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Determination of Parameters of the Dipole Moment of the CO_2 Molecule

机译:CO_2分子偶极矩参数的确定

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Analytic expressions are obtained for vibrational transition moments of the first, second, and third orders using the eigenfunctions in the second-order perturbation theory. These expressions can be used to solve the inverse electrooptical problem for the ~(12)C~(16)O_2 molecule. The resonance interactions were taken into account by solving secular equations. The mixing coefficients for the eigenfunctions were calculated with an accuracy of 0.1%. The experimental data on purely vibrational transition moments <μ>~2 used in the solution were obtained by averaging the data available in the literature with the weights that are inversely proportional to the error, resulting in mean-square deviations of (0.1-10)%. Five parameters of the dipole moment of the Σ_u symmetry were calculated using 29 values of the transition moments; five parameters of the π_u symmetry were calculated using 27 values of the transition moments. The accuracy of the solution of the inverse problem is characterized by the quantity Q =[Σ(δμ_i~(theor)/δμ_i~(exp))~2/(n-m)~(1/2), where δμ_i~(theor) is the deviation of calculations from the experiment, δμ_i~(exp) is the experimental error, i is the number of the experimental data used, and m is the number of parameters smaller than unity.
机译:使用二阶微扰理论中的本征函数,获得了一阶,二阶和三阶振动跃迁的解析表达式。这些表达式可用于解决〜(12)C〜(16)O_2分子的反电光学问题。通过求解长期方程考虑了共振相互作用。本征函数的混合系数的计算精度为0.1%。通过使用与误差成反比的权重对文献中可获得的数据进行平均,获得溶液中使用的纯振动跃迁<μ>〜2的实验数据,得出均方差为(0.1-10) %。使用29个跃迁矩值计算了Σ_u对称性的偶极矩的五个参数。使用过渡矩的27个值计算了π_u对称性的五个参数。反问题的解的精确度的特征在于数量Q = [∑(δμ_i〜(theor)/δμ_i〜(exp))〜2 /(nm)〜(1/2),其中δμ_i〜(theor)是计算与实验的偏差,δμ_i〜(exp)是实验误差,i是使用的实验数据的数量,m是小于1的参数的数量。

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