Improving convergence of experimental and computed vertical ionization energies using the ionization potential equation‐of‐motion coupled‐cluster with singles and doubles method,International Journal of Quantum Chemistry

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Improving convergence of experimental and computed vertical ionization energies using the ionization potential equation‐of‐motion coupled‐cluster with singles and doubles method
International Journal of Quantum Chemistry ( IF 2.3 ) Pub Date : 2020-06-27 , DOI: 10.1002/qua.26261
Marissa Buzzanca ₁ , Brandon Brummeyer ₁ , Jonathan H. Gutow ₁

Affiliation

Comparison of statistically evaluated experimental vertical ionization energies (IEs) for 53 medium‐sized molecules (6‐34 atoms) with ionization potential equation‐of‐motion coupled‐cluster with singles and doubles (IP‐EOMCCSD) computations shows that discrepancies between computed and experimental results can be accounted for with a combination of experimental and theoretical contributions. Discrepancies can be minimized by extrapolating computations to the complete basis set limit and correcting for vibrational zero‐point energy (ZPE) while comparing with experimental IEs calculated as the intensity‐weighted mean band position to account for band asymmetries. This procedure reduced the average discrepancy for ethylene, (E )‐2‐butene, 2,5‐dihydrofuran, and pyrrole from 0.25 to 0.05 eV. Agreement between reported vertical IEs and computations without either making adjustments as described in this paper or using complete simulation of the ionization spectrum should be considered fortuitous. The comparisons made in this work show that estimates of vertical and adiabatic IE made using IP‐EOMCCSD extrapolated to the complete basis set limit and corrected for vibrational ZPE can be used with reasonable confidence when experimental values are not available.

中文翻译：

使用单点和双点法的电离势运动方程耦合簇提高实验和计算的垂直电离能的收敛性

对经统计评估的53种中等大小分子（6-34原子）的实验垂直电离能（IE）与电离势运动方程式-单/双耦合方程组（IP-EOMCCSD）的比较表明，计算值和计算值之间存在差异实验结果可以用实验和理论贡献相结合来说明。通过将计算外推到完整的基集极限并校正振动零点能量（ZPE），同时与以强度加权平均谱带位置计算的实验IE进行比较以解决谱带不对称性，可以将差异最小化。此过程减少了对乙烯的平均差异，（Ë）-2-丁烯，2,5-二氢呋喃和吡咯的0.25至0.05 eV。在报告的垂直IE与计算之间未达成本文所述的调整或未对电离光谱进行完全模拟的情况下，应认为是偶然的。在这项工作中进行的比较表明，当没有实验值可用时，使用IP-EOMCCSD外推至完整基集极限并针对振动ZPE进行校正的垂直和绝热IE的估计值可以放心使用。

更新日期：2020-08-03

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