气相中HRnCCH和X(X=H2O,NH3)反应机理的理论研究

doi:10.7503/cjcu20130863

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (2): 344.doi: 10.7503/cjcu20130863

气相中HRnCCH和X(X=H₂O,NH₃)反应机理的理论研究

高成贵¹, 隆正文¹(), 谭兴凤², 龙波^1,²(), 张为俊³, 龙超云¹, 秦水介¹

1. 贵州大学物理系, 贵阳 550025
2. 贵州民族大学信息工程学院, 贵阳 550025
3. 中国科学院安徽光学精密机械研究所环境光谱实验室, 合肥 230031

收稿日期:2013-09-05 出版日期:2014-02-10 发布日期:2013-12-30
作者简介:联系人简介: 隆正文, 男, 教授, 博士生导师, 主要从事大气化学研究. E-mail:sci.zwlong@gzu.edu.cn; 龙波, 男, 博士, 副教授, 主要从事大气化学研究. E-mail : longbo@gzmu.edu.cn
基金资助:
国家自然科学基金(批准号: 41165007)、贵州省科学技术基金(批准号: 黔科合J字[2011]2107, 黔科合J字[2012]2189)、中国科学院大气成分与光学重点实验室开放课题(批准号: JJ1107)和贵州大学研究生创新基金(批准号: 2013023)资助

Theoretical Investigation on the Reaction Between HRnCCH and X(X=H₂O, NH₃) in Gas Phase^†

GAO Chenggui¹, LONG Zhengwen^1,^*(), TAN Xingfeng², LONG Bo^1,^2,^*(), ZHANG Weijun³, LONG Chaoyun¹, QIN Shuijie¹

1. Department of Physics, Guizhou University, Guiyang 550025, China
2.College of Information Engineering, Guizhou Minzu University, Guiyang 550025, China
3.Laboratory of Environment Spectroscopy, Anhui Institute of Optics and Fine Mechanics,Chinese Academy of Sciences, Hefei 230031, China

Received:2013-09-05 Online:2014-02-10 Published:2013-12-30
Contact: LONG Zhengwen,LONG Bo E-mail:sci.zwlong@gzu.edu.cn;longbo@gzmu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.41165007), the Science and Technology Foundation of Guizhou Province, China(Nos.20102107, 20122189), the Open Research Fund of Key Laboratory of Atmospheric Composition and Optical Radiation, Chinese Academy of Sciences(No.JJ1107) and the Graduate Innovation Foundation of Guizhou University, China(No.2013023)

摘要/Abstract

摘要：

在CCSD(T)//MP2/aug-cc-pVTZ-pp理论水平上, 研究了HRnCCH与大气中H₂O及NH₃分子反应的机理, 反应主要包括HRnCCH与HRnOH及HRnNH₂之间的转化、 H₂O和NH₃在HRnCCH中的碳碳三键上的加成反应以及HRnCCH与双分子水反应等. 结果表明, HRnCCH与H₂O反应生成HCCH和HRnOH及HRnCCH与NH₃反应生成HCCH和HRnNH₂的能垒分别为54.1和75.2 kJ/mol, 而生成HRnCHC(OH)H, HRnC(OH)CH₂, HRnCHC(NH₂)H和HRnC(NH₂)CH₂的活化能分别为219.6, 220.5, 174.4和182.4 kJ/mol, 此结果表明HRnCCH反应性较弱且是稳态存在的. 此外, 在HRnCCH与H₂O反应中加入单个水分子, 仍然生成HRnCHC(OH)H, 但反应活化能却降低了96.4 kJ/mol, 说明水分子对该反应有明显的催化作用.

关键词: HRnCCH, 量子化学计算, 反应机理, 水, 氨气

Abstract:

The reaction mechanisms of HRnCCH with H₂O, NH₃ were explored at the CCSD(T)//MP2/aug-cc-pVTZ-pp level of theory. This investigation involved the conversion between HRnCCH and HRnOH, HRnCCH and HRnNH₂, and the water, water dimer, and ammonia gas molecule addition to the C≡C bond in the HRnCCH, respectively. The calculated results show that the HCCH+HRnOH is produced by the reaction of HRnCCH+H₂O with an activated barrier of 54.1 kJ/mol and HCCH+HRnNH₂ is yielded via the reaction of HRnCCH+NH₃ with a estimated barrier of 75.2 kJ/mol. However, the formations of HRnCHC(OH)H, HRnC(OH)CH₂, HRnCHC(NH₂)H and HRnC(NH₂)CH₂ have the respective barrier of 219.6, 220.5, 174.4 and 182.4 kJ/mol. Therefore, the reactivity of HRnCCH is of quite weakness at the environments investigated herein, which indicates that HRnCCH could be existed under these conditions. In addition, the second water molecule introduced into the HRnCCH+H₂O reaction leads to the remarkable reduction for the barrier of the formation of HRnCHC(OH)H to 123.2 kJ/mol, in which the second water molecule plays a strong catalytic role in the reaction of HRnCCH with water.

Key words: HRnCCH, Quantum chemical calculation, Reaction mechanism, Water, Ammonia gas

中图分类号:

O641

TrendMD:

高成贵, 隆正文, 谭兴凤, 龙波, 张为俊, 龙超云, 秦水介. 气相中HRnCCH和X(X=H₂O,NH₃)反应机理的理论研究. 高等学校化学学报, 2014, 35(2): 344.

GAO Chenggui, LONG Zhengwen, TAN Xingfeng, LONG Bo, ZHANG Weijun, LONG Chaoyun, QIN Shuijie. Theoretical Investigation on the Reaction Between HRnCCH and X(X=H₂O, NH₃) in Gas Phase^†. Chem. J. Chinese Universities, 2014, 35(2): 344.

