UMP2 method was performed to study the reaction mechanism of CH2 with HNCO.The geometrical configurations of reactants,intermediates,transition states and products were optimized by UMP2 method at the 6-311++G（d,p）l...UMP2 method was performed to study the reaction mechanism of CH2 with HNCO.The geometrical configurations of reactants,intermediates,transition states and products were optimized by UMP2 method at the 6-311++G（d,p）level.The energies of stationary points along the pathways were calculated at QCISD（T）/6-311++G（d,p）.Intermediates and transition states were confirmed by the results of vibration analysis and IRC calculation.From the results of the reaction mechanism of CH2 with HNCO,it is shown that in this reaction there exist three pathways,which are CH2（S）+HNCO→IM1→TS1→CH3+NCO;CH2（S）+HNCO→IM2→TS2→CH2CONH,CH2（T）+HNCO→IM3→TS3→CH2NH+CO,and CH2（T）+HNCO→IM3→TS3→CH2NH+CO.展开更多
The reaction of the CH3 radical with molecular HNCO was examined using MP2 method at the 6311++g**basis set level.The geometry configures of reactants,intermediates,transition states and products were optimi...The reaction of the CH3 radical with molecular HNCO was examined using MP2 method at the 6311++g**basis set level.The geometry configures of reactants,intermediates,transition states and products were optimized.The result shows that the reaction CH3+HNCO→CH4+NCO is an absorbing hydrogen atomprocess,and there is a hydrogenbond complex(M) produced by the interaction of reactants,the energy of which is 813kJ/mol,less than that of the reactants.展开更多
The NH(a^1Δ)+CO(X^1Σ+) product channel for the photodissociation of isocyanic acid(HNCO) on the first excited singlet state S1 has been investigated by means of time-sliced ionvelocity map imaging technique at photo...The NH(a^1Δ)+CO(X^1Σ+) product channel for the photodissociation of isocyanic acid(HNCO) on the first excited singlet state S1 has been investigated by means of time-sliced ionvelocity map imaging technique at photolysis wavelengths around 201 nm. The CO productwas detected through (2+1) resonance enhanced multiphoton ionization (REMPI). Imageswere obtained for CO products formed in the ground and vibrational excited state (v=0 and v=1). The energy distributions and product angular distributions were obtained from the CO velocity imaging. The correlated NH(a^1Δ) rovibrational state distributions were determined.The vibrational branching ratio of 1NH (v=1/v=0) increases as the rotational state of CO(v=0) increases initially and decreases afterwards, which indicates a special state-tostate correlation between the 1NH and CO products. About half of the available energy was partitioned into the translational degree of freedom. The negative anisotropy parameter indicates that it is a vertical direct dissociation process.展开更多
Ab initio method has been employed to investigate the hydrogenbond between two HNCO molecules. Two types of hydrogen-bondings in HNCO dimers have been found, one type is N-H…O, the other is N-H…N. The latter is a li...Ab initio method has been employed to investigate the hydrogenbond between two HNCO molecules. Two types of hydrogen-bondings in HNCO dimers have been found, one type is N-H…O, the other is N-H…N. The latter is a little stabler than that of the former. The stabilization energies of the two types of dimers are estimated to be 13KJ/mol-21KJ/mol.展开更多
The reaction mechanism of CH2F radical with HNCO was investigated by density functional theory （DFT） at the B3LYP/6-311＋＋G（d,p） level. The geometries of the reactants, the intermediates, the transition states an...The reaction mechanism of CH2F radical with HNCO was investigated by density functional theory （DFT） at the B3LYP/6-311＋＋G（d,p） level. The geometries of the reactants, the intermediates, the transition states and the products were optimized. The transition states were verified through the vibration analysis. The relative energies were calculated at the QCISD（T）/6-311＋＋G^＊＊//B3LYP/6-311＋＋G（d,p） level. Seven feasible reaction pathways of the reaction were studied. The results indicate that the pathway （5） is the most favorable to occur, so it is the main pathway of the reaction.展开更多
文摘UMP2 method was performed to study the reaction mechanism of CH2 with HNCO.The geometrical configurations of reactants,intermediates,transition states and products were optimized by UMP2 method at the 6-311++G（d,p）level.The energies of stationary points along the pathways were calculated at QCISD（T）/6-311++G（d,p）.Intermediates and transition states were confirmed by the results of vibration analysis and IRC calculation.From the results of the reaction mechanism of CH2 with HNCO,it is shown that in this reaction there exist three pathways,which are CH2（S）+HNCO→IM1→TS1→CH3+NCO;CH2（S）+HNCO→IM2→TS2→CH2CONH,CH2（T）+HNCO→IM3→TS3→CH2NH+CO,and CH2（T）+HNCO→IM3→TS3→CH2NH+CO.
文摘The reaction of the CH3 radical with molecular HNCO was examined using MP2 method at the 6311++g**basis set level.The geometry configures of reactants,intermediates,transition states and products were optimized.The result shows that the reaction CH3+HNCO→CH4+NCO is an absorbing hydrogen atomprocess,and there is a hydrogenbond complex(M) produced by the interaction of reactants,the energy of which is 813kJ/mol,less than that of the reactants.
基金supported by the National Science Foundation of Anhui Province(No.1608085QA19)the National Science Foundation of China(No.11604052)+3 种基金the Natural Science Research Project of Education Department of Anhui Province(No.2014KJ020)the PhD Research Startup Foundation of Fuyang Normal University(No.FSB201501005)the Quality Engineering Project of Anhui Province(No.2017jyxm0277)the Open Foundation of State Key Laboratory(Nos.SKLMRD-K201611,SKLMRD-K201711 and SKLMRD-K201810)
文摘The NH(a^1Δ)+CO(X^1Σ+) product channel for the photodissociation of isocyanic acid(HNCO) on the first excited singlet state S1 has been investigated by means of time-sliced ionvelocity map imaging technique at photolysis wavelengths around 201 nm. The CO productwas detected through (2+1) resonance enhanced multiphoton ionization (REMPI). Imageswere obtained for CO products formed in the ground and vibrational excited state (v=0 and v=1). The energy distributions and product angular distributions were obtained from the CO velocity imaging. The correlated NH(a^1Δ) rovibrational state distributions were determined.The vibrational branching ratio of 1NH (v=1/v=0) increases as the rotational state of CO(v=0) increases initially and decreases afterwards, which indicates a special state-tostate correlation between the 1NH and CO products. About half of the available energy was partitioned into the translational degree of freedom. The negative anisotropy parameter indicates that it is a vertical direct dissociation process.
文摘Ab initio method has been employed to investigate the hydrogenbond between two HNCO molecules. Two types of hydrogen-bondings in HNCO dimers have been found, one type is N-H…O, the other is N-H…N. The latter is a little stabler than that of the former. The stabilization energies of the two types of dimers are estimated to be 13KJ/mol-21KJ/mol.
基金Ⅵ. ACKN0WLEDGMENTS This work was supported Natural Science Foundation by the Sichuan Province （No.05JY029-038-2） and the Sichuan Province Youth Science Foundation （No.04ZQ026-043）.
文摘The reaction mechanism of CH2F radical with HNCO was investigated by density functional theory （DFT） at the B3LYP/6-311＋＋G（d,p） level. The geometries of the reactants, the intermediates, the transition states and the products were optimized. The transition states were verified through the vibration analysis. The relative energies were calculated at the QCISD（T）/6-311＋＋G^＊＊//B3LYP/6-311＋＋G（d,p） level. Seven feasible reaction pathways of the reaction were studied. The results indicate that the pathway （5） is the most favorable to occur, so it is the main pathway of the reaction.
