Enthalpy changes of the reactions involved in our previous papers have been re-examined at the G2(MP2) and G2 levels. The G2(MP2) and G2 energies of Ar, Ar+,ArAr+, ArCl+, ArF+, ArH+, ArHe+, ArNe+, ArO+, ArS+, H2+, He,...Enthalpy changes of the reactions involved in our previous papers have been re-examined at the G2(MP2) and G2 levels. The G2(MP2) and G2 energies of Ar, Ar+,ArAr+, ArCl+, ArF+, ArH+, ArHe+, ArNe+, ArO+, ArS+, H2+, He, HeCl+, HeF+, HeO+,HeS+, Ne, NeCl+, NeF+, NeO+ and NeS+ have been calculated. The G2(MP2) and G2 results for all of the interested reactions have also been compared with those of the previous MP2/6-31G** and MP4/6-311G (2df, 2pd) calculations. All of the G2(MP2) and G2 reaction enthalpies are improved from the MP2 and MP4 level of calculations when compared with the experimental data for the four categories of reactions as (1) iso-electronic, isogyric; (2) valence isoelectronic, isogyric; (3) isogyric and (4)non-isogyric reactions with the average absolute deviations of 5.10, 4.60, 7.70 and 9.20 for G2(MP2) and 4.18, 5.19, 6.78 and 6.49kJ·mol-1 for G2, respectively. The individural deviation for almost all of the reactions involved in this work is not more than±13kJ·mol-1 for G2(MP2) and ±8.4kJ·mol-1 for G2. In this paper, an additional number of reactions examined at the G2(MP2) and G2 levels as well as at the MP2/6-31G** and MP4/6-311G (2df, 2pd) levels of calculations have also been reported. The MP2, MP4, G2(MP2) and G2 total energies for the interested chemical species have been calculated if these energies have not been reported in literatures. All of the reaction energies at different levels have been compared with the experimental data in a nummber of reactions devided into the above four categories. The average absolute deviations are 25.9, 36.0, 29.2 and 40.1 for MP2; 8.41, 18.3, 17.2 and 18.3 for MP4; 9.41, 5.98, 4.85 and 6.90 for G2(MP2) and 6.69, 4.06, 3.85 and 4.60 kJ·mol-1 for G2, respectively. It is clear that the MP2 calculation did quite poor for all of the foux categories of reactions and the MP4 did well only for the isoelectronic and isogyric reactions. The G2(MP2) and G2 reproduce the eaperimental reaction enthalpy changes very well for all reactions in the four categories. The individural deviation for almost all of the reactions involved in this work is not more than ±13kJ·mol-1 for G2(MP2) and ±8.4kJ·mol-l for G2 while it may be more than ±84kJ·mol-1 for MP2/6-31G**.展开更多
The atomization energies for BeF, BeF2, BF, BF2, BF3, BO, CF and CF2;electronic affoties for B, BO, CF, Li and LiF; ionization potentials(IP1) for BeF, BF2, BO,CF, CF2, CN, NO and NO2, IP2 for C, N and CF have been ca...The atomization energies for BeF, BeF2, BF, BF2, BF3, BO, CF and CF2;electronic affoties for B, BO, CF, Li and LiF; ionization potentials(IP1) for BeF, BF2, BO,CF, CF2, CN, NO and NO2, IP2 for C, N and CF have been calculated at the G2(MP2) and G2 ab initio levels. These molecules are in their gaseous and ground electronic states with the temperature respect to 298K. The G2(MP2) results are compared with those of the G2 and the theoretical results are compared with those of the experiments as shown in Table 2 through Table 5. The G2(MP2) results for these 24 energies are in good agreement with those of the G2. Their deviations are within±10kJ·mol-1 and the average absolute deviation is 3.2kJ·mol-1. When compared with theories, the experimental results are in fairly agreement in most cases. For the larger deviations, we suppose that the experimental heat of formation for BeF is a little bit too low by about 10-20kJ.mol-1, the electronic affinities for B, BO, CF and LiF are suggested to be re-exandned, the experimental ionization potentials (IP1) for BeF, BF2 and CN are suggested to some further study and the IP2 for CF must be in error in the NBS Tables.展开更多
To study The MALDI-TOF- Mass Spectfometry of silver phenylacetylide in order to investigate The state of aggregation of The functionalized transition metal coordinated compounds including clusters and determine The de...To study The MALDI-TOF- Mass Spectfometry of silver phenylacetylide in order to investigate The state of aggregation of The functionalized transition metal coordinated compounds including clusters and determine The degree of ploymerization of the Silver phenylacetylide. Methods: The silver phenylacetylides were analyzed by The method of MALDI-TOF-MS. Results: The main members of The silver phenylacetylide were tetramer and pentamer The degree of polymerization was found to be up to twelve. Conclusion: The polymerization series of The silver phenylacetylide are according to The formula: Mn= nM+ Ag, (n = 1.2.3... ).展开更多
