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过渡金属离子Pt^+和甲烷气相反应机理的理论研究(英文) 被引量：2

Theoretical investigation on the gas phase reaction mechanism of transition-metal ion Pt^+ with methane
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摘要 采用密度泛函理论(DFT)中的B3LYP方法研究了二重态和四重态Pt+与甲烷反应的机理.通过几何构型优化和频率计算,分别获得三个过渡态,并利用内禀反应坐标(IRC)计算进行了验证.在更高的基组水平上计算了单点能,并详细讨论了二重态和四重态的势能面.结果表明在二重态势能面上的反应具有比较低的能垒,是一个放热反应,所以该反应更易于在二重态上进行.氧化加成生成中间体HPt(CH3)+的步骤需要克服一个小小的能垒. The mechanism of the reaction between Pt^＋ （doublet and quartet）and CH4 was investigated with B3LYP method in density functional theory（DFT）. The transition states were characterized by geometry optimization and frequency computation, confirmed by the intrinsic reaction coordination（IRC） calculation. The single point energies were performed at higher basis set level and compared for the two potential energy surfaees（PES）. The PESes（doublet and quartet）were discussed in detail. The results showed that the groundstate doublet state has lower energy barrier and is exoergic. Therefore, the reaction on the doublet PES is favorable. The process of the oxidative addition to form the intermediate HPt （CH3）^ ＋ have to overcome a low barrier on the doublet PES.
作者 王丙星 朱井义 胡晓萍 郭玮 王艳秋
机构地区 中国科学院大连化学物理研究所分子反应动力学国家重点实验室 哈尔滨师范大学化学系
出处 《原子与分子物理学报》 CAS CSCD 北大核心 2008年第4期745-749,共5页 Journal of Atomic and Molecular Physics
基金 哈尔滨师范大学科研基金(KM2005-02)
关键词 密度泛函 甲烷 Pt^+ H2 势能面 反应机理 density functional theory（DFT）, methane, Pt^＋ , H2, potential energy surface, reaction mecha-nism
分类号 O641 [理学—物理化学]
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参考文献17

  • 1Allison J, Freas R B, Ridge D P. Cleavage of alkanes by transition-metal ions in the gas-phase[J]. J. Am. Chem. Soc., 1979, 101:1332.
  • 2Irikura K K, Be.auchamp J L. Methane oligomerlzation in the gas-phase by 3rd-row transition-metal ions[J ]. J. Am. Chem. Soc., 1991, 113:2769.
  • 3Sievers M R, Chen Y M, Haynes C L, et al. Activation of CH4, C2H6, and C3H8 by gas-phase Nb^+ and the therrncchemistry of Nb-ligand complexes [J ]. Int. J. Mass Spectrom., 2000, 196 : 149.
  • 4Armentrout P B. Activation of CH4 by gas-phase Mo^+ , and the thermochemistry of Mo-ligand complexes[J]. J. Phys. Chem. A, 2006, 110:8327.
  • 5Armentrout M M, Li F X, Armentrout P B. Is spin conserved in heavy metal systems? Experimental and theoretical studies of the reaction of Re^+ with methane [J], J. Phys. Chem. A, 2004, 108:9660.
  • 6Zhang X G, Liyanage R, Armentrout P B. Potential energy surface for activation of methane by Pt^+ : a combined guided ion beam and DFT study[ J ]. J, Am. Chem, Soc,, 2001, 123:5563.
  • 7Liu F, Zhang X G, Armentrout P B. Activation of CH4 by gas-phase Ni^+ and the thermochemistry of Ni-ligand complexes[J]. Phys. Chem. Chem. Phys. , 2005, 7: 1054.
  • 8Armentrout P B, Sievers M R. Activation of CH4 by gas-phase Zr^+ and the thermochemistry of Zr-ligand complexes[J]. J. Phys, Chem, A, 2003, 107:4396.
  • 9Kummerlowe G, Balteanu I, Sun Z, et al. Activation of methane and methane-d(4)by ionic platinum clusters [J]. Int. J. Mass Spectrom. , 2006, 254:183.
  • 10Pavlov M, Blomberg M R A, Siegbahn P E M, etal.Pt^+ -catalyzed oxidation of methane: theory and exper- iment[J]. J. Phys. Chem. A, 1997, 101:1567.

同被引文献42

  • 1SHAYESTEH A, LAVROV V V, KOYANAGI G K, et al. Reactions of atomic cations with methane: gas phase room-temperature kinetics and periodicities in reactivity[J]. J Phys Chem: A, 2009, 113 (19) : 5602-5611.
  • 2LI Fengxia, ZHANG Xiaoguang, ARMENTROUT P B. The most reactive third-row transition metal: guided ion beam and theoretical studies of the activation of methane by Ir^+ [J]. Int J Mass Spectrom, 2006, 255/256 : 279-300.
  • 3PARKE L G, HINTON C S, ARMENTROUT P B. Experimental and theoretical studies of the activation of methane by Ta^+ [J]. J Phys ChemiC, 2007, 111 (48) : 17773-17787.
  • 4SANTO E D, MICHELINI M C, RUSSO N. Meth- ane C--H bond activation by gas-phase Th^+ and U^+ : reaction mechanisms and bonding analysis[J]. Organometallics, 2009, 28(13) ..3716-3726.
  • 5LI Jia, CHEN Xianyang, QIU Yixiang, et al. Spinflip reaction of Re ^+ CH4 a relativistic density functional theory investigation[J]. J Phys Chem: A, 2009, 113(30):8471-8477.
  • 6SCHRODER D, SHAIK S, SCHWARZ H. Two-state reactivity as a new concept in organometallic chemistry[J]. Acc Chem Res, 2000, 33(3), 139-145.
  • 7PERRY J K, OHANESSIAN G, GODDARD W A. Mechanism and energetics for dehydrogenation of methane by gaseous iridium ions[J]. Organometallics, 1994, 13(5) :1870-1877.
  • 8IRIKURA K K, BEAUCHAMP J L. Electronic structure considerations for methane activation by third-row transition-metal ions[J]. J Phys Chem, 1991, 95(21): 8344-8351.
  • 9HARVEY J N, ASCHI M, SCHWARZ H, et al. The singlet and triplet states of phenyl cation;a hybrid approach for locating minimum energy crossing points between non-interacting potential energy surfaces[J]. Theor Chem Acc, 1998, 99:95-99.
  • 10LEE C, YANG W, PARR R G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density[J]. Phys Rev..B, 1988, 37(2) :785-789.

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原子与分子物理学报
2008年 第4期

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