Asian Journal of Nanoscience and Materials 2 (2019) 439-447

Asian Journal of Nanoscience and

Materials
Journal homepage: www.ajnanomat.com

Original Research Article

A computational study of thermophysical, HOMO, LUMO,
vibrational spectrum and UV-visible spectrum of
cannabicyclol (CBL), and cannabigerol (CBG) using DFT
Md Nuruzzaman Sarkera , Ajoy Kumerb,* , Mohammad Jahidul Islama , Sunanda Paulc
a Department of Physics, European University of Bangladesh, Dhaka-1216, Bangladesh
b Department of Chemistry, European University of Bangladesh, Dhaka-1216, Bangladesh
c Department of Biochemistry and Molecular Biology, University of Chittagong, Chittagong, Hathazari-4334, Bangladesh

ARTICLE INFORMATION ABSTRACT

Received: 16 June 2019 Cannabicyclol, also called CBL, is one of the least known and studied isomer
Received in revised: 12 July 2019 of cannabinoids in the cannabis plant, and it is the precursor of the different
Accepted: 12 July 2019 cannabinoids found in marijuana plant having with widespread medicinal
Available online: 1 August 2019 use. In this work, the thermophysical properties of CBL such as, free energy,
entropy, dipole moment, binding energy, nuclear energy, electronics energy,
DOI: 10.26655/AJNANOMAT.2019.4.8 and heat of formation were estimated using density functional theory for
developing use as pharmaceutical pursues. In addition, the chemical
reactivity properties including highest occupied molecular orbital (HOMO),
KEYWORDS lowest unoccupied molecular orbital (LUMO), HOMO-LUMO gap, ionization
Cannabis potential, electronegativity, hardness, softness, and electron affinity were
HOMO evaluated. It was found that, the magnitude of HOMO was -8.98 and -8.53,
LUMO LUMO was 0.19, -0.31 and HOMO –LUMO gap was -9.17 and -8.22 eV of CBL
and CBG, respectively. The vibrational spectrum and electronics spectrum
DFT
were simulated for identification and characterization. These studies
vibrational spectrum and electronics provided a proper and predictable data for further use in any chemical and
spectrum pharmaceutical purpose.

Corresponding author, email: [email protected] (A. Kumer).

Tel.: +8801770568699.
A computational study of thermophysical … 440
Graphical Abstract

Cannabicyclol (CBL) Cannabivarin (CBV)

Introduction feel. Other effects include altered senses,

altered sense of time, changes in mood,
Cannabis sativa is the world's most impaired body movement, difficulty with
recognizable plant for some medical useable thinking and problem-solving, impaired
chemicals. There are two types of cannabis memory, hallucinations (when taken in high
plants of flowers, male or female. Male flowers doses), delusions (when taken in high doses),
grow in stretched out clusters along the leaves psychosis (when taken in high doses) [6, 7].
and turn yellow and die after blossoming. Cannabis has a psychoactive and physical
Female flowers grow in spike-like clusters and effect when someone accepts it more than a
remain dark green for a month after limited dose [8]. Consumption of immediate
blossoming, until the seed ripens [1]. effects from eating cancer includes
Marijuana refers to absorbed leaf, flowers, entertainment, increased Cummins, body
stalks, and seeds from cannabis sativa or pictures, hearing, visual illusion, and ataxia.
cannabis indica plant [2, 3]. The plant contains Recently, more than 100 natural species of
the mind-altering chemical THC and other cannabis have been detected from the
similar compounds [4]. Tetrahydrocannabinol cannabis sativa plant, which are active in the
(THC), and Cannabinoids (CBD) are the main two-most active pharmacology in the region.
psychoactive chemical in marijuana and other Some immediate unexpected side effects
drugs. Some people may smoke marijuana in include reduction in short-term memory, dry
hand-rolled cigarettes (joints) or in pipes or mouth, impaired motor skills and eye
water pipes (bongs) [5]. The THCs can supply reddening [9]. In addition to a personal change
very large amount of tea to the body, and their between perception and mood, increased
use has sent some people to the emergency heart rate among the most common short-
room. Another danger is to prepare this term physical and nervous effects, hunger and
exhaust, which usually involves the boutine food costs, reducing blood pressure, short-
(light fluid). Many people burn in the fire and term and memory loss of work cannabis
they are severely burned using a booting for impeded the ability of driving a person.
tea at home. CBG cannabis strains are used
Marijuana over activates parts of the brain therapeutically as an antidepressant, and as a
that contain the highest number of these functioning painkiller, killer to bacterial
receptors. This causes the "high" that people growth, reduce inflammation, inhibit cell
M.N. Sarker et al. 441

