effects of central aluminum on spectroscopic properties of ... · 1/4/2019 · corresponds to...

Advanced Studies in Theoretical Physics

Vol. 13, 2019, no. 2, 87 - 101

HIKARI Ltd, www.m-hikari.com

https://doi.org/10.12988/astp.2019.81141

Effects of Central Aluminum on Spectroscopic

Properties of Hexadeca Fluorinated

Phthalocyanine

Handrin A. Ibrahim

Molecular Physics, Kirkuk University

College of Science, Physics Department, Kirkuk, Iraq

Abdlhadi M. Ghaleb

Atomic Physics, Kirkuk University


Abdulhakim Sh. Mohammed

Molecular Physics, Kirkuk University


This article is distributed under the Creative Commons BY-NC-ND Attribution License.

Copyright © 2019 Hikari Ltd.

Abstract

The effects of aluminum atom at double-decker on spectral properties of pure

hexadeca fluorinated phthalocyanine F16Pc in gas phase is performed. Theoretical

computations (viz., electronic structures, by density functional theory calculations

(DFT) were studied. Ultraviolet (UV-vis) spectra calculated by time dependent

density functional theory (TD-DFT) revealed the absorption spectrum peak for

AlF16Pc is a significant red-shifted compared to the F16Pc, this corresponds to

decrease in the optical band gap from Eg = 1.98 eV to Eg = 1.39 eV. The frontier

orbitals surface is changed by an addition the central aluminum atom, many

supplemental orbitals introduce in energies by addition the aluminum atom, these

leads to red shift that observed in Q-band. And electrostatic potential of

fluorinated phthalocyanine molecules more electronegative is consists around the

88 Handrin A. Ibrahim, Abdlhadi M. Ghaleb and Abdulhakim Sh. Mohammed

terminal nitrogen atoms, but for aluminum fluorinated phthalocyanine molecule

whole surface region have the equal charge.

Keywords: Hexadeca fluorinated phthalocyanines; optical properties; energy gap;

excitation processes; electrostatic potentials; DFT

Abbreviations:

DFT – Density Functional Theory

TD-DFT – Time Dependent Density Functional Theory

URHF – Unrestricted Hartree–Fock

SCF – Self-Consistent Field

HOMO – Highest Occupied Molecular Orbital

LOMO – Lowest Unoccupied Molecular Orbital

Eg – Band Gap Energy

λmax – Wave Length at maximum Oscillator Strength

UV-vis – Ultraviolet-visible

ESP – Electrostatic Potential

ESPMs – Electrostatic Potential Molecular Surface Maps

1. Introduction

Recently, the researchers have testified the quick development of the organic

semiconductors, that provides the number of a merits, for instance, flexibility,

lower cost, easy to synthesis, ability of huge production, and the less weight [1],

Thus, which have capability to an absorb light, electrical conducting, and is light

emit that united with the material structure which easily can modified by the

chemical synthesis [2]. presence a double bonds conjugated into their molecular

structures owe their its semiconducting properties. Carbon atoms that forming

double bonds conjugated are the sp2 hybridized and gives rise to σ-bonds and π-

bonds, whose energy levels split into the occupied bonding orbitals with lower

energy and the unoccupied anti-bonding orbitals with higher energy [3]. The

phthalocyanine (Pc) molecules are belong in the organic semiconductors which

offer significant potential for the fundamental and applied sciences. The Pc

distinguish itself as one from the most stabilized organic materials which show no

remarkable degradation beneath air exposure, its temperature stabilization up to

the about 400◦C [4], that has excellent stabilization against light, heat, oxygen and

moisture, cost low, have good selectivity and sensitivity [5], chemical and thermal

stability, and as well catalytic [6]. And possibility of tune those properties by

insert various metals to macrocycles central bore or by introduce different

substituents in their rings peripheries [7]. which is make them a great interest in

the various technological and scientific fields [5], and since have been utilized

molecules from a family of metal phthalocyanine and fluorinated metal

Effects of central aluminum on spectroscopic properties 89

phthalocyanine already have been applied extensively to the many molecular

devices in the various fields [8], such as organic solar cell, organic light-emitting

