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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Simulated photoelectron spectra of the cyanide-water anion via quasiclassical molecular dynamics
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Simulated photoelectron spectra of the cyanide-water anion via quasiclassical molecular dynamics

机译：准经典分子动力学模拟氰化物-水阴离子的光电子能谱

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摘要

We present the simulated photoelectron spectrum (PES) for cyanide-water CN(H2O)- based on quasiclassical trajectory molecular dynamics (QCT-MD). Using density functional theory to generate trajectories and to calculate vertical detachment energies, we obtain simulated spectra that are in qualitative agreement with experiment. We obtain a theoretical 12 → 300 K temperature red shift of 0.1 eV as compared to an experimental redshift of 0.25 eV. The calculated linewidths of 0.3 eV are in excellent agreement with experiment. Our trajectories show that the temperature red shift as being dominated by dynamics within the basin of the N-bound minimum, however, at 300 K we predict conversion into the basin of the C-bound minimum, equilibrating at a 80:20 ratio of N- vs C-bound mixture. We discuss the potential advantages of QCT-MD over anharmonic Franck-Condon analysis such as natural incorporation of anharmonicity (as necessary for weakly bound systems), and reduced computational scaling, but also drawbacks such as neglect of final-state (e.g., Duschinsky) effects.
机译：我们提出了基于准经典轨迹分子动力学（QCT-MD）的氰化物-水CN（H2O）-的模拟光电子能谱（PES）。使用密度泛函理论生成轨迹并计算垂直脱离能，我们获得了与实验定性吻合的模拟光谱。与0.25 eV的实验性红移相比，我们获得了0.1 eV的理论12→300 K温度红移。计算得出的0.3 eV的线宽与实验非常吻合。我们的轨迹表明，温度的红移受N界最小值盆地内的动力学支配，但是，在300 K时，我们预测转换为C界最小值盆地内的氮的比例为80:20 -与C结合的混合物。我们讨论了QCT-MD相对于非谐Franck-Condon分析的潜在优势，例如自然掺入非谐性（对于弱约束系统是必需的）和减少的计算规模，还讨论了诸如忽略最终状态（例如Duschinsky）的缺点效果。

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