growth in tumour and cancer cells, promote energies in order to determine the interesting
bone growth, and low-affinity antagonist. It is molecular properties and chemical quantities
also beneficial for the treatment of psoriasis, are calculated as the following equation
glaucoma, multiple sclerosis and skin diseases. (𝜇) = −
𝐼+𝐴
(1)
2
On the other hand, the similar cannabis is CBL 𝐼−𝐴
() = (2)
in basis of structure which is famous for the 2
1
use of poisonous effect. If anybody takes the (𝑆) =

(3)
dose of 8mg per kilo of bodyweight, very few 𝐼+𝐴
() = (4)
minute he/she is death. The main limitation of 2
𝜇2
CBG, CBL has no vast research. In our study, a () =
2
(5)
theoretical investigation was estimated for
physiochemical and chemical reactivity using Materials and methods
DFT of computational overview. This
theoretical investigation of physical, chemical, Computing methods for simulation
thermochemical and HOMO, LUMO profile was
The molecular modeling program permits
established using computational tools. To
to build and analyze different molecular
estimate the chemical reactivity, the
structures and determine the molecular,
electrophilicity (ω), the chemical potential (μ),
electronic, and biological properties. To create
electronegativity (χ), hardness (η) and
the spatial chemical structure of each
softness (S) be put into a molecular orbital’s
calculated molecule, the two-dimensional
framework parameter were calculated and
structure of the molecule shall be built step-
compared our previous work [10‒13]. It was
by-step by drawing. Then hydrogen atoms are
found for simulating of different organic acid,
automatically added from building option and
ionic liquids, cannabis and other molecule
chemical structure is converted into a 3D
from A. Kumer et al., that the HOMO LUMO gap
structure. The first step in getting the main
is about 2.0 to 5.0 eV and has a temperature
characteristic parameters of molecules is to
activity on entropy and heat capacity [14‒17]
optimize the molecular structure to obtain a
which is use full theoretical parameter for
configuration characterized by minimum free
further any uses in both of chemical industries
energy. In sitting the DFT was fixed via 6G-
and pharmaceutical industries [14, 18‒20]. In
31G*, and B3-LYP [21]. After completing
this work, using DFT method, we calculate the
optimization, the theoretical properties of the
electrophilicity (ω), the chemical potential (μ),
studied compound such as free energy,
electronegativity (χ), hardness (η) and
entropy, dipole moment, binding energy,
softness (S) be put into a molecular orbital’s
nuclear energy, electronics energy, the heat of
framework, thermophysical and spectroscopy
formation, the HOMO, LUMO are recorded. The
study.
QSAR properties of molecules like charge
The HOMO and LUMO energies are used for
density, surface area grid, volume, LogP,
the determination of global reactivity
polarizability, refractivity, molecular mass,
descriptors. It is important that
were calculated. Using the computing in
electrophilicity (ω), the chemical potential (μ),
vibrational optimization, the UV-visible
electronegativity (χ), hardness (η) and
spectroscopy and IR spectroscopy were
softness (S) be put into a molecular orbital’s
determined.
framework. We focus on the HOMO and LUMO
A computational study of thermophysical … 442

Result and discussion bond angle, partial charge, and bond torsion. In
Figure 1, the molecular orbital diagrams are
Optimized structure presented having both of molecular symmetry
The optimized molecular structure and asymmetry properties. In the Figure 1, red
provides some information about the color is oxygen atom, white color is hydrogen,
molecular properties including, bond length, and cyan is carbon.

