Lavín C, Velasco A M, Vega M V, Marín I, Pitarch-Ruiz J, Sánchez Marín J
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, E-47005 Valladolid, Spain.
J Phys Chem A. 2009 Jun 25;113(25):7155-60. doi: 10.1021/jp900464q.
Theoretical absorption oscillator strengths for transitions involving Rydberg states in molecular formaldehyde as well as cross sections for photoionization Rydberg channels associated with the production of the lowest parent ion electronic state are reported. The calculations have been performed with the molecular quantum defect orbital (MQDO) method. A test on the MQDO f values has been its comparison with previous experiments and calculations and its compliance with the expected systematic trends along the Rydberg series. The use of the MQDO method as an alternative to ab initio methods, which find serious difficulties in calculating spectral intensities in formaldehyde, is proposed. We hope that the spectroscopic data, many of them reported here for the first time, may be useful for the interpretation of the vacuum ultraviolet spectrum of this molecule.
本文报道了涉及分子甲醛中里德堡态跃迁的理论吸收振子强度，以及与最低母体离子电子态产生相关的光离化里德堡通道的截面。计算采用了分子量子亏损轨道（MQDO）方法。对MQDO f值的一项检验是将其与先前的实验和计算结果进行比较，并考察其是否符合沿里德堡系列预期的系统趋势。有人提出使用MQDO方法作为从头算方法的替代方法，因为从头算方法在计算甲醛的光谱强度时遇到了严重困难。我们希望这里首次报道的许多光谱数据可能有助于解释该分子的真空紫外光谱。
