外电场下GaN的特性研究
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摘要
以6-311G(3df,3pd)为基组,采用B3PW91方法优化得到GaN基态分子的几何结构,并探究了电场对GaN分子基态能量、电荷布居数、键长、偶极矩、振动频率、红外光谱强度、HOMO、LUMO能级影响.研究表明:无电场时,谐振频率值为576.2218 cm~(-1),与实验值484.9 cm~(-1)很接近.有电场时,键长、偶极矩、能隙Eg、电荷布居数、红外谱强度、HOMO和LUMO能级随电场的增大而减小;谐振频率和分子总能量随电场的增加而增加.谐振频率和红外谱强度对电场有着明显的依赖关系,这对材料的光学特性研究有提供理论参考.
Calculations using density functional theoretical( B3PW91) method with 6-311 G( 3df,3 pd) basis sets were performed on the total energies,equilibrium structures,dipole moments,atomic charge distributions,infrared intensities,harmonic frequencies,highest occupied molecular orbital( HOMO) energy levels,lowest unoccupied molecular orbital( LUMO) energy levels,and energy gaps of the ground state Ga N molecules under different intense electric fields. The results show that the harmonic frequency( f = 576. 2218 cm~(-1)) is close to experiment with data( f = 484. 9 cm~(-1)). With the increase of the external field,the bond length,electric dipole moment,atomic charge distribution,energy gap,infrared intensities,HOMO and LUMO energy are proved to decrease. But harmonic frequencies and total energy are proved to increase. The external electric field has a significant effect on the harmonic frequencies and infrared intensities. These will provide important theoretical reference for the studies of optic properties with materials.
Calculations using density functional theoretical( B3PW91) method with 6-311 G( 3df,3 pd) basis sets were performed on the total energies,equilibrium structures,dipole moments,atomic charge distributions,infrared intensities,harmonic frequencies,highest occupied molecular orbital( HOMO) energy levels,lowest unoccupied molecular orbital( LUMO) energy levels,and energy gaps of the ground state Ga N molecules under different intense electric fields. The results show that the harmonic frequency( f = 576. 2218 cm~(-1)) is close to experiment with data( f = 484. 9 cm~(-1)). With the increase of the external field,the bond length,electric dipole moment,atomic charge distribution,energy gap,infrared intensities,HOMO and LUMO energy are proved to decrease. But harmonic frequencies and total energy are proved to increase. The external electric field has a significant effect on the harmonic frequencies and infrared intensities. These will provide important theoretical reference for the studies of optic properties with materials.
引文
[1]Alivisatos A P.Semiconductor clusters,nanocrystals,and quantum dots[J].Science,1996,271:933.
[2]Ramvall P,Riblet P,Nomura S,et al.Optical properties of Ga N quantum dots[J].J.Appl.Phys.,2000,87:3883.
[3]Xie C K,Xu F Q,Deng R,et al.Studies on electronic structure of Ga N(001)surface[J].Acta Phys.Sin.,2002,51:2606(in Chinese)[谢长坤,徐法强,邓锐,等.Ga N(0001)表面的电子结构研究[J].物理学报,2002,51:2606]
[4]Liang L,Niu P J,Yu L Y.Influence of electron beam irradiation on Ga N-based blue LED[J].Laser&Optoelectronics Prog,2010,47:102301(in Chinese)[梁亮,牛萍娟,于莉媛.电子束辐照对Ga N基蓝光LED性能的影响[J].激光与光电子学进展,2010,47:102301]
[5]Lang J H,Gu B,Xu Y,et al.The Ga N-based semiconductor materials LDs[J].Laser Tech.,2003,27:321(in Chinese),[郎佳红,顾彪,徐茵,等.Ga N基材料半导体激光器综述[J].激光技术,2003,27:321]
[6]Nakamura S.The roles of structural imperfections in In Ga N-based blue light-emitting diodes and laser diodes[J].Science,1998,281:956.
[7]Li Y H,Xu P S,Pan H B,et al.First-principle study on Ga N(1010)surface structure[J].Acta Phys.Sin.,2005,54:317(in Chinese)[李拥华,徐鹏寿,潘海滨,等.Ga N(1010)表面结构的第一性原理计算[J].物理学报,2005,54:317].
[8]Chen X L,Cao Y G,Lan Y C,et al.Synthesis and structure of nanocrystal-assembled bulk Ga N[J].J.Cryst.Growth,2000,209:208.
[9]Zhou M,Andrews L.Reactions of laser-ablated Ga,In,and Tl atoms with nitrogen atoms and molecules.infrared spectra and density functional calculations of Ga N,NGa N,NIn N,and the M3N and MN3molecules[J].J.Phys.Chem.A,2000,104:1648.