The compound reacts with 2-(Methylthio)thiophene (C5H6S2) while refluxing in xylene to afford a methylthio-tetramanganese product 4, in which C5H6S2 is cleaved with loss of thiophene. The crystal structure of 4 has be...The compound reacts with 2-(Methylthio)thiophene (C5H6S2) while refluxing in xylene to afford a methylthio-tetramanganese product 4, in which C5H6S2 is cleaved with loss of thiophene. The crystal structure of 4 has been studied by direct method. Based on the 21 685 unique reflections collected using MoKα of X-ray radiation and a CCD-based detector, it is refined to an agreement index (R1) of 0.079 0. The cell is triclinic with dimensions: a=1.719 49 nm, b=1.959 2 nm, c=2.632 6 nm and α=79.733°, β=71.407°, γ=89.387°. There are 12 unit cells of 4 in the cell, with space group P1.展开更多
文摘Enthalpy changes of the reactions involved in our previous papers have been re-examined at the G2(MP2) and G2 levels. The G2(MP2) and G2 energies of Ar, Ar+,ArAr+, ArCl+, ArF+, ArH+, ArHe+, ArNe+, ArO+, ArS+, H2+, He, HeCl+, HeF+, HeO+,HeS+, Ne, NeCl+, NeF+, NeO+ and NeS+ have been calculated. The G2(MP2) and G2 results for all of the interested reactions have also been compared with those of the previous MP2/6-31G** and MP4/6-311G (2df, 2pd) calculations. All of the G2(MP2) and G2 reaction enthalpies are improved from the MP2 and MP4 level of calculations when compared with the experimental data for the four categories of reactions as (1) iso-electronic, isogyric; (2) valence isoelectronic, isogyric; (3) isogyric and (4)non-isogyric reactions with the average absolute deviations of 5.10, 4.60, 7.70 and 9.20 for G2(MP2) and 4.18, 5.19, 6.78 and 6.49kJ·mol-1 for G2, respectively. The individural deviation for almost all of the reactions involved in this work is not more than±13kJ·mol-1 for G2(MP2) and ±8.4kJ·mol-1 for G2. In this paper, an additional number of reactions examined at the G2(MP2) and G2 levels as well as at the MP2/6-31G** and MP4/6-311G (2df, 2pd) levels of calculations have also been reported. The MP2, MP4, G2(MP2) and G2 total energies for the interested chemical species have been calculated if these energies have not been reported in literatures. All of the reaction energies at different levels have been compared with the experimental data in a nummber of reactions devided into the above four categories. The average absolute deviations are 25.9, 36.0, 29.2 and 40.1 for MP2; 8.41, 18.3, 17.2 and 18.3 for MP4; 9.41, 5.98, 4.85 and 6.90 for G2(MP2) and 6.69, 4.06, 3.85 and 4.60 kJ·mol-1 for G2, respectively. It is clear that the MP2 calculation did quite poor for all of the foux categories of reactions and the MP4 did well only for the isoelectronic and isogyric reactions. The G2(MP2) and G2 reproduce the eaperimental reaction enthalpy changes very well for all reactions in the four categories. The individural deviation for almost all of the reactions involved in this work is not more than ±13kJ·mol-1 for G2(MP2) and ±8.4kJ·mol-l for G2 while it may be more than ±84kJ·mol-1 for MP2/6-31G**.
文摘The atomization energies for BeF, BeF2, BF, BF2, BF3, BO, CF and CF2;electronic affoties for B, BO, CF, Li and LiF; ionization potentials(IP1) for BeF, BF2, BO,CF, CF2, CN, NO and NO2, IP2 for C, N and CF have been calculated at the G2(MP2) and G2 ab initio levels. These molecules are in their gaseous and ground electronic states with the temperature respect to 298K. The G2(MP2) results are compared with those of the G2 and the theoretical results are compared with those of the experiments as shown in Table 2 through Table 5. The G2(MP2) results for these 24 energies are in good agreement with those of the G2. Their deviations are within±10kJ·mol-1 and the average absolute deviation is 3.2kJ·mol-1. When compared with theories, the experimental results are in fairly agreement in most cases. For the larger deviations, we suppose that the experimental heat of formation for BeF is a little bit too low by about 10-20kJ.mol-1, the electronic affinities for B, BO, CF and LiF are suggested to be re-exandned, the experimental ionization potentials (IP1) for BeF, BF2 and CN are suggested to some further study and the IP2 for CF must be in error in the NBS Tables.
文摘To study The MALDI-TOF- Mass Spectfometry of silver phenylacetylide in order to investigate The state of aggregation of The functionalized transition metal coordinated compounds including clusters and determine The degree of ploymerization of the Silver phenylacetylide. Methods: The silver phenylacetylides were analyzed by The method of MALDI-TOF-MS. Results: The main members of The silver phenylacetylide were tetramer and pentamer The degree of polymerization was found to be up to twelve. Conclusion: The polymerization series of The silver phenylacetylide are according to The formula: Mn= nM+ Ag, (n = 1.2.3... ).
文摘The compound reacts with 2-(Methylthio)thiophene (C5H6S2) while refluxing in xylene to afford a methylthio-tetramanganese product 4, in which C5H6S2 is cleaved with loss of thiophene. The crystal structure of 4 has been studied by direct method. Based on the 21 685 unique reflections collected using MoKα of X-ray radiation and a CCD-based detector, it is refined to an agreement index (R1) of 0.079 0. The cell is triclinic with dimensions: a=1.719 49 nm, b=1.959 2 nm, c=2.632 6 nm and α=79.733°, β=71.407°, γ=89.387°. There are 12 unit cells of 4 in the cell, with space group P1.