Cannabicyclol (CBL) Cannabivarin (CBV)

Figure 1. Optimized structure in the cylinder shape

Thermophysical and thermo-dynamical The bond dipole moment is the idea of an

properties electric dipole moment to measure the
polarity of a chemical bond within a molecule.
The binding free energy of the optimized
In view of pharmaceutical industries, the
molecules is calculated by performing
dipole moment was a parameter for the drug
molecular simulation by DFT method. The
by which a drug is to be used open or close
molecule with minimum binding energy will
packet. If any drug has a dipole moment, it can
have the maximum binding affinity and higher
be able to absorb the ultraviolet light and have
biological active. According to this more
a possibility of properties. From Table 1, it was
negative value, we can consider a more
found that CBL, and CBL have 1.34 and 1.25 D.
effective drug. In this case CBV is less biological
active than CBL.

Table 1. Thermophysical properties

Properties CBL CBV
Total energy, (kcal/mol) -81584.1 -73293.88
Free energy, (kcal/mol) -81584.1 -73293.88
Dipole moment, (D) 1.34 1.25
RMS gradient,(kcal/mol) 0.09 0.01
Binding energy, (kcal/mol) -5328.21 -4579.94
Heat of formation, (kcal/mol) -57.34 -67.67
Electronic energy, (kcal/mol) -697039.42 -561522.88
Nuclear energy, (kcal/mol) 615455.31 488228.99

Temperature effect on nntropy and heat In case of thermo chemistry, the entropy
capacity and heat capacity are the key factor for
M.N. Sarker et al. 443

determining the reaction environment. In case in a cell, sharp suggests. That increase in
of drug design, entropy, which Sharp focuses disorder can be detected as heat flowing into
on in a biomedical system, obliges the the water surrounding the drug-target bond.
direction of all chemical reactions towards Here, it is found that temperature has activity
disorder. Therefore, it is this phenomenon that in any single system for bioactive molecule.
determines how tightly a drug binds to its From the Table 2, we can see that with
target protein or molecules. When a drug binds increasing the temperature of any molecular
to its target, its entropy decreases, so disorder system, the entropy and heat capacity well
must increase somewhere else in the cell, poorly increased means that disorder
usually in the abundant water molecules found decreases.

Table 2. Data for entropy and heat capacity

273 K 298 K 323 K
Entropy Heat capacity, Entropy Heat capacity, Entropy Heat capacity,
(kcal/mol-deg) (kcal/mol- (kcal/mol-deg))
deg))
CBL 0.14 0.07 0.15 0.08 0.16 0.09
CBV 0.13 0.07 0.14 0.08 0.15 0.09

Chemical reactivity parameters HOMO and LUMO give information on the

possible electronic transition, chemical
HOMO LUMO in different levels stability, and chemical strength. The HOMO
Te terms of HOMO and LUMO are also and LUMO also indicate the electrophilic and
considered as frontier orbitals on basis nucleophilic attraction region in molecule. In
of frontier molecular orbital theory. The Table 3, includes the magnitude of HOMO,
energy levels of the molecular orbitals order LUMO in different levels.

Table 3. Data for HOMO LUMO

CBL CBV
HOMO(0), eV -8.98 -8.53
HOMO(-1), eV 0.19 -0.31
LUMO, (0), eV 0.19 -0.31
LUMO, (-1), eV -8.98 -8.53

HOMO, and LUMO picture in zero level neucleophilic can be attracted. On the other
hand, green color indicates the positive charge
In the molecular orbital diagram, it is found area where the electrophilic groups are
that where region is to be attracted the attached. In CBL is less reactive in both of the
neucleophilic or electrophilic reagent. From neucleophilic or electrophilic reaction than
the Figure 2, the blue color mentions the CBV.
negative charge region where only

