Vertical vs. adiabatic ionization energies in solution and gas-phase: probing ionization-induced reorganization in conformationally-mobile bichromophoric actuators using photoelectron spectroscopy, electrochemistry and theory†,Physical Chemistry Chemical Physics

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Vertical vs. adiabatic ionization energies in solution and gas-phase: probing ionization-induced reorganization in conformationally-mobile bichromophoric actuators using photoelectron spectroscopy, electrochemistry and theory†
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2018-09-24 00:00:00 , DOI: 10.1039/c8cp02936a
Maxim V. Ivanov _{1,

2,

3,

4} , Denan Wang _{1,

2,

3,

4} , Depeng Zhang _{1,

2,

3,

4} , Rajendra Rathore _{1,

2,

3,

4} , Scott A. Reid _{1,

2,

3,

4}

Affiliation

Ionization-induced structural and conformational reorganization in various π-stacked dimers and covalently linked bichromophores is relevant to many processes in biological systems and functional materials. In this work, we examine the role of structural, conformational, and solvent reorganization in a set of conformationally mobile bichromophoric donors, using a combination of gas-phase photoelectron spectroscopy, solution-phase electrochemistry, and density functional theory (DFT) calculations. Photoelectron spectral analysis yields both adiabatic and vertical ionization energies (AIE/VIE), which are compared with measured (adiabatic) solution-phase oxidation potentials (E_ox). Importantly, we find a strong correlation of E_ox with AIE, but not VIE, reflecting variations in the attendant structural/conformational reorganization upon ionization. A careful comparison of the experimental data with the DFT calculations allowed us to probe the extent of charge stabilization in the gas phase and solution and to parse the reorganizational energy into its various components. This study highlights the importance of a synergistic approach of experiment and theory to study ionization-induced structural and conformational reorganization.

中文翻译：

溶液和气相中的垂直与绝热电离能：利用光电子能谱，电化学和理论探测构象移动双发色致动器中的电离诱导的重组†

在各种π堆积的二聚体和共价连接的双色团中，电离诱导的结构和构象重组与生物系统和功能材料中的许多过程有关。在这项工作中，我们结合气相光电子能谱，溶液相电化学和密度泛函理论（DFT）计算，研究了结构，构象和溶剂重组在一组构象可移动的双色供体中的作用。光电子能谱分析会同时产生绝热和垂直电离能（AIE / VIE），并将其与测得的（绝热）溶液相氧化电势（E _ox）进行比较。重要的是，我们发现E _ox有很强的相关性与AIE（而非VIE）合作，反映了电离后伴随的结构/构象重组的变化。通过将实验数据与DFT计算进行仔细比较，我们可以探究气相和溶液中电荷稳定的程度，并将重组能量解析为各种成分。这项研究强调了实验和理论的协同方法对研究电离诱导的结构和构象重组的重要性。

更新日期：2018-09-24

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