[10]Song B,Cao P.Theoretical study of structures of Ga3N3cluster[J].Phys.Lett.A,2002,300:485.
[11]Song B,Cao P.Theoretical study of structures of Ga5N5cluster[J].Phys.Lett.A,2002,306:57.
[12]Song B,Cao P,Li B.Theoretical study of the structure of a Ga6N6cluster[J].Phys.Lett.A,2003,315:308.
[13]Song B,Cao P L.Geometric and electronic structures of small Ga N clusters[J].Phys.Lett.A,2004,328:364.
[14]Kandalam A K,Pandey R,Blanco M A,et al.First principles study of polyatomic clusters of Al N,Ga N,and In N.1.Structure,stability,vibrations,and ionization[J].J.Phys.Chem.B,2000,104:4361.
[15]Kandalam A K,Blanco M A,Pandey R.Theoretical study of AlnNn,GanNn,and InnNn(n=4,5,6)clusters[J].J.Phys.Chem.B,2002,106:1945.
[16]Bel Bruno J J.The structure of small gallium nitride clusters[J].Heteroa.Chem.,2000,11:281.
[17]Costales A,Pandey R.Density functional calculations of small anionic clusters of Group III nitrides[J].J.Phys.Chem.A,2003,107:191.
[18]Ma WJ,Zhang J,Wang Y B,et al.Quantum chemical study on structure and stability of GamN(m=1~9)clusters[J].Acta Chim.Sin.2007,65:1110(in Chinese)[马文瑾,张静,王艳宾,等.GamN(m=1~9)团簇结构与稳定性的量子化学研究[J].化学学报,2007,65:1110].
[19]Wu Y G,Li S X,Hao J X,et al.Properties of ground state and spectrum of Cd Se in different external electric fields[J],Acta Phys.Sin.,2015,64:55(in Chinese)[吴永刚,李世雄,郝进欣,等.外电场下Cd Se的基态性质和光谱特性研究[J].物理学报,2015,64:55]
[20]Li S X,Wu Y G,Linghu R F,et al.Ground state properties and excitation properties of Zn Se under different external electric?elds[J],Acta Phys.Sin.,2015,64:78(in Chinese)[李世雄,吴永刚,令狐荣锋,等.Zn Se在外电场下的基态性质和激发特性研究[J].物理学报,2015,64:78]
[21]Huang D H,Wang B,et al.Molecular structure and spectrum of Aluminium Nitride molecule under the external electric Field[J].Acta Chim.Sin.,2008,66:1599.
[22]Ma M Z,Zhu Z H,Chen X J,et al.Hybrid CISDFT method to study electric field effects on electronic excited states of ethylene[J]Chin.Phys.Soc.B,2005,14:1101.
[23]Cooper G,Burton G R,Chan W F,et al.Absolute oscillator strengths for the photoabsorption of silane in the valence and Si 2p and 2s regions(7.5–350 e V)[J].Chem.Phys.,1995,196:293.
[24]Yin Y H,Wang L.Structure and properties of Ag Br under an external electric field[J].J.At.Mol.Phys.,2017,34:9(in Chinese)[尹跃洪,王莉.外电场下Ag Br分子的结构及性质[J].原子与分子物理学报,2017,34:9]
[25]Liu J G,Zhang Q,An X T,et al.Molecular structure and excited states for vinyl acetate under the external electric field[J].J.At.Mol.Phys.,2017,34:42(in Chinese)[刘建国,张倩,安振涛,等.外电场作用下乙酸乙烯酯的分子结构和激发态[J].原子与分子物理学报,2017,34:42]
[2]Ramvall P,Riblet P,Nomura S,et al.Optical properties of Ga N quantum dots[J].J.Appl.Phys.,2000,87:3883.
[3]Xie C K,Xu F Q,Deng R,et al.Studies on electronic structure of Ga N(001)surface[J].Acta Phys.Sin.,2002,51:2606(in Chinese)[谢长坤,徐法强,邓锐,等.Ga N(0001)表面的电子结构研究[J].物理学报,2002,51:2606]
[4]Liang L,Niu P J,Yu L Y.Influence of electron beam irradiation on Ga N-based blue LED[J].Laser&Optoelectronics Prog,2010,47:102301(in Chinese)[梁亮,牛萍娟,于莉媛.电子束辐照对Ga N基蓝光LED性能的影响[J].激光与光电子学进展,2010,47:102301]
[5]Lang J H,Gu B,Xu Y,et al.The Ga N-based semiconductor materials LDs[J].Laser Tech.,2003,27:321(in Chinese),[郎佳红,顾彪,徐茵,等.Ga N基材料半导体激光器综述[J].激光技术,2003,27:321]
[6]Nakamura S.The roles of structural imperfections in In Ga N-based blue light-emitting diodes and laser diodes[J].Science,1998,281:956.