CBL CBV
A computational study of thermophysical … 444

HOMO

CBL CBV
LUMO

Figure 2. The frontier orbitals: a) HOMO and b) LUMO

HOMO LUMO gap, ionization potential, and 11.0 eV and In CBL and CBV have -9.17 and -
electron affinity 8.22 eV LUMO –HOMO gap. The energy gap is
used to determine the molecular electrical
The LUMO-HOMO gap is the most
transport properties. In addition, according to
important parameter for the chemical
Koopmans’ theorem, the energy gap, Egap,
reactivity. A LUMO- HOMO gap is considered as
defined as the difference between HOMO and
the high reactivity, as given Table 3. A. Kumer
LUMO energy [22].
et. al. (2019) published some series of papers
where the HOMO, LUMO gap was almost 8.0 to
Egap = ( ELUMO − EHOMO ) ≈ IP − EA
The ionization potential (I) and electron 𝐼 = −𝐸𝐻𝑂𝑀𝑂 (6)
affinity (A) can be estimated from the HOMO 𝐴 = −𝐸𝐿𝑈𝑀𝑂 (7)
and LUMO energy values as following and
magnitude is listed in Table 4.
Table 4. Data for LUMO- HOMO gap (ΔE), IP, and EA
CBL CBV
HOMO, LUMO gap, eV -9.17 -8.22
Ionization potential (I), eV 8.98 8.53
Electron affinity (A), eV -0.19 0.31

Chemical potential, electronegativity, Chemical potential of the species is such

hardness, and softness that the particles given can be absorbed or
released due to the change in the number of
M.N. Sarker et al. 445

particles. According to electrochemistry, ions, opposite to the chemical potential. An atom

molecule or species do not always have a with high electronegativity attracts electrons
tendency to go from higher to lower chemical strongly, while an atom with low
potential, but they do always go from higher to electronegativity attracts them weakly.
lower electrochemical potential. The Electronegativity values are used to predict
electrochemical potential completely how different atoms will behave when bonded
characterizes all of the influences on an ion's to each other, making this an important skill in
motion, while the chemical potential includes basic chemistry. The electronegativity of CBL
everything except the electric force. On the and CBV was found from Table 5 about -4.39
other hand, the electronegativity is a measure eV and -4.42 eV and chemical potential is 4.39
of how strongly an atom attracts the electrons eV and 4.42 eV respectively.
in a bond which is completely equal and
Table 5. Chemical reactivity and chemical kinetics
CBL CBV
Hardness, (η) 4.58 4.11
Softness (S) 0.21 0.24
Electrophilicity (ω) 2.10 2.20
Chemical potential (μ) -4.39 -4.42
Electronegativity, (χ) 4.39 4.42

Vibrational spectra for FT-IR cm-1 is considered for the presence of OH

group. In the other hand, the 2500-2200 cm-1
The existence of the functional groups in spectrum for C-H in benzene ring is identified
the organic molecule can be identified through which is given in Figure 3 and Table 6 included
the vibrational spectroscopy in the principle. the data for optimized condition to calculate
In the cannabis, a strong peak in 3400-3500 vibrational spectrum.

CBL

CBV

Figure 3. Vibrational spectrum for IR

A computational study of thermophysical … 446

Table 6. Data for optimized condition to calculate vibrational spectrum

Normal Mode Degeneracy Frequency Intensity Symmetry
CBL 1 1 21.55 0.043 1A
CBV 1 1 -36.66 0.062 1A

UV spectrum vibration level conjugation and oxygen-based

lone pair of electrons is determined by those of
UV visible spectroscopy combines the spectrum found in 120-30 nm as a broad peak
angular concentration located inside an shown in Figure 4 and Table 7 included the
organic resin or compounds. In the case of data for optimized condition to calculate
cannabis, the conjugation of UV visible electronics spectrum.
spectroscopy with their opposite conjugation,

CBL

CBV

Figure 4. Vibrational spectrum for UV

Table 7. Data for optimized condition to calculate electronic spectrum

Transition Degeneracy Spin Wavelength Oscillator
Multiplicity Strength
CBL 1 1 Triplet 161.49 0.0
CBV 1 1 Triplet 182.65 0.0

