Wn (n= 16)团簇吸附CO的密度泛函研究

张秀荣; 王杨杨; 李维军; 袁爱华

doi:10.7498/aps.62.053603

摘要

采用密度泛函理论(density functional theory, DFT) 在B3LYP/LANL2DZ基组水平上对钨团簇吸附CO分子进行了系统研究. 结果表明, WnCO团簇的基态结构是在Wn团簇中性或阴离子基态结构的基础上吸附CO生长而成; CO的吸附以端位吸附为主,桥位吸附为辅; CO分子在Wn团簇表面发生的是非解离性吸附. 与优化的CO键长(0.116 nm)相比,吸附后C-O键长变长(0.1200.123 nm), 表明吸附后C-O键被削弱, CO分子被活化了.稳定性分析表明,在所研究的团簇中, W3CO和W5CO团簇的稳定性较强;自然键轨道(NBO)分析表明, W原子与CO分子相互作用的本质是CO分子内的杂化轨道与W原子6s, 5d, 6p和6d轨道相互作用的结果.

关键词:

Abstract

CO molecules adsorbed on the Wn clusters are systematically investigated by using density functional theory at the B3LYP/LANL2DZ level.The result indicates that the ground state structures of WnCO clusters are generated when CO molecules are adsorbed on Wn clusters or anionic cluster. We find that among the molecular adsorption states exists mainly the form of end-on type geometry, and that the bridge site adsorption type geometry plays a supplementary role. On the face, the adsorption is a non-dissociative adsorption. The CO bond length increases 0.1200.123 nm in WnCO cluster (compared with 0.116 nm in free CO molecule), which demonstrates that the CO molecules are activated. The stability analysis shows that W3CO and W5CO clusters are more stable than other clusters; natural bond orbital (NBO) analysis indicate that the interaction between W atom and CO molecule is primarily contributed by hybridization of molecular orbits within CO and 6s, 5d, 6p and 6d orbits of W atoms.

Keywords:

作者及机构信息

1.
江苏科技大学数理学院, 镇江 212003;

2.
江苏科技大学材料科学与工程学院, 镇江 212003;

3.
江苏科技大学生物与化学工程学院, 镇江 212003

基金项目: 国家自然科学基金(批准号: 51072072)和江苏省自然科学基金 (批准号: BK2010343)资助的课题.

Authors and contacts

1.
School of Mathematics and Physics, Jiangsu University of Science and Technology, Zhenjiang 212003, China;

2.
School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China;

3.
School of Biology and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 51072072), and the Natural Science Foundation of Jiangsu Province, China (Grant No. BK2010343).

