排序方式: 共有219条查询结果,搜索用时 62 毫秒
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反应体系的势能面,对了解反应的微观过程起着重要的作用,它的特征决定了化学反应的机理.原则上,由反应体系的Schrodinger方程的解,可得到体系能量随核间距变化的函数,从而获得势能面.除少数简单反应外,几乎无法精确求得复杂反应体系的势能面.因而,除从头算法外,人们先后发展了计算势能面的一些半经验方法.对某一反应,文献中可能记载好几个势能面,因此,在分析反应或计算反应的各物理量时,应当说明所应用的是何种势能面.我们曾指出,过渡态熵的可靠性,有赖于提供过渡态参数的势能面.本文从下述基元反应 相似文献
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共轭体系分子轨道能的共振同系规律 总被引:2,自引:0,他引:2
同系线性规律已有较多研究.最近戴乾圜等用共振论阐释了同系线性规则,提出了共振同系因子,并用式(1)计算了电子吸收光谱数据的线性相关性. 相似文献
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The HeIα PES of indazole (1a), 3-bromoindazole (2a) and their isomeric nitro derivatives 1b-e and 2b-e have been recorded. It has been found that the lowest π^-^1 ionization energies (I1)^m, (I2)^m are moved towards higher energies under the influence of the nitro group, but that there is no significant dependence of the size of the shifts (ΔI1)^m, (ΔI2)^m on the position of the group. The result, which is at variance with the predications derived from a naive perturbation treatment based on the π orbitals of 1a, has been explained as being due to "orbital switching" in the substituted derivatives. 相似文献
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In this paper, nineteen FD mass spectra of cyclic nucletides are repoted. The results indicated that only (M+ + H) peak presents in the spectra of cy-AMP, cy-CMP and cy-UMP. The derivatives of cy-AMP (except 7) have M+, (M+ + H) peaks, and the main fragments corresponding to (B + 1), (T + 1) peaks as shown in Fig. 1 in the Chinese Text. The adenosine 3', 5'-cyclic phosphite and its derivatives with P(III) are somewhat different as compared with P(Ve. In some cases neither M+ nor (M+ + H) is present in their spectra, but there are some characteristic peaks. Their fragmentation process has been shown in Fig. 2 in the Chinese Text. 相似文献
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采用DFT/B3LYP方法研究了化合物Mo(CO)~n^+(n=1~6)的基态可能构型,对于各n值,基态可能构型(电子态)依次为:直线型(^6∑^+),直线型(^6∑~g^+),C~2~υ(^2A~2)或D~3~h(^6A~1),D~4~H(^4A~1~g),C~2~ν(^2B~2)或C~4~ν'(^2B~1),D~3~d(^2A~1~g)。计算结果表明,对于n≥3时,碎片离子的构型与体系自旋多重度关系敏感。进一步计算了Mo-CO键的逐级解离能,计算值与实验结果能较好吻合,并从Mo原子4d和5s轨道杂化角度来解释该键解离能随n值的非单调变化。 相似文献
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Horst-Heino von Borzeszkowski Hans-Jürgen Treder 《General Relativity and Gravitation》1997,29(4):455-466
According to Poincaré, only the epistemological sum of geometry and physics is measurable. Of course, there are requirements of measurement to be imposed on geometry because otherwise the theory resting on this geometry cannot be physically interpreted. In particular, the Weyl-Cartan space problem must be solved, i.e., it must be guaranteed that the comparison of distances is compatible with the Levi-Civita transport. In the present paper, we discuss these requirements of measurement and show that in the (purely affine) Einstein-Schrödinger unified field theory the solution of the Weyl-Cartan space problem simultaneously determines the matter via Einstein's equations. Here the affine field i
kl represents Poincaré's sum, and the solution of the space problem means its splitting in a metrical space and in matter fields, where the latter are given by the torsion tensor i
[kl]. 相似文献
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本文用量子化学CNDO/2方案计算,取文献中吡咯骨架原子的结构参数,再优化锂嵌入聚吡咯的几何参数.结果表明不管是Li+离子还是中性Li原子,嵌入单个吡咯上还是嵌入两个吡咯之间,它与吡咯环四个碳原子平面的距离都为0.210到0.216nm.且锂与碳原子键合,形成多中心键,锂嵌入聚吡咯后,固有的Ca=Cs双键的键级和键能明显减弱.这与前一报中发现IR谱的1560cm-1吸收峰消失相一致.锂正离子嵌入聚吡咯后,使吡咯的前沿π*空轨道的能量由正变为负值,而成为电子接受体(正极).遍及全部聚吡咯的π*LUMO和HOMO使得聚吡咯呈现导电性能. 相似文献