This study investigates some aspects of interaction between 1 and 4 benzoquinone (BQ) and fluoro derivatives of 1, 4-BQ on surface of zinc oxide nanopatricles theoretically with using density functional method (B3LYP) and 6-31G as basis set. The significant quantities include HOMO, LUMO, chemistry potential, hardness and dipole moment have been computed and compared. The highest gap energy and the most hardness can be referred to the 1, 4- difluoro benzoquinone compared with two another derivatives, 2,5- and 2,6- difluoro benzoquinone. This interaction showed that these
groups stabilize the rest of zinc oxide as blend.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/2054

Bahman, Barati

Mohsen, Oftadeh

SocioEconomic Challenges Journal (Sumy State University)

284                  Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part II             
 
THEORETICAL STUDY OF 1 AND 4 BENZOQUINONE 
AND DIFLUORO DERIVATIVES OF BENZOQUINONE ON 
ZINC OXIDE NANO PARTICLES BY DFT METHOD 
Mohsen Oftadeh*, Bahman Barati 
 
Chemistry Department, Payame Noor University, 19395-4697, Tehran, I. R. of Iran 
 
ABSTRACT 
This study investigates some aspects of interaction between 1 and 4 benzoquinone 
(BQ) and fluoro derivatives of 1, 4-BQ on surface of zinc oxide nanopatricles 
theoretically with using density functional method (B3LYP) and 6-31G as basis set. The 
significant quantities include HOMO, LUMO, chemistry potential, hardness and dipole 
moment have been computed and compared. The highest gap energy and the most 
hardness can be referred to the  1, 4- difluoro benzoquinone compared with two another 
derivatives, 2,5- and 2,6- difluoro benzoquinone. This interaction showed that these 
groups stabilize the rest of zinc oxide as blend. 
 
Key words: gap energy, DFT, zinc oxide blend, benzoquinone, dipole moment, 
hardness 
 
INTRODUCTION 
With development of scientific programs and powerful computer pro-
grams many theoretical studies have been possibly done on the material scienc-
es. These studies will communicate between mid-conductive metal oxide and 
other blends. These mid-conductive are important and they use as catalyst on 
photo catalytic systems, destroy environmental pollutions, transistors, and sun-
ny cells [1-3]. For instance, the mid-conductive of zinc oxide (ZnO) is an ionic 
mid-conductive as grain color, energy wide band in 3.37 ev, and free energy in 
60 MV in room’s temperature and has important role on making industry catal-
yses systems [4-5]. Quinones are blends that can be coupled with DNA. Para 
benzoquinone has known and has been shown that it is anti aromatic [6].  Hy-
droquinone and specially its form oxide have poisoning effects on bio mole-
cules [7]. Quantum chemistry obtains a lot of information about electronic 
structure and numeral frame. In this research, in order to do computations, we 
used density functional theory (DFT). High computational time for the large 
molecular systems was main motivation for using DFT. At present, DFT is a 
standard device for solution of quantum chemistry problems, especially in nano 
calculations [8, 9].   
                                               
* e-mail: m_oftadeh@pnu.ac.ir 
Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part II              285 
 
COMPUTATIONAL METHOD 
Accordance to theoretical concepts, benzoquinone and difluoro derivatives 
are enough small and have tended to theoretical computations. In this research, 
the interaction of  these compounds with the surface of zinc oxide (ZnO)n in 
wurtzite have been investigated  by using Gaussian 03 program at B3LYP/6-
31G** level of theory. The significance quantities, like as HOMO and LUMO 
energies, gap energies, chemical potentials (P), hardness and dipole moments (P) 
were computed and compared.  
RESULTS AND DISCUSSION 
First 1, 4-BQ and Fluoro derivatives of 1, 4-BQ was studied at B3LYP/6-
31G** level of theory. The results have been collected in Table 1.  
 
Table  1 – HOMO, LUMO, gap energy, potential energy, hardness and dipole 
moment calculated at B3LYP/6-31G** level of theory in gas phase for 1,4-BQ and their 
fluro derivatives  
Molecule 
HOMO 
(Hartree) 
LOMO 
(Hartree) 
Gap energy 
(Hartree) 
µ 
(Hartree) 
Ș 
(Hartree) 
P 
(Debye) 
BQ -0.2759 -0.1413 0.1346 -0.2086 0.0673 0.0007 
2F BQ -0.2899 -0.1519 0.1380 -0.2209 0.0690 1.7316 
23DF BQ -0.3050 -0.1623 0.1428 -0.2336 0.0714 2.8427 
25DF BQ -0.3057 -0.1617 0.1440 -0.2367 0.0720 0.0045 
26DF BQ -0.3007 -0.1626 0.1381 -0.2317 0.06901 1.0844 
235 TF BQ -0.3149 -0.1720 0.1429 -0.2435 0.0714 2.7600 
FLORIN -0.3194 -0.1819 0.1375 -0.2507 0.0688 0.0072 
 
