首页> 外文期刊>Molecular Physics:An International Journal at the Interface Between Chemistry and Physics >Iodide solvation in tetrahydrofuran clusters: I−(THF) n (1 ≤ n ≤ 30)
【24h】

Iodide solvation in tetrahydrofuran clusters: I−(THF) n (1 ≤ n ≤ 30)

机译:四氢呋喃簇中的碘化物溶剂:I (THF) n (1≥n≥30)

获取原文
获取原文并翻译 | 示例
       

摘要

The solvent structure and binding motif of iodide-doped tetrahydrofuran clusters, I−(THF) n (1 ≤ n ≤ 30) are investigated with anion photoelectron imaging, molecular dynamics simulations, and ab initio calculations of vertical detachment energies. Experimentally, a dramatic decrease in the iodide differential stabilization energy and concomitant change in the mass spectrum at n = 9 suggest that the first solvation shell closes at n = 9-10 THF molecules, in rough agreement with the theoretical result of n = 7-9 determined from the computation of relaxed and unrelaxed solvent distribution densities. Analysis of the vertical detachment energy vs. inverse cluster radius suggests the iodide atom is maximally coordinated around n = 9. Decomposition of the interaction energies of I−(THF), its vertically-detached complement, and the (THF)2 dimer, employing the absolutely-localized molecular orbital energy decomposition analysis (ALMO EDA) scheme, highlights the dependence of electron binding and detachment on both electrostatics and polarization, with direct evidence of the fundamental importance of polarizability to a description of detachment. Experimental and theoretical evidence for an anionic electronically excited state is also presented; computed excitation energies and their attendant characters are discussed. The results are interpreted within the framework of the inefficient packing that occurs in bulk neat THF.View full textDownload full textKeywordsion solvation, photoelectron spectroscopy, clusters, charge-dipole interactionsRelated var addthis_config = { ui_cobrand: "Taylor & Francis Online", services_compact: "citeulike,netvibes,twitter,technorati,delicious,linkedin,facebook,stumbleupon,digg,google,more", pubid: "ra-4dff56cd6bb1830b" }; Add to shortlist Link Permalink http://dx.doi.org/10.1080/00268976.2012.679637
机译:碘化物掺杂的四氢呋喃簇,I ˆ (THF) n (1≥n≥1 ¤30)用阴离子光电子成像,分子动力学模拟和垂直脱离能的从头算来研究。实验中,碘化物微分稳定能和n 9的质谱变化的显着减少表明,第一个溶剂化壳在n = 9-10 THF分子中关闭,在粗糙n 7 = 9-9的理论结果一致,从松弛和无松弛的溶剂分布密度的计算确定。垂直脱离能量与反簇半径的分析表明,碘原子在n == 9附近得到最大协调。利用绝对局限的分子轨道能量分解I ˆ (THF),其垂直分离的补体和(THF) 2 二聚体的相互作用能分解分析(ALMO EDA)方案突出了电子结合和分离对静电和极化的依赖性,并直接证明了极化性对分离的描述至关重要。还提供了阴离子电子激发态的实验和理论证据。讨论了计算出的激发能及其伴随特性。结果是在散装纯THF中发生的低效率包装的框架内解释的。查看全文下载全文关键字溶剂化,光电子能谱,簇,电荷-偶极相互作用相关的var addthis_config = {ui_cobrand:“泰勒和弗朗西斯在线” citeulike,netvibes,twitter,technorati,美味,linkedin,facebook,stumbleupon,digg,google,更多”,发布:“ ra-4dff56cd6bb1830b”};添加到候选列表链接永久链接http://dx.doi.org/10.1080/00268976.2012.679637

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱:kefu@zhangqiaokeyan.com

京公网安备:11010802029741号 ICP备案号:京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有
  • 客服微信

  • 服务号