单中心非正交组态相互作用单激发向开壳层单重态参考态的推广：理论及其在乙酰丙酮价态-芯态泵浦-探测态中的应用
Generalization of one-center non orthogonal configuration interaction singles to open shell singlet reference states: Theory and application to valence-core pump-probe states in acetylacetone
AI总结：
提出1C-NOCIS 2eOS理论计算双电子开壳层单重态的芯激发态，通过包含芯空穴弛豫和自旋适应准确模拟泵浦-探测NEXAS，并在水和乙酰丙酮等体系中验证了其高效性。
摘要：
我们提出了一种单中心非正交组态相互作用单激发（1C-NOCIS）理论，用于计算具有两个未配对电子的初始单重态的芯激发态。该模型被称为1C-NOCIS双电子开壳层（2eOS），适用于计算与泵浦-探测时间分辨（TR）NEXAS实验相关的闭壳层分子价激发态的K边近边X射线吸收光谱（NEXAS）。通过包含芯空穴弛豫效应和显式自旋适应，1C-NOCIS 2eOS只需轻微位移即可匹配实验，不存在因自旋污染导致的伪影，并且能够捕捉超越跃迁至单占分子轨道（SOMO）的光谱高能区域。对水和胸腺嘧啶的计算展示了激发态NEXAS的不同关键特征，即芯至SOMO跃迁以及与基态类似跃迁中的位移和自旋分裂。最后，对乙酰丙酮在其π至π星单重激发态激发后碳K边的TR-NEXAS模拟——这是一项近期开展的实验——展示了1C-NOCIS 2eOS基于非绝热分子动力学模拟高效模拟NEXAS的能力。
英文摘要：
We formulate a one-center non-orthogonal configuration interaction singles (1C-NOCIS) theory for the computation of core excited states of an initial singlet state with two unpaired electrons. This model, which we refer to as 1C-NOCIS two-electron open-shell (2eOS), is appropriate for computing the K-edge near-edge X-ray absorption spectra (NEXAS) of the valence excited states of closed-shell molecules relevant to pump-probe time-resolved (TR) NEXAS experiments. With inclusion of core hole relaxation effects and explicit spin adaptation, 1C-NOCIS 2eOS requires mild shifts to match experiment, is free of artifacts due to spin contamination, and can capture the high-energy region of the spectrum beyond the transitions into the singly occupied molecular orbitals (SOMO). Calculations on water and thymine illustrate the different key features of excited-state NEXAS, namely the core-to-SOMO transition as well as shifts and spin-splittings in the transitions analogous to those of the ground state. Finally, simulations of the TR-NEXAS of acetylacetone after excitation onto its pi to pi-star singlet excited state at the carbon K-edge - an experiment carried out recently - showcases the ability of 1C-NOCIS 2eOS to efficiently simulate NEXAS based on non-adiabatic molecular dynamics simulations.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