参考文献

[1]	Monteiro R D S, Paes L W C, Carneiro J W D M, Aranda D A G 2008 J. Clust. Sci. 19 601
[2]	Daniel M C, Astruc D 2004 Chem. Rev. 104 293
[3]	Liang P, Wang L, Xiong S Y, Dong Q M, Li X Y 2012 Acta Phys. Sin. 61 053101 (in Chinese) [梁培, 王乐, 熊斯雨, 董前民, 李晓艳 2012 61 053101]
[4]	Liang T, Flynn S D, Morrison A M, Douberly G E 2011 J. Phys. Chem. A 115 7437
[5]	Chen Y H, Cao Y J, Ren B X 2010 Acta Phys. Sin. 59 8015 (in Chinese) [陈玉红, 曹一杰, 任宝兴 2010 59 8015]
[6]	Wang Y J, Wang C Y, Wang S Y 2011 Chin. Phys. B 20 036801
[7]	Ferrin P, Kandoi S, Nilekar A U, Mavrikakis M 2012 Surf. Sci. 606 679
[8]	Li M, Zhang J Y, Zhang Y, Wang T M 2012 Chin. Phys. B 21 067302
[9]	Tian F Y, Shen J 2011 Chin. Phys. B 20 123101
[10]	Jin R, Chen X H 2012 Acta Phys. Sin. 61 093103 (in Chinese) [金蓉, 谌晓洪 2012 61 093103]
[11]	Xi Y J, Li Y, Wu D, Li Z R 2012 Comput. Theor. Chem. 994 6
[12]	Yuan J M, Hao W P, Li S H, Mao Y L 2012 Acta Phys. Sin. 61 087301 (in Chinese) [袁键美, 郝文平, 李顺辉, 毛宇亮 2012 61 087301]
[13]	Yamaguchi W, Murakami J 2005 Chem. Phys. 316 45
[14]	Xu R, Wang X L, Zeng Z 2009 Acta Phys. Sin. 58 S72 (in Chinese) [徐勇, 王贤龙, 曾雉 2009 58 S72]
[15]	Zhang X R, Ding X L, Dai B, Yang J L 2005 J. Mol. Struct: Theochem. 757 113
[16]	Qin Y X, Wang F, Shen W J, Hu M 2012 Acta Phys. Sin. 61 057301 (in Chinese) [秦玉香, 王飞, 沈万江, 胡明 2012 61 057301]
[17]	Hoegaerts D, Sels B F, Vos D E D, Verpoort F, Jacobs P A 2000 Catal. Today 60 209
[18]	Li G H, Tian W, Tang J Y, Ma C A 2007 Acta Phys. Chim. Sin. 23 1370 (in Chinese) [李国华, 田伟, 汤俊艳, 马淳安 2007 物理化学学报 23 1370]
[19]	Santos V C D, Bail A, Okada H D O, Ramos L P, Ciuffi K J, Lima O J, Nakagaki S 2011 Energ. Fuel 25 2794
[20]	Xu X S, Li L, Sun M, Yin S H 2010 J. Liaoning Normal Univ. (Natural Science Edition) 33 36 (in Chinese) [许雪松, 李磊, 孙敏, 尹淑慧 2010 辽宁师范大学学报(自然科学版) 33 36]
[21]	Holmgren L, Andersson M, Rosen A 1998 J. Chem. Phys. 109 3232
[22]	Zhang X R, Kang Z L, Li Y 2011 Chin. J. Comput. Phys. 28 598 (in Chinese) [张秀荣, 康张李, 李杨 2011 计算物理 28 598]
[23]	Zhang X R, Ding X L, Fu Q, Yang J L 2008 J. Mol. Struct: Theochem. 867 17
[24]	Moitra A, Solanki K 2011 Comput. Mater. Sci. 50 2291
[25]	Chen H T, Musaev D G, Lin M C 2008 J. Phys. Chem. C 112 3341
[26]	Ishikawa Y, Kawakami K 2007 J. Phys. Chem. A 111 9940
[27]	Holmgren L, Andersson M, Persson J L, Rosen A 1995 Nanostruct. Mater. 6 1009
[28]	Lyon J T, Gruene P, Fielicke A, Meijer G, Rayner D M 2009 J. Chem. Phys. 131 184706
[29]	Weidele H, Kreisle D, Recknagel E, Icking-Konert G S, Handschuh H, Gantefor G, Eberhardt W 1995 Chem. Phys. Lett. 237 425
[30]	Shane M S, Adam W S, Michael D M 2002 J. Chem. Phys. 116 993
[31]	Lide D R 1995 CRC Handbook of Chemisty and Physics, 73rd edn. (Boca Raton: CRC Press) pp 9-15
[32]	Ge G X, Yang Z Q, Cao H B 2009 Acta Phys. Sin. 58 6128 (in Chinese) [葛桂贤, 杨增强, 曹海滨 2009 58 6128]
[33]	Zhang X R, Cui Y N, Hong L L 2009 J. Comput. Theor. Nanosci. 6 640