The results showed that 2, 3, 5, 6-tetrafluro-1, 4-BQ has the most variation 
in  HOMO  and  LUMO  compared  with  BQ.  So  the  flurination  of  BQ  leads  to  
increase of the gap energy. Also they cause to increase the hardness and stabi-
lize the BQ. 2, 3-difluro-1, 4-BQ has the highest dipole moment.   The next step 
included the optimization of the (ZnO)4n, n=1-3, clusters by using B3LYP/6-
31G** method which the results have been showed in table 2. By attention to 
the results of table 2, it shows the HOMO and LUMO levels of energy decrease 
by increasing the size of ZnO cluster. The highest gap energy and stability are 
related to (ZnO)12. 
 
Table 2 – HOMO, LUMO, gap energy, potential energy, hardness and di-
pole moment calculated at B3LYP/6-31G** level of theory in gas phase for 
(ZnO)2n, n=1-3, clusters  
(ZnO)4n 
n=1,2,3 
HOMO 
(Hartree) 
LOMO 
(Hartree) 
Gap energy 
(Hartree) 
µ 
(Hartree) 
Ș 
(Hartree) 
P 
(Debye) 
(ZnO)4 -0.2462 -0.1318 0.1144 -0.1890 0.0572 0.0262 
(ZnO)8 -0.2408 -0.1250 0.1158 -0.1829 0.0579 0.0154 
(ZnO)12 -0.2371 -0.1118 0.1252 -0.1745 0.0626 0.8476 
286                  Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part II             
 
This is the quantum size effect. (ZnO)12 cluster has the lowest potential 
energy and it’s stability is high. This cluster has the highest hardness and dipole 
moments.      
The third step was the computing of these quantities for the 1, 4-BQ de-
rivatives adsorbent on the (ZnO)8 cluster by the method. Table 3 showed these 
results for the combined systems.   
 
Table  3  – HOMO, LUMO, gap energy, potential energy, hardness and dipole 
moment calculated at B3LYP/6-31G** level of theory in gas phase for combined 1, 4-
BQ derivatives and (ZnO)8 cluster systems 
System HOMO 
(Hartree) 
LOMO 
(Hartree) 
Gap energy 
(Hartree) 
µ 
(Hartree) 
Ș 
(Hartree) 
P 
(Debye) 
(ZNO)8+BQ -0.2230 -0.1803 0.0426 -0.2017 0.0213 7.1316 
(ZNO)8+2FBQ -0.2270 -0.1878 0.0393 -0.2074 0.0196 4.7501 
(ZNO)8+23DF BQ -0.2263 -0.1981 0.0282 -0.2122 0.0141 7.1735 
(ZNO)8+25DFBQ -0.2391 -0.1667 0.0724 -0.2029 0.0362 7.6515 
(ZNO)8+26DFBQ -0.2391 -0.1669 0.0722 -0.2030 0.0361 2.3461 
(ZNO)8+235TFBQ -0.2314 -0.2062 0.0252 -0.2188 0.0126 3.4259 
(ZNO)8+FLORINE -0.2312 -0.2009 0.0303 -0.2161 0.0151 0.7346 
 
The flurination of the BQ cause to decrease the HOMO and to vary the 
LUMO compared to the BQ on the ZnO cluster. The highest HOMO is related 
to the 2, 6-difluro-1, 4-BQ, and the highest variation on the LUMO is related to 
2, 3, 5-trifluro-1, 4-BQ. The lowest chemical potential energy and the highest 
hardness are related to 2, 3, 5, 6-tetrafluro-1, 4-BQ and 2, 5-difluro-1, 4-BQ, 
respectively. So the second system has the highest stabilize. Such trend was 
observed in dipole moments for the systems so that the highest value is related 
to 2, 5-difluro-1, 4-BQ.     
Also, we observed that fluoro blends of 1, 4-BQ cause to be changing on 
(LUMO) and (HOMO) energy in comparison with 1, 4-BQ when they are ab-
sorbed on the surface of ZnO cluster. The quantities of the gap energy showed 
that 2 ,5-difluoro-1, 4-BQ has the highest hardness and stability in comparison 
with rest of zinc blends. 
After absorption of 1, 4-BQ and fluoro derivatives on the surface of the 
zinc oxide blends, the HOMO and LUMO energies of zinc oxide blends de-
crease and  increase, respectively. By attention to the gap energies and there-
fore to the hardness, 2 ,5-difluoro-1, 4-BQ and 2 ,6-difluoro-1 ,4-BQ cause to 
be more stability of zinc oxide in comparison with the rest of  fluoro blends. 
CONCLUSIONS 
The stability of the blends affects on what ever the size of blends and it 
became greater the stability of blend when the size will be increased. Also, the 
results showed that the fluorine groups on the benzoquinone cause to be chang-
Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part II              287 
 
