o range, with the energy

barrier height of 2.58 kcal/mol (at 1  36.8o ). This is in good agreement with some previous ab-

9
 ACCEPTED MANUSCRIPT

initio calculations, where the energy barrier height of 2.49 kcal/mol (at 1  37.0o ) was obtained

for the biphenyl unit of liquid crystal molecules [36]. The potential energy profile of 2 exhibits
two equivalent energy minima on a full 0-360o range, having the energy barrier height of 2.69
kcal/mol (at 2  59.4o ). This is also in close agreement with previously reported ab-initio values
for the phenylcyclohexane unit in which the energy barrier was found to be 2.76 kcal/mol (at
2  63o ) [36]. Similar patterns were obtained in the PES scans of 1 and 2 , respectively for

T
the BCH5-F2, BCH5-F3, and BCH5 molecules.

IP
CR
US
Figure 3. The dihedral angles ( 1 and 2 ) considered to find out the distortions in the core
AN
geometry as a function of fluorine substituents.
M
ED
PT
CE
AC

Figure 4. Conformational energy profile for the rotation of dihedral angle φ1 of BCH5-F1.

10
 ACCEPTED MANUSCRIPT

T
IP
CR
US
Figure 5. Conformational energy profile for the rotation of dihedral angle φ2 of BCH5-F1.
AN
Table 1. Optimal values of dihedral
angles in all four molecules
Compound Dihedral Dihedral
M

Angle (φ1) Angle (φ2)

BCH5-F1 36.8˚ 59.4˚
ED

BCH5-F2 35.0˚ 66.5˚

BCH5-F3 35.6˚ 59.4˚
37.5˚ 62.6˚
PT

BCH5

For all four molecules, values of the two dihedral angles ( 1 and 2 ) are listed in Table 1.
CE

The value 1 remains very close in all four compounds; however, 2 is slightly higher in the
BCH5 molecule but significantly larger in the BCH5-F2 molecule. Possibly, the asymmetric
AC

fluorine substitution causes this twisting. Szczucinski et al [37], through the quantum chemistry
calculations of longitudinal and lateral dipole moment components of various three-ring
fluorinated compounds, demostrated that the exchange of a hydrogen atom for fluorine atom
increases twisting of the neighboring rings due to the appearance of a large component of lateral
dipole moment. This is also evident from our calculated results of dipole moments which are
shown in Figure 6. For each structure, the direction of the net dipole moment is displayed using a
red arrow. We found that BCH5-F1, BCH5-F3, and BCH5 exhibit negligible values of transverse

11
 ACCEPTED MANUSCRIPT

dipole moment. On the other hand, BCH5-F2 has a significant value of transverse dipole moment
which markedly affects the direction of the net dipole moment. Hence, we can deduce that the
insertion of the second fluorine atom, by enhancing the lateral dipole moment of the molecule,
disrupts the symmetry of the molecule and therefore generates the molecular twisting. However,
the third fluoro substituent tends to cancel the lateral dipole influence of the second fluoro
substituent and, therefore the longitudinal dipole is increased more substantially [2]. In another
study, Haldar et al [14] also noticed the change of some properties in di-fluoro derivatives

T
compared to mono- and tri-fluoro derivatives.

IP
CR
US
AN
M

Figure 6.: The direction (arrowhead) of the net dipole moment in (I) BCH5-F1 (μ=2.07D), (II)
ED

BCH5-F2 (μ=3.48D) and (III) BCH5-F3 (μ=4.07) (IV) BCH5 (μ=0.05D).

PT

4.3 Effect of Fluorine Substitution on Refractive Indices

The next objective of this work is to explore the effect of fluorine substitution on refractive
CE

indices of BCH liquid crystals. The first requirement is to obtain a reliable estimation of molecular
polarizabilities from a gas-phase molecule, and then to apply a suitable analytical expression
AC

relating molecular polarizabilities and bulk refractive indices. In the current work, we have applied
the Vuks’ method for this purpose. Molecular polarizabilities of all four molecules were calculated
in the 486.0-656.0 nm range. Using equations (3.1) and (3.2), as discussed in section 2, the
corresponding refractive indices and birefringence were calculated.

