高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (7): 1181.

• 研究论文 • 上一篇    下一篇

直链小碳簇Cn(n=7~10)微正则解离速率常数的RRKM理论计算(Ⅱ)

王海燕, 黄荣彬, 陈宏, 张强, 郑兰荪   

  1. 固体表面物理化学国家重点实验室厦门大学化学系, 厦门 361005
  • 收稿日期:2000-06-09 出版日期:2001-07-24 发布日期:2001-07-24
  • 通讯作者: 郑兰荪(1954年出生),男,教授,博士生导师,从事团簇及其动力学的研究.E-mail:lszheng@xmu.edu.cn E-mail:lszheng@xmu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:29773040;29890210

Calculation of RRKM Microcanonical Dissociation Rate Constant of Small Linear Carbon Clusters Cn(n=7~10)(Ⅱ)

WANG Hai-Yan, HUANG Rong-Bin, CHEN Hong, ZHANG Qiang, ZHENG Lan-Sun    

  1. State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen 361005, China
  • Received:2000-06-09 Online:2001-07-24 Published:2001-07-24

摘要: 用从头算法研究直链小碳簇C7,C8,C9和C10的解离通道及其动力学.在MP2/6-31G*精度上优化了这些碳簇及其过渡态的结构,并对它们进行了振动分析.计算了各解离通道的活化能,并根据RRKM理论估算了各个通道的微正则解离速率,计算结果说明它们的主要解离通道为裂解C3碎片的方式,这与实验所观察到的小碳簇的解离方式完全一致.

关键词: RRKM理论, 速率常数, 解离, Cn(n=7~10)

Abstract: Ab initio calculation has been applied to calculating the dissociated pathways of small carbon clusters. Linear C7, C8, C9 and C10 and their transition states were optimized at MP2/6-31G* level, and their vibration frequencies were also calculated and analyzed. Based on the calculations, activation energies of the clusters were computed and their microcanoncial decomposition rates of different dissociation pathways were estimated by RRKMtheory. The calculation resultshows that the small carbon clusters tend to lose a C3 fragment during dissociation. It is also the main dissociation channel observed in the dissociation experiments of carbon cluster ions with a linear or ring configuration.

Key words: RRKM theory, Rate constant, Dissociation, Cn(n =710)

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