Gałyńska Marta, Tecmer Paweł, Boguslawski Katharina
Institute of Physics, Faculty of Physics, Astronomy, and Informatics, Nicolaus Copernicus University in Toruń, Grudziadzka 5, 87-100 Toruń, Poland.
J Phys Chem A. 2024 Dec 26;128(51):11068-11073. doi: 10.1021/acs.jpca.4c06904. Epub 2024 Dec 12.
We introduce the electron attachment equation-of-motion pair coupled cluster doubles (EA-EOM-pCCD) ansatz, which allows us to inexpensively compute electron affinities, energies of unoccupied orbitals, and electron attachment spectra. We assess the accuracy of EA-EOM-pCCD for a representative data set of organic molecules for which experimental data are available, as well as the electron attachment process in uranyl dichloride. EA-EOM-pCCD provides more reliable energies for electron attachment properties than its ionization potential EOM counterpart. The advantage of EA-EOM-pCCD is demonstrated for rylene and rylene diimide units of different chain lengths, where it outperforms the more elaborate EOM-DLPNO-CCSD flavors, reducing errors by an order of magnitude.
我们引入了电子附着运动方程对耦合簇双激发（EA-EOM-pCCD）近似，这使我们能够廉价地计算电子亲合能、未占据轨道的能量以及电子附着光谱。我们评估了EA-EOM-pCCD对于一组有实验数据可用的代表性有机分子数据集的准确性，以及二氯化铀中的电子附着过程。与电离势的EOM对应方法相比，EA-EOM-pCCD为电子附着性质提供了更可靠的能量。对于不同链长的苝和苝二酰亚胺单元，EA-EOM-pCCD的优势得到了证明，它优于更精细的EOM-DLPNO-CCSD方法，将误差降低了一个数量级。