12
 ACCEPTED MANUSCRIPT

T
IP
CR
US
Figure 7. Wavelength-dependent refractive indices for BCH5 (circles), BCH5-F1 (squares),
BCH5-F2 (stars), and BCH5-F3 (down-ward triangles). The solid lines represent the fittings using
AN
the extended Cauchy model (Equation 4 5). The fitting parameters are listed in Table 2.
M
ED
PT
CE
AC

Figure 8. Wavelength-dependent birefringence for BCH5 (circles), BCH5-F1 (squares), BCH5-

F2 (stars), and BCH5-F3 (down-ward triangles). The solid lines represent the fittings using the
extended Cauchy model (Equation 4 5). The fitting parameters are listed in Table 2.

The calculated refractive indices, ne and no, as a function of wavelength, are shown in
Figure 7. The circles, squares, stars, and down-ward triangles represent the calculated refractive

13
 ACCEPTED MANUSCRIPT

indices of BCH5, BCH5-F1, BCH5-F2, and BCH5-F3, respectively. In addition, in Figure 8, the
difference between ne and no was also plotted to determine the wavelength dispersion of
birefringence. By using the extended Cauchy model, equations (5.1) and (5.2), with the determined
fitting parameters  Ae , Be , Ce  and  Ao , Bo , Co  , we also obtained the fitting curves for the
dispersion of refractive indices and birefringence. The curves of best fit are shown as solid lines
in Figure 7 and Figure 8 and the fitting parameters are listed in Table 2. It appears from the results
that refractive indices and birefringence slightly decrease over the accessible wavelength range.

T
For BCH5-F1, the extraordinary refractive index decreases from ne=1.68 at 486.0 nm to 1.66 at

IP
656.0 nm. However, for BCH5, the ne decreases from 1.73 to 1.70 in the same wavelength range.

CR
The ordinary refractive index also decreases with almost no significant slope. Similar trends were
observed for BCH5-F2 and BCH5-F3 molecules. Birefringence for BCH5-F1 decrease from 0.31
at 486.0 nm to 0.29 at 656.0 nm and from 0.33 to 0.31 for BCH5 molecule. Among all four liquid

US
crystals, values of refractive indices were found highest for the non-fluorinated BCH5 molecule.
As the number of fluorine substituents was increased, refractive indices decreased subsequently.
AN
Incorporating the fluorine atoms can affect refractive indices via different mechanisms
simultaneously. The decrease in refractive indices is primarily attributed to the lower molecular
M

packing density [38], which is due to the greater steric volume of fluorine relative to hydrogen.
Furthermore, the electronic polarization is always lowered with fluorine substitution. The low
ED

polarizability of a C–F bond relative to a C–H bond has traditionally been invoked as a possible
cause for this [39]. Likewise, according to our calculations, the values of polarizability anisotropy
PT

for BCH5 molecule were highest in comparison to those of the fluorinated BCH5 LCs, as can be
seen in Figure 9. In all the investigated BCH LCs, the polarizability anisotropies were found about
CE

27-29 Å3. These results are in good agreement with some previous DFT calculation where these
values were calculated about 30 Å3 [17, 18] in BCH5-F1 and BCH5-F3 LCs. It is noteworthy that,
over the entire wavelength range, the refractive index values can be arranged in the following
AC

order, compound BCH5 > BCH5-F1 > BCH5-F2 > BCH5-F3, as depicted in Figure 7 and 8. The
fitting curves obtained by the extended Cauchy’s model are in excellent agreement with the
calculated data points. These results are in accord with literature where it was reported that with
the increase of fluorine substituents in liquid crystals, the refractive indices decrease [40].
However, illustrating a systematic wavelength dependence of refractive indices in the investigated
LCs, no measurement could be traced in literature to compare with the calculated results. Hence,
we propose a systematic experimental investigation of refractive indices in the fluorinated BCH
liquid crystals which would further testify the validity of our results.

14
 ACCEPTED MANUSCRIPT

T
IP
CR
US
Figure 9: Wavelength dependence of polarizability anisotropy for BCH5 (circles), BCH5-F1
(squares), BCH5-F2 (stars), and BCH5-F3 (down-ward triangles).
AN
M
ED
PT
CE
AC

Figure 10. Variation of the average refractive index (blue squares) and birefringence (red circles)
as a function of the number of fluorine substituents in BCHs.