diodes (OLED) [9], organic field-effect transistors (OFETs) [10], organic

photovoltaic cell (OPV) [11], organic thin-film transistors (OTFT) [12], display

devices, nonlinear optics [13], sensors of gas [8]. And also used in the medical

applications [5], such as, potential photosensitizer for the photodynamic cancer

remedy [14], biosensor devices and antimicrobial activity [15], photodynamic

therapy [16]. In all those applications a position of frontier energy levels (lowest

unoccupied molecular orbital-LUMO, highest occupied molecular orbital-

HOMO) is a high relevance not only the potentials redox as well as contact

properties and conduction type that determined by this levels [17]. inasmuch their

wonderful performance, metal phthalocyanine (MPc) are very promised species

for the organic electrons. Among them, fluorinated metal phthalocyanine

(MF16Pc) currently of great interest because of their remarkable electrons

transition properties [18]. In present contribution, we studied effect of hexadeca

fluorinated phthalocyanine F16Pc toward central aluminum atom at double-decker

AlF16Pc in the gas phase. To this end, molecular structure, excitation processes,

optical properties for optimized structures, energy band gap and the electrostatic

potentials surface maps (ESPMs) were studied.

2. Calculation method

To understanding geometrical and the electronic structure of pure F16Pc and

aluminum F16Pc fluorinated phthalocyanine in neutral and the doublet states, the

computational studies by the density functional theory method were performed

with a Becke three-parameters hybrid exchange, and Lee–Yang–Parr the

correlation functional (B3LYP) was selected to these computations [19,20]. All

calculations performed by Gaussian 09 software package [21]. The F16Pc have

been an optimized by B3LYP/6-31G(d,p) and AlF16Pc B3LYP/6-31G as a basis

set utilizing unrestricted Hartree–Fock (URHF) as an open shell unrestricted self-

consistent field (SCF) calculation. (highest occupied molecular orbital–HOMO),

(lowest unoccupied molecular orbital–LUMO), electrons density distribution in

HOMO and LOMO and the HOMO–LUMO band gap energy (Eg) were

calculated. UV–vis spectra, oscillator strength and excitation processes for the

optimized structure have been calculated by the time dependent density functional

theory (TD-DFT) with B3LYP at 6-31G(d,p)/ 6-31G basis set [22]. After

calculated optimized structure the electrostatic potentials (ESP) utilizing same

basis set and level of theory on the pure and aluminum hexadecafluorinated

phthalocyanines were estimate by a Mulliken population analysis.

3. Results and Discussion

3.1. Molecular geometry

Theoretical calculations of planar geometry for the free–metal and aluminum

fluorinated phthalocyanine was found. However, the optimized geometry structure


that performed in the ground state by DFT method with B3LYP functional using

6-31G(d,p) for F16Pc and 6-31G for AlF16Pc as a basis set, which corresponding

with true minimum on the potential energy surface have been confirmed by an

absence of the imaginary values for vibrational frequencies calculated [23]. The

convergence of optimization was reach when the total energy and forces

convergence are less than 1×10-8 a.u and 1×10-3 a.u, respectively. The

convergence of energy changes smaller than 3×10-6 Ha. maximum force is smaller

than 1×10-4 Ha/bohr., root mean square force smaller than 1×10-4 bohr, the

maximum displacement is smaller than 1×10-3 Ha/bohr and root mean square

displacement smaller than 1×10-3 bohr.

The energy-minimized structure of F16Pc and AlF16Pc with atom numbering are

shown in Figure 1. The minimum energy global, zero-point vibrational energy,

rotational constants and dipole moments that obtained of the geometry optimized

are presented in the Table 1.

3. 3. UV–vis spectra analysis

The UV-vis-NIR absorption spectrum of F16Pc in the gas phase is shown in

Figure 2. The optical spectrum calculated by TD-DFT method with B3LYP

functional using 6-31G(d,p) for F16Pc and 6-31G for AlF16Pc as a basis set.