施引文献

[1]	Monteiro R D S, Paes L W C, Carneiro J W D M, Aranda D A G 2008 J. Clust. Sci. 19 601
[2]	Daniel M C, Astruc D 2004 Chem. Rev. 104 293
[3]	Liang P, Wang L, Xiong S Y, Dong Q M, Li X Y 2012 Acta Phys. Sin. 61 053101 (in Chinese) [梁培, 王乐, 熊斯雨, 董前民, 李晓艳 2012 61 053101]
[4]	Liang T, Flynn S D, Morrison A M, Douberly G E 2011 J. Phys. Chem. A 115 7437
[5]	Chen Y H, Cao Y J, Ren B X 2010 Acta Phys. Sin. 59 8015 (in Chinese) [陈玉红, 曹一杰, 任宝兴 2010 59 8015]
[6]	Wang Y J, Wang C Y, Wang S Y 2011 Chin. Phys. B 20 036801
[7]	Ferrin P, Kandoi S, Nilekar A U, Mavrikakis M 2012 Surf. Sci. 606 679
[8]	Li M, Zhang J Y, Zhang Y, Wang T M 2012 Chin. Phys. B 21 067302
[9]	Tian F Y, Shen J 2011 Chin. Phys. B 20 123101
[10]	Jin R, Chen X H 2012 Acta Phys. Sin. 61 093103 (in Chinese) [金蓉, 谌晓洪 2012 61 093103]
[11]	Xi Y J, Li Y, Wu D, Li Z R 2012 Comput. Theor. Chem. 994 6
[12]	Yuan J M, Hao W P, Li S H, Mao Y L 2012 Acta Phys. Sin. 61 087301 (in Chinese) [袁键美, 郝文平, 李顺辉, 毛宇亮 2012 61 087301]
[13]	Yamaguchi W, Murakami J 2005 Chem. Phys. 316 45
[14]	Xu R, Wang X L, Zeng Z 2009 Acta Phys. Sin. 58 S72 (in Chinese) [徐勇, 王贤龙, 曾雉 2009 58 S72]
[15]	Zhang X R, Ding X L, Dai B, Yang J L 2005 J. Mol. Struct: Theochem. 757 113
[16]	Qin Y X, Wang F, Shen W J, Hu M 2012 Acta Phys. Sin. 61 057301 (in Chinese) [秦玉香, 王飞, 沈万江, 胡明 2012 61 057301]
[17]	Hoegaerts D, Sels B F, Vos D E D, Verpoort F, Jacobs P A 2000 Catal. Today 60 209
[18]	Li G H, Tian W, Tang J Y, Ma C A 2007 Acta Phys. Chim. Sin. 23 1370 (in Chinese) [李国华, 田伟, 汤俊艳, 马淳安 2007 物理化学学报 23 1370]
[19]	Santos V C D, Bail A, Okada H D O, Ramos L P, Ciuffi K J, Lima O J, Nakagaki S 2011 Energ. Fuel 25 2794
[20]	Xu X S, Li L, Sun M, Yin S H 2010 J. Liaoning Normal Univ. (Natural Science Edition) 33 36 (in Chinese) [许雪松, 李磊, 孙敏, 尹淑慧 2010 辽宁师范大学学报(自然科学版) 33 36]
[21]	Holmgren L, Andersson M, Rosen A 1998 J. Chem. Phys. 109 3232
[22]	Zhang X R, Kang Z L, Li Y 2011 Chin. J. Comput. Phys. 28 598 (in Chinese) [张秀荣, 康张李, 李杨 2011 计算物理 28 598]
[23]	Zhang X R, Ding X L, Fu Q, Yang J L 2008 J. Mol. Struct: Theochem. 867 17
[24]	Moitra A, Solanki K 2011 Comput. Mater. Sci. 50 2291
[25]	Chen H T, Musaev D G, Lin M C 2008 J. Phys. Chem. C 112 3341
[26]	Ishikawa Y, Kawakami K 2007 J. Phys. Chem. A 111 9940
[27]	Holmgren L, Andersson M, Persson J L, Rosen A 1995 Nanostruct. Mater. 6 1009
[28]	Lyon J T, Gruene P, Fielicke A, Meijer G, Rayner D M 2009 J. Chem. Phys. 131 184706
[29]	Weidele H, Kreisle D, Recknagel E, Icking-Konert G S, Handschuh H, Gantefor G, Eberhardt W 1995 Chem. Phys. Lett. 237 425
[30]	Shane M S, Adam W S, Michael D M 2002 J. Chem. Phys. 116 993
[31]	Lide D R 1995 CRC Handbook of Chemisty and Physics, 73rd edn. (Boca Raton: CRC Press) pp 9-15
[32]	Ge G X, Yang Z Q, Cao H B 2009 Acta Phys. Sin. 58 6128 (in Chinese) [葛桂贤, 杨增强, 曹海滨 2009 58 6128]
[33]	Zhang X R, Cui Y N, Hong L L 2009 J. Comput. Theor. Nanosci. 6 640

