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采用基于密度泛函理论中的广义梯度近似，在考虑自旋多重度的情况下，对YnNO（n=1–12）团簇进行了构型优化，以及稳定性和成键特性分析，结果表明：n=5，7，8，10时，NO吸附使相应的Yn团簇基态结构发生了明显变化，吸附后，所有尺寸中的N–O键长明显伸长，振动频率减弱，表明NO在Yn团簇表面发生的是解离性吸附，N–Y，O–Y键的共同作用使YnNO团簇具有很大的吸附能；特别是n=3，5，8时，N–O键断裂，吸附能值分别为9.92，9.24，9.82 eV. YnNO和Yn 的二阶能量差分变化趋势表明，NO 吸附对Yn团簇稳定性和成键特性均产生较大影响. N，O原子sp3轨道杂化时孤对电子的出现导致N–O键断裂，增强了N–Y和O–Y间的成键能力，使Y3NO，Y5NO，Y8NO团簇表现出了很好的稳定性.The geometry structures, stabilities and chemical bonding properties of the YnNO(n=1–12) clusters are studied in the generalized gradient approximation based on the density functional theory with the consideration of spin multiplicities. The results show that NO adsorption changes the basic frameworks of the corresponding Yn clusters with n=5, 7, 8, 10. The obvious elongation of N–O bond length and the attenuate vibrational frequency indicate that the adsorption of NO on Yn cluster can be regarded as the dissociative adsorption. The chemical bondings of N–Y and O–Y both simultaneously play an important role in enlarging the adsorption energy of YnNO clusters. Specially, Y3NO, Y5NO, and Y8NO have the giant adsorption energies (9.92, 9.24, and 9.82 eV) coupled with the break of the N–O bond. The calculated second-order energy differences suggest that the NO adsorption has influences on the stabilities and bonding properties of Yn clusters. The appearance of the couple electrons, arising from the sp3 hybridization of N and O atom, not only leads to the fracture of N–O bond, but also enhances the ability to form N–Y bond and O–Y bond, which has important effects on the high stabilities of Y3NO, Y5NO, and Y8NO clusters.
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Keywords:
- clusters /
- NO adsorption /
- basic structures /
- stabilities
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[1] Guo L 2013 J. Phys. Chem. A 117 3458
[2] Li W J, Yang H H, Chen H S 2013 Acta Phys. Sin. 62 053601(in Chinese) [李文杰, 杨慧慧, 陈宏善 2013 62 053601]
[3] Fang C H, Shang J X, Liu Z H 2012 Acta Phys. Sin. 61 047101 (in Chinese) [房彩虹, 尚家香, 刘增辉 2012 61 047101]
[4] Zhang X R, Wang Y Y, Li W J, Yuan A H 2013 Acta Phys. Sin. 62 053603 (in Chinese) [张秀荣, 王杨杨, 李维军, 袁爱华 2013 62 053603]
[5] Kuang X J, Wang X Q, Liu G B 2010 Catal. Lett. 137 247
[6] Tian F Y, Shen J, Wang Y X 2010 J. Phys. Chem. A 114 1616
[7] Wang Y J, Wang C Y, Wang S Y 2011 Chin. Phys. B 20 036801
[8] Li M, Zhang J Y, Zhang Y, Wang T M 2012 Chin. Phys. B 21 067302
[9] Wang Y Y, Zhang D J, Liu C B 2011 Sci. China Chem. 54 194
[10] He C Z, Wang H, Huai L Y, Liu J Y 2013 Chem. J. Chinese Univ. 34 946 (in Chinese) [何朝政, 王会, 淮丽媛, 刘靖尧 2013 高等学校化学学报 34 946]
[11] Sun L H, Hu J F, Gao F, Zhang Y J, Qin H W 2011 Physica B 406 4105
[12] Ghosh P, Pushpa R, de Gironcoli S, Narasimhan S arxiv: 0709 4365
[13] Danilczuk M, Lund A 2010 Chem. Phys. Lett. 490 205
[14] L B, Linghu R F, Song X S, Li Y F, Yang X D 2012 Acta Phys. Sin. 61 226801 (in Chinese) [吕兵, 令狐荣锋, 宋晓书, 李应发, 杨向东 2012 61 226801]
[15] Xu X L, Chen W K, Wang X, Lu C H, Li Y 2007 Chinese J. Inorg. Chem. 23 1375 (in Chinese) [徐香兰, 陈文凯, 王霞, 陆春海, 李奕 2007 无机化学学报 23 1375]
[16] Osterberg U, Margulis W 1986 Opt. Lett. 11 516
[17] Xu C, Ai X 2001 Int. J. Ref. Mater. Hard Mater. 19 85
[18] Patel D, Liddle S T, Mungur S A, Rodden M, Blake A J, Arnold P L 2006 Chem. Commun. 10 1124
[19] Delley B 1990 J. Chem. Phys. 92 508
[20] Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865
[21] Delley B 2002 Phys. Rev. B 66 155125
[22] Fang L, Chen X, Shen X, Liu Y, Lindsay D M, Lomabrdi J R 2002 Low Temp. Phys. 26 752
[23] Yuan H K, Chen H, Kuang A L, Ahmed A S, Xiong Z H 2007 Phys. Rev. B 75 174412
[24] Walch S P, Bauschlicher Jr C W, 1983 Chem. Phys. Lett. 94 290
[25] Lide D R 1998 CRC Handbook of Chemistry and Physics (Boca Raton: CRC Press) p9
[26] Herzberg G 1946 Molecular Spectra and Molecular Structure ii Infrare and Raman Spectra of Polyatomic Molecules (New York: Lancaster Press) p365
[27] Lin M H, Xie Z X 2008 Structural Chemistry (Beijing: Science Press) pp119–121 (in Chinese) [林梦海, 谢兆雄 2008 结构化学 (北京: 科学出版社) 第119–121页]
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