Absorption maxima Q band is a first band gap energy of F16Pc, in the visible

region as a first peak. This band have a board interval from 472 − 1094 nm and

correspond to the energy band gap Eg = 1.98 eV. Q band is the excitonic

transitions or vibronic states that represents the first π‒π* of fluorinated

phthalocyanine materials. The second energy band gap is named B band

correspond to electronic transition from π–π* that represents by a second single

peak in energy band gap Eg = 3.26 eV in the UV-vis region [24,25].

Figure 3 illustrates the UV-vis-NIR absorption spectra for pure and aluminum

F16Pc. Absorption spectrum peak for AlF16Pc is a significant red-shifted compared

to the F16Pc, and additionally the absorption spectrum curve covers a wide range

610–1520 nm of visible spectrum. This large red shift in an absorption spectrum

corresponds to decrease in the optical band gap from Eg = 1.98 eV to Eg = 1.39

eV. And due to the difference in spin multiplicity, density and energy for

electrons symbiosis to aluminum atom and hydrogen atoms respectively.

3. 4. Electronic properties

Figure 4 illustrates the general shapes of the frontier orbitals for F16Pc that

change by an addition the central aluminum atom. Interestingly, despite distorted

geometries, the underlying symmetry to parent molecule is largely preserved, with

a small perturbation. when electron-releasing by metal the orbitals generally

destabilized. This effect greater for HOMO, that has a large probability density

about all the 16 reactive positioning, than the LUMOs, that have a density only

upon the eight locations. many supplemental orbitals introduce in energies by

addition the aluminum atom. These new orbitals likely play in the band expanding

and also would have the effect on a peak position when they begin to mix with

HOMO−LUMO transition. These leads to red shift that observed in Q-band.

Despite that, total energies are slightly minimized by the presence of fluorine

atoms [18]. As well as, intermolecular charge transition from donor to an acceptor


groups through the single–double bond that conjugated with path can induced

large variations for both the dipole moment and polarizability of molecule [26]. 3.5. Electrostatic potential surface

The electrostatic potentials of F16Pc and AlF16Pc are calculated by DFT/B3LYP

/6-31G(d,p), 6-31G, theory level, respectively. Figure 5. illustrates three-

dimensional electrostatic potential molecular surfaces maps (EPMs) of F16Pc, the

region (tend to blue) represent the electrostatic potentials positive generated when

the overlap of the positive charged particle in molecule, which reveals the

repulsion region, that representing deficiency of electrons particularly in benzene

rings compounds exclusively of the carbon atoms, make this zone as more

electrically positive. however, the region (tend to red) denote negative

electrostatic potential-areas affluent in electrons, and that reveals an attraction

region, in case of fluorinated phthalocyanine molecules more electronegative is

consists around the terminal nitrogen atoms, but for aluminum fluorinated

phthalocyanine whole surface region of molecule have the zero charge [27]. an

intensity of that is proportional with absolute value of potential energy, while

green indicate the surface regions where the electrostatic potentials are near to

zero. Electrostatic potential increase within a following order: red < orange

<yellow < green < blue [28]. The properties appear via electrostatic potentials

surface (EPs) based on charge density define from molecule wave function maps

of the electrostatic potential molecular Median interaction to a point charged

positively with the nuclei and an electrons of molecule [27]. as expressed below.

where V(r) is the electrostatic effect that a resultant created at the r point by both

the nuclei and electrons of molecule, ZA is a charge on nuclei A, located in RA

and ρ(r') electron density function for molecule. Two contributions terms in

potential first caused by nuclei and second by the electrons, respectively [28].

𝑉(𝑟) = ∑𝑍𝐴

|𝑅𝐴 − 𝑟|⁄

A

− ∫𝜌(𝑟)

|𝑟′ − 𝑟|⁄ 𝑑𝑟′

4. Conclusion

In present study, effects of central aluminum atom on the hexadecafluorinated

phthalocyanine in the gas phase, on electronic structure, electron density

distributions at the HOMO and LUMO, UV–vis-NIR spectra, and their

electrostatic potential surface maps were studied, by DFT/ B3LYP/ 6-31G(d,p), 6-

31G method for F16Pc and AlF16Pc respectively. The results reveals that the

structural parameters changed to addition aluminum atom, UV–vis spectra of

aluminum hexadecafluorinated phthalocyanine has one broad band compared to

hexadecafluorinated phthalocyanine has two band this is returns to difference in

spin multiplicity, density and energy for electrons symbiosis for aluminum atom

and hydrogen atoms respectively, these lead to the calculated HOMO – LUMO

gaps for F16Pc and AlF16Pc are 1.984 and 1.39 eV respectively. The calculated


LUMO and HOMO energies display that charge convey and π-electron

delocalization happening within molecule, also the frontier orbitals were changed

