Long-Range Corrected DFT Meets GW: Vibrationally Resolved Photoelectron Spectra from First Principles.
Long-Range Corrected DFT Meets GW: Vibrationally Resolved Photoelectron Spectra from First Principles.
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DOI：
10.1021/acs.jctc.5b00820
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发表时间：
2015-10
影响因子：
5.5
通讯作者：
Lukas Gallandi;T. Körzdörfer
中科院分区：
文献类型：
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作者：
Lukas Gallandi;T. Körzdörfer
我们提出了一个完全非经验和计算效率的方案来计算高可靠的振动分辨光电子能谱的分子从第一原理。为此，我们将非经验调谐的远程校正混合泛函与G0W0近似中的非自一致多体摄动理论结合起来，并基于dft计算频率的Franck-Condon多模分析。振动分析可以将gw计算的光谱与中性和阴离子分子的气相紫外光电子测量结果进行直接比较。将计算得到的峰值最大值与实验结果进行直接比较，电离势、电子亲和力和基本间隙的平均绝对误差低于0.1 eV，在类似的数值成本下明显优于常用的G0W0方法。
We propose an entirely nonempirical and computationally efficient scheme to calculate highly reliable vibrationally resolved photoelectron spectra for molecules from first principles. To this end, we combine nonempirically tuned long-range corrected hybrid functionals with non-self-consistent many-body perturbation theory in the G0W0 approximation and a Franck-Condon multimode analysis based on DFT-calculated frequencies. The vibrational analysis allows for a direct comparison of the GW-calculated spectra to gas-phase ultraviolet photoelectron measurements of neutral and anionic molecules, respectively. Direct comparison of the calculated peak maxima with experiment yields mean absolute errors below 0.1 eV for ionization potentials, electron affinities, and fundamental gaps, clearly outperforming commonly used G0W0 approaches at similar numerical costs.