苯酚-水团簇C_6H_5OH(H_2O)_n(n=1-6)结构与电子性质的密度泛函理论研究
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摘要
利用密度泛函理论,在B3LYP/6-31+G(d, p)基组水平上对苯酚-水团簇C_6H_5OH(H_2O)_n(n=1-6)的可能构型进行全优化,得到了团簇的稳定结构;在B3LYP/6-311++G(d, p)基组水平上计算得到了各团簇构型的总能量和结合能,结果显示,在团簇尺寸较小(n≤5)时,团簇C_6H_5OH(H_2O)_n的最稳定结构为平面的环状结构,团簇尺寸较大(n>5)时,团簇C_6H_5OH(H_2O)_n的最稳定结构为三维立体结构.通过对团簇结合能的二阶差分、最高占据轨道与最低空轨道之间的能隙、费米能级和电离能的分析发现,团簇C_6H_5OH(H_2O)_2的最低能量结构具有较高的稳定性,可能具有幻数结构.
Using density functional theory, the possible geometrical structures of C_6H_5OH(H_2O)_(n )(n=1-6) clusters were fully optimized at the B3 LYP/6-31+G(d, p) level and the stable structures were attained. The total energies and binding energies of the clusters were calculated at the B3 LYP/6-311++G(d, p) level, and the result shows that the most stable structure of the C_6H_5OH(H_2O)_n(n=1-6)clusters is the plane circular structure when the n≤5, while it would have three-dimensional structure when the n>5. The second order difference of the binding energys, the HOMO-LUMO energy gaps, the Fermi levels, and the ionization potentials reveal that the lowest energy structure of the C_6H_5OH(H_2O)_2 cluster is more stable than any others in this series, and it is probably a magic number structure.
Using density functional theory, the possible geometrical structures of C_6H_5OH(H_2O)_(n )(n=1-6) clusters were fully optimized at the B3 LYP/6-31+G(d, p) level and the stable structures were attained. The total energies and binding energies of the clusters were calculated at the B3 LYP/6-311++G(d, p) level, and the result shows that the most stable structure of the C_6H_5OH(H_2O)_n(n=1-6)clusters is the plane circular structure when the n≤5, while it would have three-dimensional structure when the n>5. The second order difference of the binding energys, the HOMO-LUMO energy gaps, the Fermi levels, and the ionization potentials reveal that the lowest energy structure of the C_6H_5OH(H_2O)_2 cluster is more stable than any others in this series, and it is probably a magic number structure.
引文
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[3] Bacic Z,Miller R E.Molecular clusters:structure and dynamics of weakly bound systems[J].J.Phys.Chem.,1996,100:13945.
[4] Peifer W R,Coolbuagh M T,GaneyF,Observation of "magic numbers" in the population distributions of the (NH3)n-1 NH2+ and (NH3)nH2+ cluster ions:implications for cluster ion structures[J].J.Chem.Phys.,1989,91:6684.
[5] Li Y,Hu Y J,Liu X H,et al.Multiphoton ionization and ab initio calculation studies of the hydrogen-bonded clusters C4H5N-(H2O)n[J].Chin.J.Chem.Phys.,2000,13:11 (in Chinese) [李玥,胡勇军,刘向红,等.C4H5N-(H2O)n氢键团簇的多光子电离与从头计算研究[J].化学物理学报,2000,13:11]
[6] Snyder E M,Purnell J,Wei S,et al.Real-time dynamics of ammonia clusters excited through the ? state:formation of the protonated cluster ions[J].Chem.Phys.,1996,207:355.
[7] Li X M,Zhang L B,Zhou L Z,et al.Theory study of the structures and IR of (C5H5N)n(H2O)m(n=1～2,m=1～4) clusters[J].Spectrosc.Spect.Anal.,2014,34:1805 (in Chinese) [李晓明,张来斌,周留柱,等.吡啶-水团簇(C5H5N)n(H2O)m(n=1～2,m=1～4)结构和红外光谱的理论研究[J].光谱学与光谱分析,2014,34:1805]
[8] Han G Z,Zh C.Gao J G,et al.Quantum chemistry study on the stable structures of C2H5OH(H2O)n (n=1-9) clusters[J].Acta Phys.-Chim.Sin.,2011,27:1361 (in Chinese) [韩光占,张超,高吉刚,等.乙醇-水分子团簇C2H5OH(H2O)n (n=1-9)稳定结构的量子化学研究[J] 物理化学学报,2011,27:1361]
[9] Ahn D S ,Lee S.Density functional theory study of acetonitrile - water clusters:structures and infrared frequency shifts[J].Bull.Korean Chem.Soc.2007,28:725.
[10] Yi M Y,Scheiner S.Proton transfer between phenol and ammonia in ground and excited electronic states[J].Chem.Phys.Lett.,1996,262:567.
[11] Tsui H H Y,Mourik T V.Ab initio calculations on phenol–water [J].Chem.Phys.Lett.,2001,350,565.
[12] Benoit D M,Clary D C.Quantum simulation of phenol-water clusters[J].J.Phys.Chem.A,2000,104:5590.
[13] Jansen A,Gerhards M.Anharmonic vibrational frequencies of proton transfer coordinates in the clusters of aromatic molecules with water[J].J.Chem.Phys.,2001,115:5445.
[14] Dimitrova Y.Theoretical study of structures and stabilities of hydrogen-bonded phenol–water complexes[J].J.Mol.Struct.,1998,455:9.
[15] Benoit D M,Chavagnac A X,Clary D C.Speed improvement of diffusion quantum monte carlo calculations on weakly bound clusters[J].Chem.Phys.Lett.,1998,283:269.
[16] Janzen Ch,Spangenberg D,Roth W,et al.Structure and vibrations of studied by infrared-ultraviolet and ultraviolet-ultraviolet double-resonance spectroscopy and ab initio theory[J].J.Chem.Phys.,1999,110:9898.
[17] Frisch M J,Trucks G W,Schlegel H B,et al.Pittsburgh PA:Gaussian,Inc.,2003.
[18] Prakash M,Gopal Samy K,Subramanian V.Benzene-water (BZWn (n=1-10)) clusters[J].J.Phys.Chem.A,2009,113,13845.
[19] Parthasarathi R,Subramanian V,Sathyamurthy N.Hydrogen bonding in phenol,water,and phenol-water clusters[J].J.Phys.Chem.A,2005,109,843.
[20] Abhishek M,Muthuramalingam P,Ravva M K,et al.Ab initio and DFT studies on methanol-water clusters[J].J.Phys.Chem.A ,2010,114,2250.
[21] Qian P,Song W,Lu L N,et al.Ab initio investigation of water clusters (H2O)n (n=2-34)[J].Int.Quantum Chem.,2010,110:1923.
[22] Wang G H.Cluster physics[M].Shanghai:Shanghai Scientific & Technical Publisher,2003 (in Chinese) [王广厚.团簇物理学[M].上海:上海科学技术出版社,2003]