For all the investigated LCs, the wavelength dependence of molecular polarizability
anisotropy is depicted in Figure 9. The polarizabilities of fluorinated BCH LCs are close to each

15
 ACCEPTED MANUSCRIPT

other but significantly different from the polarizabilities of non-fluorinated BCH compound.
Figure 10 shows the variation of the average refractive index and birefringence as a function of
the number of fluorine substituents in BCHs. The data in this figure were collected at 589.0 nm
wavelength. The decrement in Δn and <n>, through the variation of fluorine substituents, is
apparently related to the reduction of ne and no as the number of fluorine atoms increased. Based
on these results, we can deduce that the insertion of fluorine atoms into these molecules has a
strong impact on their optical properties refractive indices.

T
IP
Table 2. Fitting parameters for the three-parameter Cauchy model.

CR
ne no
LC Material
Ae Be(λ-2) Ce(λ-4) Ao Bo(λ-2) Co(λ-4)

US
BCH5 1.6779 1.1252 5.4027 1.3878 0.2945 2.4126
BCH5-F1 1.6360 0.9220 6.2816 1.3621 0.2664 2.1829
BCH5-F2 1.5999 0.8799 5.9369 1.3384 0.3574 0.3848
AN
BCH5-F3 1.5672 0.8903 4.7500 1.3214 0.2244 1.8382
M

5 Conclusions:
The work reported here represents the correlation between the fluorine substitution manner
ED

and some of the optical properties in four BCH liquid crystals. With respect to the optical
properties, ne, no, <n> and Δn of all four analogues LCs were evaluated. The optical properties
PT

refractive indices of all four liquid crystals in this series are expected to be comparable since the
chemical structures of the mesogenic units and flexible terminal chains are similar, so the
CE

differences we observed can be attributed simply to the multiple fluorine substitutions at various
terminal positions. Furthermore, the profound effects of fluorine substitution on the core geometry
AC

were noticed. In conclusion, we could also confirm that the optical constants refractive indices of
investigated BCH liquid crystals do not exhibit appreciable wavelength dependence from 486.0 to
656.0 nm. However, the manner of fluorine-substitution including the number and positions
largely influence the optical properties refractive indices. The differential fluorine substitution
effect on optical properties refractive indices is notably manifested through the significantly
different results of the non-fluorinated BCH5 and other fluorinated molecules. Smaller is the
number of fluorine substituents, higher is the values of refractive index.

16
 ACCEPTED MANUSCRIPT

6 References
[1]. P. G. de Gennes, J. Prost, The Physics of Liquid Crystals, 2nd Edition, Clarendon Press,
1995.
[2]. M. Hird, Fluorinated liquid crystals-properties and applications, Chem. Soc. Rev. 36(12)
(2007) 2070-2095.
[3]. R. E. Banks, B. E. Smart, J. C. Tatlow (Eds.), Organofluorine Chemistry: Principles and

T
Commercial Applications, Springer Science & Business Media, 2013.

IP
[4]. Y. Arakawa, H. Tsuji, The effect of fluorine substitutions on the refractive index properties
for π-conjugated calamitic nematic materials, Phase Trans. 90(6) (2017) 549-556.

CR
[5]. F. Guittard, E. T. de Givenchy, S. Geribaldi, A. Cambon, Highly fluorinated thermotropic
liquid crystals: An update, J. Fluor. Chem. 100(1-2) (1999) 85-96.

US
[6]. M. Pytlarczyk, J. Herman, P. Harmata, S. Urban, P. Kula, The influence of the
dialkylphenyltolane’s difluorosubstitution on mesomorphic and dielectric properties, Liq.
AN
Cryst. (2018) 1-10. Doi: https://doi.org/10.1080/02678292.2018.1446557
[7]. A. Debnath, P. K. Mandal, Effect of fluorination on the phase sequence, dielectric and
M

electro-optical properties of ferroelectric and antiferroelectric mixtures, Liq. Cryst. (2017)

1-11.
ED

[8]. S. Yamada, S. Hashishita, T. Asai, T. Ishihara, T. Konno, Design, synthesis and evaluation
of new fluorinated liquid crystals bearing a CF 2 CF 2 fragment with negative dielectric
PT

anisotropy, Org. Biomol. Chem. 15(6) (2017) 1495-1509.