图/表 7

Table 1 Properties of the studied H-bonded complexesa

H-Bond type	E_HB/(kJ·mol^-1)	R(H…X)/nm	R(Y…H)/nm	$ν ˙$ (Y…H)/cm^-1
RC1(H₂O…HRnCCH)	4.6	0.2435	0.1807	1761.99
RC2(H₃N…HRnCCH)	7.5	0.2277	0.1806	1699.26
RC3(HRnCCH…OH₂)	5.1	0.2238	0.1069	3403.46
RC4(HRnCCH…NH₃)	3.7	0.2318	0.1072	3351.37
HCCH…OH₂	1.4^b	0.2186 ^b	0.1067 ^b	3392.80 ^b
HCCH…NH₃	1.7 ^b	0.2259 ^b	0.1071 ^b	3334.88 ^b

Table 1 Properties of the studied H-bonded complexesa

H-Bond type	E_HB/(kJ·mol^-1)	R(H…X)/nm	R(Y…H)/nm	$ν ˙$ (Y…H)/cm^-1
RC1(H₂O…HRnCCH)	4.6	0.2435	0.1807	1761.99
RC2(H₃N…HRnCCH)	7.5	0.2277	0.1806	1699.26
RC3(HRnCCH…OH₂)	5.1	0.2238	0.1069	3403.46
RC4(HRnCCH…NH₃)	3.7	0.2318	0.1072	3351.37
HCCH…OH₂	1.4^b	0.2186 ^b	0.1067 ^b	3392.80 ^b
HCCH…NH₃	1.7 ^b	0.2259 ^b	0.1071 ^b	3334.88 ^b

Fig.1 Optimized geometries of H2O…HRnCCH and H3N…HRnCCH and their corresponding transition states and products at MP2/aug-cc-pVTZ-pp level of theory Bond lengths are in nm.

Fig.2 Potential energy profiles at CCSD(T)//MP2/aug-cc-pVTZ-pp level of theoryThe reactions begin with the forming of hydrogen-bonded reactant complexes: (A) X…HRnCCH(X=H2O or NH3);(B) HRnCCH…OH2; (C) HRnCCH…NH3.

Table 2 Activated energies(ΔE), enthalpies(ΔH), free energies(ΔG) for the HRnCCH+X(X=H2O, NH3) reactions added with zero-point correction included at 298 K

Reaction	ΔH^a /(kJ·mol^-1)	ΔG^a/(kJ·mol^-1)	ΔE^a/(kJ·mol^-1)	ΔE^b/(kJ·mol^-1)	T1^c
HRnCCH+H₂O	0	0	0	0	0.012, 0.010
RC1	-2.9	14.0	-4.9	-4.6	0.012
TS1	42.8	79.5	47.8	54.1	0.012
P1	22.7	29.8	27.0	-2.9	0.013, 0.013
RC3	-5.1	15.6	-75.2	-5.1	0.012
TS3	207.9	248.3	214.3	219.6	0.015
TS3a	214.2	254.2	220.5	220.5	0.016
P3	-72.9	-30.9	-66.1	-89.7	0.013
P3a	-76.0	-35.2	-69.5	-92.5	0.013
HCCH+H₂O			222.2, 241.8, 243.9^d
HRnCCH+NH₃	0	0	0	0	0.012, 0.008
RC2	-5.7	15.9	-7.0	-7.5	0.012
TS2	67.2	102.8	71.6	75.2	0.012
P2	23.5	23.6	25.7	43.1	0.011, 0.013
RC4	-7.3	14.6	-8.1	-3.7	0.012
TS4	165.9	209.6	173.2	174.4	0.014
TS4a	174.4	217.7	181.7	182.4	0.014
P4	-75.5	-31.0	-67.7	-86.6	0.012
P4a	-105.9	-63.4	-99.3	-114.2	0.013
HCCH+NH₃			181.2, 182.0, 190.4, 192.9^d

Fig.3 Optimized geometries of HRnCCH…OH2 and HRnCCH…NH3 and their corresponding transition states and products at the MP2/aug-cc-pVTZ-pp level of theoryBond lengths are in nm.

Fig.4 Optimized geometries of RCH2O(A) and TSH2O(B) at the MP2/aug-cc-pvtz-pp level of theory Bond lengths are in nm.

Table 3 Activated energies(ΔE), enthalpies(ΔH) and free energies(ΔG) for the HRnCCH…H2O+H2O reactions with zero-point correction included at 298 K

Reaction	ΔH^a /(kJ·mol^-1)	ΔG^a/(kJ·mol^-1)	ΔE^a/(kJ·mol^-1)	ΔE^b/(kJ·mol^-1)	T1^c
HRnCCH…H₂O+H₂O	0.0	0.0	0.0	0.0	0.012, 0.010
R $C H 2 O$	-45.1	16.6	-41.8	-55.3	0.012
T $S H 2 O$	110.8	196.4	122.9	123.2	0.016

Table 3 Activated energies(ΔE), enthalpies(ΔH) and free energies(ΔG) for the HRnCCH…H2O+H2O reactions with zero-point correction included at 298 K

Reaction	ΔH^a /(kJ·mol^-1)	ΔG^a/(kJ·mol^-1)	ΔE^a/(kJ·mol^-1)	ΔE^b/(kJ·mol^-1)	T1^c
HRnCCH…H₂O+H₂O	0.0	0.0	0.0	0.0	0.012, 0.010
R $C H 2 O$	-45.1	16.6	-41.8	-55.3	0.012
T $S H 2 O$	110.8	196.4	122.9	123.2	0.016

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气相中HRnCCH和X(X=H₂O,NH₃)反应机理的理论研究

Theoretical Investigation on the Reaction Between HRnCCH and X(X=H₂O, NH₃) in Gas Phase^†

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