叠氮化氰的光解离机理

引用本文: 慈成刚, 段雪梅, 刘靖尧, 孙家钟. 叠氮化氰的光解离机理[J]. 物理化学学报, 2010, 26(10): 2787-2792. doi: 10.3866/PKU.WHXB20100914 shu

Citation: CI Cheng-Gang, DUAN Xue-Mei, LIU Jing-Yao, SUN Chia-Chung. Photodissociation Mechanism of Cyanogen Azide[J]. Acta Physico-Chimica Sinica, 2010, 26(10): 2787-2792. doi: 10.3866/PKU.WHXB20100914 shu

叠氮化氰的光解离机理

基金项目:
国家自然科学基金(20333050, 20303007, 20973077) 和教育部新世纪优秀人才支持计划(NCET) 资助项目 (20333050, 20303007, 20973077) 和教育部新世纪优秀人才支持计划(NCET)

摘要:

采用多参考态方法, 在MRCI+Q//CAS(10, 9)/6-311+G(2df)水平上对叠氮化氰(N₃CN)的光解离机理进行理论研究.优化得到基态(S0)和低激发态(S1、S2、T1)势能面上的极小点、过渡态、内转换交叉点(IC-S1/S0)和隙间窜跃交叉点(ISC-S1/T1)的结构和能量, 构建反应势能面. 在MRCI+Q//CAS(10, 9)水平上计算N₃CN 的垂直激发能, 并和实验值进行对比. 结果表明, 在S0、S1、S2 和T1 态势能面上, N—N 键断裂生成N₂+NCN 是主要解离途径, 而C—N 键断裂通道是次要通道. 实验观测到220 nm 处的吸收峰对应分子由S0 态到S1 态的激发, 对应主要光解离产物为NCN[a¹Δ_g]; 而在275 nm 处的吸收峰则对应分子被激发到T1 态, 然后直接生成基态产物NCN[X³Σ^-_g ].我们的理论结果与实验测量符合得很好.

关键词:

English

Photodissociation Mechanism of Cyanogen Azide

1.
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry,Jilin University, Changchun 130023, P. R. China
Received Date: 04 May 2010
Available Online: 27 September 2010
Fund Project:
国家自然科学基金(20333050, 20303007, 20973077) 和教育部新世纪优秀人才支持计划(NCET) 资助项目

Abstract:

We investigated the photodissociation mechanism of cyanogen azide (N₃CN) at the MRCI+Q//CAS(10,9)/6-311+G(2df) level of theory using the multi-reference state method. The optimized structures and energies of the minima, transition states, singlet/singlet conical intersection and singlet/triplet crossing points of the ground and low-lying excited states were obtained to explore the potential energy surfaces of N₃CN. The vertical excited energies calculated at the MRCI+Q//CAS(10, 9) level were compared with the experimental data. It is shown that N—N bond fission to form N₂+NCN is the predominant dissociation pathway on the S0, S1, S2, and T1 surfaces whereas the C—N bond fission channel is the minor pathway. The 220 nm absorption peak observed experimentally corresponds to an excitation from the S0 to the S1 state leading to the major photodissociation product NCN[a¹Δ_g]. The 275 nm absorption peak corresponds to the S0-T1 transition leading to the formed ground-state product NCN[X³Σ^-_g ] via the barrierlessly direct dissociation in the T1 state. Our theoretical results agree well with experimental observations.

Key words:

Reaction mechanism
/ Cyanogens azide
/ Photodissociation
/ Potential energy surface intersectionpoint

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

叠氮化氰的光解离机理

English

Photodissociation Mechanism of Cyanogen Azide

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叠氮化氰的光解离机理

English

Photodissociation Mechanism of Cyanogen Azide

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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