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首页> 外文期刊>Chemical Physics: A Journal Devoted to Experimental and Theoretical Research Involving Problems of Both a Chemical and Physical Nature >Hole-burning spectra of tropolone-(CO_2)_n (n = 1,2) van der Waals complexes and density functional study
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Hole-burning spectra of tropolone-(CO_2)_n (n = 1,2) van der Waals complexes and density functional study

机译：对苯二酚-（CO_2）_n（n = 1,2）范德华配合物的空穴燃烧光谱和密度泛函研究

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摘要

The hole-burning, fluorescence excitation, and dispersed fluorescence spectra of jet-cooled tropolone (TRN)-(CO_2)_n (n = 1,2) complexes are measured to investigate the structures of the complexes and the effects of intermolecular interaction on proton tunneling in TRN. The electronic transitions of TRN-(CO_2)_n (n = 1,2) are well separated in the hole-burning spectrum. Only the transitions of one species have been identified for the 1:1 and 1:2 complexes. Structures of TRN-(CO_2)_n (n = 1,2) are optimized by the density functional theory calculations at the B3LYP/cc-pVDZ level. Three local minima have been obtained for both the 1:1 and 1:2 complexes. In the 1:1 complex CO_2 is bonded in the molecular plane close to a solvation site, C=O (Isomer I), C=O … H-O (Isomer II), or C=O (Isomer III). These complexes are stabilized mainly by the dipole-quadrupole interaction, and the binding energies for these complexes are estimated to be much smaller than those for the hydrogen-bonded complexes. Isomer I and II are plausible candidates for the observed species. The calculations imply that asymmetry of the double-minimum potential well along the tunneling coordinates of TRN-(CO_2)-1 is large enough to quench proton tunneling. This prediction is consistent with the nonobservation of the tunneling splittings even for the excitation of the tunneling promoting mode v_(13)(a_1) or v_(14)(a_1) of TNR.
机译：测量了射流冷却的对苯二酚（TRN）-（CO_2）_n（n = 1,2）配合物的空穴燃烧，荧光激发和分散荧光光谱，以研究配合物的结构以及分子间相互作用对质子的影响TRN中的隧道。 TRN-（CO_2）_n（n = 1,2）的电子跃迁在空穴燃烧光谱中被很好地分离。对于1：1和1：2配合物，仅确定了一个物种的过渡。 TRN-（CO_2）_n（n = 1,2）的结构通过B3LYP / cc-pVDZ水平的密度泛函理论计算得到优化。对于1：1和1：2配合物，已获得三个局部最小值。在1：1的配合物中，CO_2在接近溶剂化位点的分子平面上键合，C = O（异构体I），C = O…H-O（异构体II）或C = O（异构体III）。这些配合物主要通过偶极-四极相互作用来稳定，据估计这些配合物的结合能比氢键结合配合物的结合能小得多。异构体I和II是观察物种的合理候选者。计算结果表明，沿着TRN-（CO_2）-1的隧穿坐标的双最小势阱的不对称性足以淬灭质子隧穿。即使对于TNR的隧道促进模式v_（13）（a_1）或v_（14）（a_1）的激发，该预测也与未观察到隧道分裂一致。

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