by an addition the aluminum. The electrostatic molecular potentials surface

displayed the difference behavior for F16Pc and AlF16Pc, fluorinated

phthalocyanine molecules more electronegative is consists around the terminal

nitrogen atoms, but aluminum fluorinated phthalocyanine all surface region of

molecule has the zero charge, because aluminum is open shell.

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Table 1. Calculated parameters of F16Pc and AlF16Pc.

Structural parameters 6-31G(d,p) 6-31G

F16Pc AlF16Pc

SCF energy (a.u) -3255.941 -3496.479

Total energy (thermal), Etotal (kcal mol-1) 217.102 203.918

Vibrational energy, Evib (kcal mol-1) 215.324 202.140

Zero-point vibrational energy, E0 (kcal mol-1) 190.142 177.171

Rotational constants (GHz)

A 0.03958 0.03949

B 0.03948 0.03942

C 0.01976 0.01972

Dipole moment (Debye)

µx 0.0003 0.0002

µy 0.0000 0.0000

µz 0.0001 -0.0034

µtotal 0.0003 0.0034


Table 2. Data of UV-vis spectral for F16Pc and AlF16Pc.

Complex HOMO LOMO Q Bond B Bond Oscillator

(eV) (eV) λmax

(nm)

Eg

(eV)

λmax

(nm)

Eg

(eV) strength

F16Pc -0.210 -0.136 626 1.984 391 3.176 0.463,

0.078

AlF16Pc -0.197 -0.157 893 1.390 − − 0.09


Table 3. Electronic Transitions of F16Pc and AlF16Pc calculated by the TD-DFT

compound λ nm f Wave function

F16Pc 631

626

412

391

381

0.399

0.463

0.030

0.078

0.075

93% (H → L+1) + 5% (H–6 → L) + …

96% (H → L) + 4% (H–6 → L+1)

94% (H–2 → L)

52% (H–4 → L) + 48 (H–2 → L+1)

92% (H–4 → L+1) + …

AlF16Pc

1073

893

0.003

0.090

28% (H–1 → L) + 4% (H → L+2) A, 68% (H →

L+1) +… B

11% (H → L+1) A, 88% (H → L) B


F16Pc + Al → AlF16Pc +

a b

Figure 1. The minimized-energy structures of F16Pc and its derivative. C, F, N, H

and Al, atoms are denote as dark green, light green, light blue, white, orange

spheres, respectively.

Figure 2. Calculated UV–vis–NIR absorption spectra of F16Pc.

400 600 800 1000 12000

10000

20000

30000

40000

Ep

slo

n

Wavelength, nm

F16Pc

B band

Q bandTD-DFT


Figure 3. Calculated UV–vis–NIR absorption spectra of F16Pc and AlF16Pc.

400 600 800 1000 1200 1400 1600 18000

10000

20000

30000

40000

E

pslo

n

Wavelength, nm

F16Pc

AlF16PcDT-DFT


LOMO LOMO

(First Excited state) (First Excited state)

HOMO (Ground state) HOMO (Ground state)

(a) F16Pc (b) AlF16Pc

Figure 4. The frontier molecular orbitals of an optimized geometry molecular

structures of the representative F16Pc and its compound. carbon are gray atoms,

nitrogen are dark blue, fluorine are light blue, first row is HOMO plot (Ground

state) and second row is LOMO plot (first excited state).


(a) F16Pc (b) AlF16Pc

Figure 5. Electrostatic potential surface (ESPs) mapping of (a) F16Pc, (b) AlF16Pc.

Received: November 17, 2019; Published: February 20, 2019

effects of central aluminum on spectroscopic properties of ... · 1/4/2019 · corresponds to...

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