ing on LUMO and HOMO energy. The quantities of the gap energy and hard-
ness for these blends showed that 2, 5- and 1,4-difluoro benzoquinone in com-
parison with rest of zinc blends, increased. After absorption of 1, 4- difluoro 
benzoquinone on the blends HOMO and LUMO decreases and increases com-
pared with the rest of blends, respectively. The highest gap energy and the most 
hardness  can  be  refer  to  the   1,  4-  difluoro  benzoquinone compared with  two 
another derivatives, 2,5- and 2,6- difluoro benzoquinone. This interaction 
showed that these groups stabilize the rest of zinc oxide as blend. 
REFERENCES 
[1]  Xueli Cheng, Feng Li and Yanyun Zhao, Journal of Molecular Structure: THE-
OCHEM 894 (2009) 121. 
[2]  J.  Pollmann,  P.  KNger,  M.  Rohlfing,  M.  Sabisch  and  D.  Vogel,  Applied  Surface  
Science 104/105 (1996) 1. 
[3]  S.  Irrera,  D.  Costa,  K.  Ogle  and  P.  Marcus,  Superlattices  and  Microstructures  46  
(2009) 19. 
[4]  A. Wander and N.M. Harrison, Surface Science 468 (2000) L851. 
[5]  A. Wander and N.M. Harrison, Surface Science 457 (2000) L342. 
[6] . Aaron Rojas-Aguilar, Honorio Flores-Lara, Melchor Martinez-Herrera and Francis-
co Ginez-Carbajal, J. Chem. Thermodynamics 36 (2004) 453. 
[7] Yuanzhi Song,  Jimin Xie,  Huoming Shu,  Ganqing Zhao Xiaomeng Lv and 
Hongyan Cai,  Bioorganic & Medicinal Chemistry 13 (2005) 5658. 
[8] A. K. Rappe, ClJ. Casewit, K. S. Colwell and W. A. Goddard, J. phys. Chem., 94 
(1990) 8897. 
[9] M. Oftadeh, L. Tavakolizadeh, J. Nano Letters, 2011, in press.  
 
 
  


Theoretical study of 1 and 4 benzoquinone and difluoro derivatives of benzoquinone on zinc oxide nano particles by dft method