[7]Li Y H,Xu P S,Pan H B,et al.First-principle study on Ga N(1010)surface structure[J].Acta Phys.Sin.,2005,54:317(in Chinese)[李拥华,徐鹏寿,潘海滨,等.Ga N(1010)表面结构的第一性原理计算[J].物理学报,2005,54:317].
[8]Chen X L,Cao Y G,Lan Y C,et al.Synthesis and structure of nanocrystal-assembled bulk Ga N[J].J.Cryst.Growth,2000,209:208.
[9]Zhou M,Andrews L.Reactions of laser-ablated Ga,In,and Tl atoms with nitrogen atoms and molecules.infrared spectra and density functional calculations of Ga N,NGa N,NIn N,and the M3N and MN3molecules[J].J.Phys.Chem.A,2000,104:1648.
[10]Song B,Cao P.Theoretical study of structures of Ga3N3cluster[J].Phys.Lett.A,2002,300:485.
[11]Song B,Cao P.Theoretical study of structures of Ga5N5cluster[J].Phys.Lett.A,2002,306:57.
[12]Song B,Cao P,Li B.Theoretical study of the structure of a Ga6N6cluster[J].Phys.Lett.A,2003,315:308.
[13]Song B,Cao P L.Geometric and electronic structures of small Ga N clusters[J].Phys.Lett.A,2004,328:364.
[14]Kandalam A K,Pandey R,Blanco M A,et al.First principles study of polyatomic clusters of Al N,Ga N,and In N.1.Structure,stability,vibrations,and ionization[J].J.Phys.Chem.B,2000,104:4361.
[15]Kandalam A K,Blanco M A,Pandey R.Theoretical study of AlnNn,GanNn,and InnNn(n=4,5,6)clusters[J].J.Phys.Chem.B,2002,106:1945.
[16]Bel Bruno J J.The structure of small gallium nitride clusters[J].Heteroa.Chem.,2000,11:281.
[17]Costales A,Pandey R.Density functional calculations of small anionic clusters of Group III nitrides[J].J.Phys.Chem.A,2003,107:191.
[18]Ma WJ,Zhang J,Wang Y B,et al.Quantum chemical study on structure and stability of GamN(m=1~9)clusters[J].Acta Chim.Sin.2007,65:1110(in Chinese)[马文瑾,张静,王艳宾,等.GamN(m=1~9)团簇结构与稳定性的量子化学研究[J].化学学报,2007,65:1110].
[19]Wu Y G,Li S X,Hao J X,et al.Properties of ground state and spectrum of Cd Se in different external electric fields[J],Acta Phys.Sin.,2015,64:55(in Chinese)[吴永刚,李世雄,郝进欣,等.外电场下Cd Se的基态性质和光谱特性研究[J].物理学报,2015,64:55]
[20]Li S X,Wu Y G,Linghu R F,et al.Ground state properties and excitation properties of Zn Se under different external electric?elds[J],Acta Phys.Sin.,2015,64:78(in Chinese)[李世雄,吴永刚,令狐荣锋,等.Zn Se在外电场下的基态性质和激发特性研究[J].物理学报,2015,64:78]
[21]Huang D H,Wang B,et al.Molecular structure and spectrum of Aluminium Nitride molecule under the external electric Field[J].Acta Chim.Sin.,2008,66:1599.
[22]Ma M Z,Zhu Z H,Chen X J,et al.Hybrid CISDFT method to study electric field effects on electronic excited states of ethylene[J]Chin.Phys.Soc.B,2005,14:1101.
[23]Cooper G,Burton G R,Chan W F,et al.Absolute oscillator strengths for the photoabsorption of silane in the valence and Si 2p and 2s regions(7.5–350 e V)[J].Chem.Phys.,1995,196:293.
[24]Yin Y H,Wang L.Structure and properties of Ag Br under an external electric field[J].J.At.Mol.Phys.,2017,34:9(in Chinese)[尹跃洪,王莉.外电场下Ag Br分子的结构及性质[J].原子与分子物理学报,2017,34:9]
[25]Liu J G,Zhang Q,An X T,et al.Molecular structure and excited states for vinyl acetate under the external electric field[J].J.At.Mol.Phys.,2017,34:42(in Chinese)[刘建国,张倩,安振涛,等.外电场作用下乙酸乙烯酯的分子结构和激发态[J].原子与分子物理学报,2017,34:42]