[1]	曹胜果, 韩佳凝, 李占海, 张振华. 扶手椅型C₃B纳米带: 结构稳定性、电子特性及调控效应. , 2023, 72(11): 117101. doi: 10.7498/aps.72.20222434
[2]	罗强, 杨恒, 郭平, 赵建飞. N型甲烷水合物结构和电子性质的密度泛函理论计算. , 2019, 68(16): 169101. doi: 10.7498/aps.68.20182230
[3]	陈璐, 李烨飞, 郑巧玲, 刘庆坤, 高义民, 李博, 周长猛. B2-和B19'-NiTi表面原子弛豫、表面能、电子结构及性能的理论研究. , 2019, 68(5): 053101. doi: 10.7498/aps.68.20181944
[4]	吴丽君, 随强涛, 张多, 张林, 祁阳. SimGen(m+n=9)团簇结构和电子性质的计算研究. , 2015, 64(4): 042102. doi: 10.7498/aps.64.042102
[5]	阮文, 余晓光, 谢安东, 伍冬兰, 罗文浪. BnY(n=1–11)团簇的结构和电子性质. , 2014, 63(24): 243101. doi: 10.7498/aps.63.243101
[6]	阮文, 谢安东, 余晓光, 伍冬兰. NaBn(n=19)团簇的几何结构和电子性质. , 2012, 61(4): 043102. doi: 10.7498/aps.61.043102
[7]	葛桂贤, 井群, 曹海宾, 杨增强, 唐光辉, 闫红霞. 密度泛函理论研究Run和RunAu(n=112)团簇的结构和电子性质. , 2011, 60(10): 103102. doi: 10.7498/aps.60.103102
[8]	张秀荣, 李扬, 杨星. WnNim(n+m=8)团簇结构与电子性质的理论研究. , 2011, 60(10): 103601. doi: 10.7498/aps.60.103601
[9]	高虹, 朱卫华, 唐春梅, 耿芳芳, 姚长达, 徐云玲, 邓开明. 内掺氮富勒烯N2@C60的几何结构和电子性质的密度泛函计算研究. , 2010, 59(3): 1707-1711. doi: 10.7498/aps.59.1707
[10]	刘立仁, 雷雪玲, 陈杭, 祝恒江. Bn(n=2—15)团簇的几何结构和电子性质. , 2009, 58(8): 5355-5361. doi: 10.7498/aps.58.5355
[11]	李喜波, 王红艳, 罗江山, 吴卫东, 唐永建. 密度泛函理论研究ScnO(n=1—9)团簇的结构、稳定性与电子性质. , 2009, 58(9): 6134-6140. doi: 10.7498/aps.58.6134
[12]	葛桂贤, 罗有华. 密度泛函理论研究MgnOn(n=2—8)团簇的结构和电子性质. , 2008, 57(8): 4851-4856. doi: 10.7498/aps.57.4851
[13]	李喜波, 罗江山, 郭云东, 吴卫东, 王红艳, 唐永建. 密度泛函理论研究Scn，Yn和Lan(n=2—10)团簇的稳定性、电子性质和磁性. , 2008, 57(8): 4857-4865. doi: 10.7498/aps.57.4857
[14]	井群, 张俊, 王清林, 罗有华. 第一性原理对GenB(n=12—19)团簇的最低能量结构及其电子性质的研究. , 2007, 56(8): 4477-4483. doi: 10.7498/aps.56.4477
[15]	王清林, 葛桂贤, 赵文杰, 雷雪玲, 闫玉丽, 杨致, 罗有华. 密度泛函理论对CoBen(n=1—12)团簇结构和性质的研究. , 2007, 56(6): 3219-3226. doi: 10.7498/aps.56.3219
[16]	杨建宋, 李宝兴. 砷化镓离子团簇的稳定性研究. , 2006, 55(12): 6562-6569. doi: 10.7498/aps.55.6562
[17]	葛桂贤, 井群, 杨致, 闫玉丽, 雷雪玲, 赵文杰, 王清林, 罗有华. 第一性原理对NaBen(n=1—12)团簇最低能量结构及其电子性质的研究. , 2006, 55(9): 4548-4552. doi: 10.7498/aps.55.4548
[18]	毛华平, 王红艳, 朱正和, 唐永建. AunY(n＝1—9)掺杂团簇的结构和电子性质研究. , 2006, 55(9): 4542-4547. doi: 10.7498/aps.55.4542
[19]	毛华平, 马美仲. Aun（n=2—9）团簇的几何结构和电子特性. , 2004, 53(6): 1766-1771. doi: 10.7498/aps.53.1766
[20]	吕瑾, 许小红, 武海顺. 3d系列 (TM)4 团簇的结构和磁性. , 2004, 53(4): 1050-1055. doi: 10.7498/aps.53.1050

计量

文章访问数: 6988
PDF下载量: 678
被引次数: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

搜索

留言板