[9]. M. K. Das, A. Pramanik, B. Das, R. Dąbrowski, A comparative study of the mesomorphic
CE

properties of fluoro-isothiocyanated and fluorinated terphenyl liquid crystals from

birefringence, static dielectric permittivity, splay elastic constant and rotational viscosity
AC

measurements, J. Phys. D: Applied Physics 45(41) (2012) 415304.

[10]. D. Pauluth, K. Tarumi, Advanced liquid crystals for television, J. Mat. Chem. 14(8) (2004)
1219-1227.
[11]. W. Piecek, P. Kula, Z. Raszewski, P. Perkowski, P. Morawiak, J. Kedzierski, R.
Dabrowski, X. Sun, An influence of a single fluorine atom position in the molecular rigid
core on physical properties of orthoconic antiferroelectric liquid crystal, Ferroelectrics
365(1) (2008) 78-87.

17
 ACCEPTED MANUSCRIPT

[12]. P. Morawiak, W. Piecek, M. Zurowska, P. Perkowski, Z. Raszewski, R. Dabrowski, K.

Czuprynski, X.W. Sun, Effect of fluorination of molecular rigid core in liquid crystal
biphenyl benzoate based homologous series, Opto-Electronics Rev. 17(1) (2009) 40-44.
[13]. I. H. Ibrahim. X-Ray Diffraction of Some Biphenylcyclohexanes (BCH's). Zeitschrift für
Naturforschung A, (1987) 42(5) 444-446.
[14]. S. Haldar, S. Barman, P. K. Mandal, W. Haase, R. Dabrowski, Influence of molecular core
structure and chain length on the physical properties of nematogenic fluorobenzene

T
derivatives, Mol. Cryst. Liq. Cryst. 528(1) (2010) 81-95

IP
[15]. M. Klasen, M. Bremer, A. Gotz, A. Manabe, S. Naemura, K. Tarumi, Calculation of optical

CR
and dielectric anisotropy of nematic liquid crystals, Jap. J. App. Phys. 37(8A) (1998) L945.
[16]. H. J. Muller, W. Haase, Refractive indices, density and order parameters for some biphenyl

US
cyclohexanes, Mol. Cryst. Liq. Crys. 409(1) (2004) 127-135.
[17]. P. Kaszynski, A. Januszko, K. L. Glab, Comparative Analysis of Fluorine-Containing
AN
Mesogenic Derivatives of Carborane, Bicyclo [2.2. 2] octane, Cyclohexane, and Benzene
using the Maier–Meier Theory, J. Phys. Chem. B 118(8) (2014) 2238-2248.
M

[18]. M. Jasinski, A. Jankowiak, A. Januszko, M. Bremer, D. Pauluth, P. Kaszynski, Evaluation

of carborane‐ containing nematic liquid crystals for electro‐ optical applications, Liq.
ED

Cryst. 35(3) (2008) 343-350.

[19]. A. Hauser, G. Pelzl, C. Selbmann, D. Demus, S. Grande, A. Petrov, Order parameter and
PT

molecular polarizabilities of liquid crystals with nematic and smectic phases, Mol. Cryst.
Liq. Cryst. 91(1-2) (1983) 97-113.
CE

[20]. M. Mitra, B. Majumdar, R. Paul, S. Paul, Molecular properties and order parameters of
Schiff's base compounds, Mol. Cryst. Liq. Cryst. 180(2) (1990) 187-199.
AC

[21]. N. Vieweg, C. Jansen, M. K. Shakfa, M. Scheller, N. Krumbholz, R. Wilk, M. Mikulics

M. Koch, Molecular properties of liquid crystals in the terahertz frequency range, Opt. Exp.
18(6) (2010) 6097-6107.
[22]. S. J. Clark, G. J. Ackland, Crain, Ab initio molecular polarisabilities of liquid crystals:
Application to DOBAMBC and 5CB, EPL (Europhysics Letters) 44(5) (1998) 578.
[23]. M. F. Vuks, Determination of the optical anisotropy of aromatic molecules from the double
refraction of crystals, Optics and Spectroscopy 20 (1966) 361.

