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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >The a~1#DELTA#_g -> X~3#SIGMA#_g~- Transition in Molecular Oxygen: Interpretation of Solvent Effects on Spectral Shifts
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The a~1#DELTA#_g -> X~3#SIGMA#_g~- Transition in Molecular Oxygen: Interpretation of Solvent Effects on Spectral Shifts

机译:分子氧中a〜1#DELTA#_g-> X〜3#SIGMA#_g〜-的转变:溶剂对光谱位移的影响的解释

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Ab initio computational methods have been used to investigate the effect of solvent on the a~1#DELTA#_g -> X~3#SIGMA#_g~- transition in molecular oxygen. For a given solvent molecule, M, energies have been obtained for the M-O_2-(a~1#DELTA#_g) complex that is in equilibrium with its surrounding outer solvent and for the M-O_2(X~3#SIGMA#_g~-) complex that is not in equilibrium with the outer solvent (i.e., the Franck-Condon state populated in the a -> X transition). These energies depend principally on the quadrupolar and higher order coupling terms between the complex and the outer solvent and only minimally on the dipolar coupling term and on dispersion interactions. Upon averaging over multiple M-O_2 orientations, each with an unique transition probability, differences between the calculated O_2(a~1#DELTA#_g) and O_2(X~3#SIGMA#_g~-) energies correlate well with the xperimental spectral data. Thus, previously published correlations between experimental a-X spectral shifts and the solvent polarizability cannot be ascribed solely to a dispersion interaction, but rather simply reflect the general importance of the solvent's electronic response in the oxygen-solvent interaction.
机译:从头算计算方法已用于研究溶剂对分子氧中a〜1#DELTA#_g-> X〜3#SIGMA#_g〜-过渡的影响。对于给定的溶剂分子,M已获得与其周围外部溶剂处于平衡状态的M-O_2-(a〜1#DELTA#_g)配合物和M-O_2(X〜3#SIGMA#)的能量_g〜-)与外部溶剂不平衡的络合物(即,在a-> X跃迁中填充的Franck-Condon状态)。这些能量主要取决于配合物和外部溶剂之间的四极和更高阶的耦合项,而仅极少地取决于偶极耦合项和色散相互作用。在平均多个M-O_2方向(每个方向具有唯一的跃迁概率)时,计算出的O_2(a〜1#DELTA#_g)和O_2(X〜3#SIGMA#_g〜-)能量之间的差异与X谱光谱密切相关数据。因此,先前发表的实验a-X光谱位移与溶剂极化率之间的相关性不能仅归因于分散相互作用,而只是反映了溶剂在氧-溶剂相互作用中电子反应的一般重要性。

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