Electronic Sumy State University Institutional Repository

284                  Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part II              THEORETICAL STUDY OF 1 AND 4 BENZOQUINONE AND DIFLUORO DERIVATIVES OF BENZOQUINONE ON ZINC OXIDE NANO PARTICLES BY DFT METHOD Mohsen Oftadeh*, Bahman Barati  Chemistry Department, Payame Noor University, 19395-4697, Tehran, I. R. of Iran  ABSTRACT This study investigates some aspects of interaction between 1 and 4 benzoquinone (BQ) and fluoro derivatives of 1, 4-BQ on surface of zinc oxide nanopatricles theoretically with using density functional method (B3LYP) and 6-31G as basis set. The significant quantities include HOMO, LUMO, chemistry potential, hardness and dipole moment have been computed and compared. The highest gap energy and the most hardness can be referred to the  1, 4- difluoro benzoquinone compared with two another derivatives, 2,5- and 2,6- difluoro benzoquinone. This interaction showed that these groups stabilize the rest of zinc oxide as blend.  Key words: gap energy, DFT, zinc oxide blend, benzoquinone, dipole moment, hardness  INTRODUCTION With development of scientific programs and powerful computer pro-grams many theoretical studies have been possibly done on the material scienc-es. These studies will communicate between mid-conductive metal oxide and other blends. These mid-conductive are important and they use as catalyst on photo catalytic systems, destroy environmental pollutions, transistors, and sun-ny cells [1-3]. For instance, the mid-conductive of zinc oxide (ZnO) is an ionic mid-conductive as grain color, energy wide band in 3.37 ev, and free energy in 60 MV in room’s temperature and has important role on making industry catal-yses systems [4-5]. Quinones are blends that can be coupled with DNA. Para benzoquinone has known and has been shown that it is anti aromatic [6].  Hy-droquinone and specially its form oxide have poisoning effects on bio mole-cules [7]. Quantum chemistry obtains a lot of information about electronic structure and numeral frame. In this research, in order to do computations, we used density functional theory (DFT). High computational time for the large molecular systems was main motivation for using DFT. At present, DFT is a standard device for solution of quantum chemistry problems, especially in nano calculations [8, 9].                                                  * e-mail: m_oftadeh@pnu.ac.ir Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part II              285  COMPUTATIONAL METHOD Accordance to theoretical concepts, benzoquinone and difluoro derivatives are enough small and have tended to theoretical computations. In this research, the interaction of  these compounds with the surface of zinc oxide (ZnO)n in wurtzite have been investigated  by using Gaussian 03 program at B3LYP/6-31G** level of theory. The significance quantities, like as HOMO and LUMO energies, gap energies, chemical potentials (P), hardness and dipole moments (P) were computed and compared.  RESULTS AND DISCUSSION First 1, 4-BQ and Fluoro derivatives of 1, 4-BQ was studied at B3LYP/6-31G** level of theory. The results have been collected in Table 1.   Table  1 – HOMO, LUMO, gap energy, potential energy, hardness and dipole moment calculated at B3LYP/6-31G** level of theory in gas phase for 1,4-BQ and their fluro derivatives  Molecule HOMO (Hartree) LOMO (Hartree) Gap energy (Hartree) µ (Hartree) Ș (Hartree) P (Debye) BQ -0.2759 -0.1413 0.1346 -0.2086 0.0673 0.0007 2F BQ -0.2899 -0.1519 0.1380 -0.2209 0.0690 1.7316 23DF BQ -0.3050 -0.1623 0.1428 -0.2336 0.0714 2.8427 25DF BQ -0.3057 -0.1617 0.1440 -0.2367 0.0720 0.0045 26DF BQ -0.3007 -0.1626 0.1381 -0.2317 0.06901 1.0844 235 TF BQ -0.3149 -0.1720 0.1429 -0.2435 0.0714 2.7600 FLORIN -0.3194 -0.1819 0.1375 -0.2507 0.0688 0.0072  The results showed that 2, 3, 5, 6-tetrafluro-1, 4-BQ has the most variation in  HOMO  and  LUMO  compared  with  BQ.  So  the  flurination  of  BQ  leads  to  increase of the gap energy. Also they cause to increase the hardness and stabi-lize the BQ. 2, 3-difluro-1, 4-BQ has the highest dipole moment.   The next step included the optimization of the (ZnO)4n, n=1-3, clusters by using B3LYP/6-31G** method which the results have been showed in table 2. By attention to the results of table 2, it shows the HOMO and LUMO levels of energy decrease by increasing the size of ZnO cluster. The highest gap energy and stability are related to (ZnO)12.  