18
 ACCEPTED MANUSCRIPT

[24]. H. E. J. Neugebauer, Clausius-Mosotti equation for certain types of anisotropic crystals,

Can. J. Phys. 32(1) (1954) 1-8.
[25]. W. Maier, G. Meier, A simple theory of the dielectric are some homogeneous criteria
oriented liquid crystal phases of nematic type, Z Naturforsch. A 16 (1961) 262-267.
[26]. S. J. Clark, C. J. Adam, D. J. Cleaver, J. Crain, Conformational energy landscapes of liquid
crystal molecules, Liq. Cryst. 22(4) (1997) 477-482.
[27]. Z. Chen, L. Jiang, H. Ma, Calculation on frequency and temperature properties of

T
birefringence of nematic liquid crystal 5CB in terahertz band, Chem. Phys. Lett. 645 (2016)

IP
205-209.

CR
[28]. S. P. Ju, S. C. Huang, K. H. Lin, H. Y. Chen, T. K. Shen, Prediction of Optical and
Dielectric Properties of 4-Cyano-4-pentylbiphenyl Liquid Crystals by Molecular

US
Dynamics Simulation, Coarse-Grained Dynamics Simulation, and Density Functional
Theory Calculation, J. Phys. Chem. C 120(26) (2016) 14277-14288.
AN
[29]. S. H. Simpson, R. M. Richardson, S. Hanna, Influence of dye molecules on the
birefringence of liquid crystal mixtures at near infrared frequencies, J. Chem. Phys.
M

127(10) (2007) 104901.

[30]. J. Li, S. Gauza, S. T. Wu, Temperature effect on liquid crystal refractive indices, J. App.
ED

Phys. 96(1) (2004) 19-24.

[31]. J. K. Vij, I. Prigogine, S. A. Rice, Advances in Liquid Crystals: A Special Volume, Vol.
PT

113, John Wiley & Sons, 2009.

[32]. J. Li, S. T. Wu, Extended Cauchy equations for the refractive indices of liquid crystals, J.
CE

App. Phys. 95(3) (2004) 896-901.

[33]. M. W. Schmidt, K. K. Baldridge, J. A. Boatz et al, General atomic and molecular electronic
AC

structure system, J. Comp. Chem. 14(11) (1993) 1347-1363.

[34]. D. Demus, T. Inukai, Calculation of molecular, dielectric and optical properties of 4'-n-
pentyl-4-cyano-biphenyl (5CB), Liq. Cryst. 26(9) (1999) 1257-1266.
[35]. S. H. Simpson, R. M. Richardson, S. Hanna, Calculation of the birefringences of nematic
liquid crystals at optical and infrared wavelengths, J. Chem. Phys. 123(13) (2005) 134904.
[36]. D. L. Cheung, S. J. Clark, M. R. Wilson, Parametrization and validation of a force field for
liquid-crystal forming molecules, Phys. Rev. E 65(5) (2002) 051709.

19
 ACCEPTED MANUSCRIPT

[37]. L. Szczucinski, R. Dąbrowski, S. Urban, K. Garbat, M. Filipowicz, J. Dziaduszek, M.

Czerwinski, Synthesis, mesogenic and dielectric properties of fluorosubstituted
isothiocyanatoterphenyls, Liq. Cryst. 42(12) (2015) 1706-1729.
[38]. D. K. Yang, Fundamentals of Liquid Crystal Devices, John Wiley & Sons, 2014.
[39]. G. Hougham, G. Tesoro, A. Viehbeck, Influence of free volume change on the relative
permittivity and refractive index in fluoropolyimides, Macromolecules 29(10) (1996)
3453-3456.

T
[40]. J. Li, X. Yang, N. Gan, B. Wu, Z. An, The effect of lateral fluorination on the properties

IP
of phenyl-tolane liquid crystals, Liq. Cryst. 42(3) (2015) 397-403.

CR
US
AN
M
ED
PT
CE
AC

20
 ACCEPTED MANUSCRIPT

T
IP
CR
US
[41].

Graphical abstract
AN
M
ED
PT
CE
AC

21
 ACCEPTED MANUSCRIPT

Highlights

 Stereoselective fluorination is an effective tool in modulating the LC properties.

 In BCH LCs, there is no significant effect of wavelength on the refractive indices.
 Contrarily, the fluorine substitution strongly influences the refractive indices.

T
IP
CR
US
AN
M
ED
PT
CE
AC

22