Conclusion temperature is changed. The chemical reactivity

was calculated using HOMO, LUMO. The best
In this research study, it was found that, it is finding of this work in term of thermochemical
possible to see a change in the physical and thermophysical and chemical reactivity in
properties of cannabis molecules. However, the views of following properties such as
heat capacity and entropy may vary as
M.N. Sarker et al. 447

electrophilicity (ω), the chemical potential (μ), [11]. Islam M.J., Sarker N., Kumer A., Paul S.
electronegativity (χ), hardness (η) and softness International journal of Advanced Biological and
(S) are almost similar in the tested molecules. Biomedical Research, 2019, 7:318
[12]. Ajoy K., Ahmed B., Sharif M , Al-Mamun A.
Disclosure statement Asian journal of physical and chemical science,
2017, 4:1
No potential conflict of interest was reported by [13]. Kumer A., Sarkar M., Nuruzzaman P.S.
Eurasian Journal of Environmental Research,
the authors.
2019, 3:1
[14]. Kumer A., Khan W. Proceeding of 8th
Orcid
international conference on green chemistry, 8th
IUPAC Conference-2018, shangri-la hotel,
Md Nuruzzaman Sarker 0000-0003-2760- bangkok, Thailand, 2018
0113 [15]. Kumer A., Sarker M.N., Paul S.
Ajoy Kumer 0000-0001-5136-6166 International Journal of Chemistry and
Technology, 2019, 3:26
Mohammad Jahidul Islam 0000-0002-4125- [16]. Kumer A., Sarker M.N., Paul S. Turkish
8222 Computational and Theoretical Chemistry, 2019,
Sunanda Paul 0000-0001-7739-4018 3:59
[17]. Kumer A., Sarker M.N., Paul S., Zannat A.
References Advanced Journal of Chemistry-Section A, 2019,
2:190
[1]. Andre C.M.H., Francois j. Frontiers in plant [18]. Hossain M.I., Kumer A. Asian Journal of
science, 2016, 7:19 Physical and Chemical Sciences, 2017, 4:1
[2]. Butsic V.B., Jacob C. Environmental Research [19]. Hossain M.I., Kumer A. Asian journal of
Letters, 2016, 11:044023 Chemical Science, 2017, 3:1
[3]. Mukherjee A., Chandra Roy S., De Bera S., [20]. Hossain M.I., Kumer A., Begum S.H. Asian
Jiang H.E., Li, Li X., Li C.S., Bera S. Genetic Journal of Physical and Chemical Science, 2018,
Resources and Crop Evolution, 2008, 55:481 5:1
[4]. Christensen H.D.F., RoI Gidley J.T., Rosenfeld [21]. Howard A., McIver J., Collins J. Hypercube
R., Boegli G., Testino L., Brine D.R., Pitt C.G., Wall Inc., Waterloo; 1994
M.E. Science, 1971, 172:165 [22]. Tsuneda T.S., Suzuki J.W., Satoshi Hirao K.
[5]. Mariani J.J.B., Daniel H., Margaret L., Frances The Journal of Chemical Physics, 2010, 133:
R. 2011. Drug and alcohol dependence, 2011, 174101
113:249 How to cite this manuscript: Md
[6]. Huestis M.A.G., David A., Heishman S.J., Nuruzzaman Sarker, Ajoy Kumer, Mohammad
Preston K.L., Nelson R.A., Moolchan E.T., Frank, Jahidul Islam, Sunanda Paul. A computational
R.A. Archives of General Psychiatry, 2001, study of thermophysical, HOMO, LUMO,
58:322 vibrational spectrum and UV-visible spectrum
[7]. Lane S.D.C., Don R., Tcheremissine O.V., of cannabicyclol (CBL), and cannabigerol
Lieving L.M., Pietras C.J. (CBG) using DFT. Asian Journal of Nanoscience
Neuropsychopharmacology, 2005, 30:800 and Materials, 2019, 2(4), 439-447. DOI:
[8]. Fleming M.P.C., Robert C. J Int Hemp Assoc, 10.26655/AJNANOMAT.2019.4.8
1998, 5:280
[9]. Kumar R.C., Pertwee R.G. Anaesthesia, 2001,
56:1059
[10]. Islam M.J., Kumer A., Sarker N., Paul S.,
Zannat A. Advanced Journal of Chemistry-Section
A, 2019, 2:316