Table 2 – HOMO, LUMO, gap energy, potential energy, hardness and di-pole moment calculated at B3LYP/6-31G** level of theory in gas phase for (ZnO)2n, n=1-3, clusters  (ZnO)4n n=1,2,3 HOMO (Hartree) LOMO (Hartree) Gap energy (Hartree) µ (Hartree) Ș (Hartree) P (Debye) (ZnO)4 -0.2462 -0.1318 0.1144 -0.1890 0.0572 0.0262 (ZnO)8 -0.2408 -0.1250 0.1158 -0.1829 0.0579 0.0154 (ZnO)12 -0.2371 -0.1118 0.1252 -0.1745 0.0626 0.8476 286                  Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part II              This is the quantum size effect. (ZnO)12 cluster has the lowest potential energy and it’s stability is high. This cluster has the highest hardness and dipole moments.      The third step was the computing of these quantities for the 1, 4-BQ de-rivatives adsorbent on the (ZnO)8 cluster by the method. Table 3 showed these results for the combined systems.    Table  3  – HOMO, LUMO, gap energy, potential energy, hardness and dipole moment calculated at B3LYP/6-31G** level of theory in gas phase for combined 1, 4-BQ derivatives and (ZnO)8 cluster systems System HOMO (Hartree) LOMO (Hartree) Gap energy (Hartree) µ (Hartree) Ș (Hartree) P (Debye) (ZNO)8+BQ -0.2230 -0.1803 0.0426 -0.2017 0.0213 7.1316 (ZNO)8+2FBQ -0.2270 -0.1878 0.0393 -0.2074 0.0196 4.7501 (ZNO)8+23DF BQ -0.2263 -0.1981 0.0282 -0.2122 0.0141 7.1735 (ZNO)8+25DFBQ -0.2391 -0.1667 0.0724 -0.2029 0.0362 7.6515 (ZNO)8+26DFBQ -0.2391 -0.1669 0.0722 -0.2030 0.0361 2.3461 (ZNO)8+235TFBQ -0.2314 -0.2062 0.0252 -0.2188 0.0126 3.4259 (ZNO)8+FLORINE -0.2312 -0.2009 0.0303 -0.2161 0.0151 0.7346  The flurination of the BQ cause to decrease the HOMO and to vary the LUMO compared to the BQ on the ZnO cluster. The highest HOMO is related to the 2, 6-difluro-1, 4-BQ, and the highest variation on the LUMO is related to 2, 3, 5-trifluro-1, 4-BQ. The lowest chemical potential energy and the highest hardness are related to 2, 3, 5, 6-tetrafluro-1, 4-BQ and 2, 5-difluro-1, 4-BQ, respectively. So the second system has the highest stabilize. Such trend was observed in dipole moments for the systems so that the highest value is related to 2, 5-difluro-1, 4-BQ.     Also, we observed that fluoro blends of 1, 4-BQ cause to be changing on (LUMO) and (HOMO) energy in comparison with 1, 4-BQ when they are ab-sorbed on the surface of ZnO cluster. The quantities of the gap energy showed that 2 ,5-difluoro-1, 4-BQ has the highest hardness and stability in comparison with rest of zinc blends. After absorption of 1, 4-BQ and fluoro derivatives on the surface of the zinc oxide blends, the HOMO and LUMO energies of zinc oxide blends de-crease and  increase, respectively. By attention to the gap energies and there-fore to the hardness, 2 ,5-difluoro-1, 4-BQ and 2 ,6-difluoro-1 ,4-BQ cause to be more stability of zinc oxide in comparison with the rest of  fluoro blends. CONCLUSIONS The stability of the blends affects on what ever the size of blends and it became greater the stability of blend when the size will be increased. Also, the results showed that the fluorine groups on the benzoquinone cause to be chang-Nanomaterials: Applications and Properties (NAP-2011). Vol. 1, Part II              287  ing on LUMO and HOMO energy. The quantities of the gap energy and hard-ness for these blends showed that 2, 5- and 1,4-difluoro benzoquinone in com-parison with rest of zinc blends, increased. After absorption of 1, 4- difluoro benzoquinone on the blends HOMO and LUMO decreases and increases com-pared with the rest of blends, respectively. The highest gap energy and the most hardness  can  be  refer  to  the   1,  4-  difluoro  benzoquinone compared with  two another derivatives, 2,5- and 2,6- difluoro benzoquinone. This interaction showed that these groups stabilize the rest of zinc oxide as blend. REFERENCES [1]  Xueli Cheng, Feng Li and Yanyun Zhao, Journal of Molecular Structure: THE-OCHEM 894 (2009) 121. [2]  J.  Pollmann,  P.  KNger,  M.  Rohlfing,  M.  Sabisch  and  D.  Vogel,  Applied  Surface  Science 104/105 (1996) 1. [3]  S.  Irrera,  D.  Costa,  K.  Ogle  and  P.  Marcus,  Superlattices  and  Microstructures  46  (2009) 19. [4]  A. Wander and N.M. Harrison, Surface Science 468 (2000) L851. [5]  A. Wander and N.M. Harrison, Surface Science 457 (2000) L342. [6] . Aaron Rojas-Aguilar, Honorio Flores-Lara, Melchor Martinez-Herrera and Francis-co Ginez-Carbajal, J. Chem. Thermodynamics 36 (2004) 453. [7] Yuanzhi Song,  Jimin Xie,  Huoming Shu,  Ganqing Zhao Xiaomeng Lv and Hongyan Cai,  Bioorganic & Medicinal Chemistry 13 (2005) 5658. [8] A. K. Rappe, ClJ. Casewit, K. S. Colwell and W. A. Goddard, J. phys. Chem., 94 (1990) 8897. [9] M. Oftadeh, L. Tavakolizadeh, J. Nano Letters, 2011, in press.      

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Theoretical study of 1 and 4 benzoquinone and difluoro derivatives of benzoquinone on zinc oxide nano particles by dft method

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