激发态吸收:参考振荡器强度,波函数和TDDFT基准

IF 5.5 1区 化学 Q2 CHEMISTRY, PHYSICAL
Jakub Širůček, Boris Le Guennic*, Yann Damour, Pierre-François Loos* and Denis Jacquemin*, 
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引用次数: 0

摘要

激发态吸收(ESA)对应于两个电子激发态之间的跃迁,是探测和理解光-物质相互作用的基本过程。为了解释时间分辨实验,确实经常需要对欧空局进行精确的建模。在这篇文章中,我们展示了来自QUEST数据库的21个中小分子的53种ESA振荡强度和71种激发态之间的垂直跃迁能量的数据集。在少数情况下,我们还研究了几何松弛对激发态几何的影响。采用8种不同的Dunning基集,在二次响应(QR) CC3形式下获得参考值。我们发现d-aug-cc-pVTZ基集总是足够的,而它的更紧凑的双-ζ对应,d-aug-cc-pVDZ,在大多数情况下表现良好。这些QR-CC3数据使我们能够评估QR-TDDFT的性能,无论是否应用tam - dancoff近似,使用一组全局和范围分离的混合(B3LYP, BH&;HLYP, CAM-B3LYP, LC-BLYP33和LC-BLYP47),以及几种低阶波函数方法,即QR-CCSD, QR-CC2, EOM-CCSD, ISR-ADC(2)和ISR-ADC(3)。我们表明,QR-TDDFT提供了可接受的ESA振荡器强度误差,CAM-B3LYP显示出特别的希望,特别是对于我们集合的最大分子,以及在frank - condon (FC)区域。我们还发现ISR-ADC(3)在该区域表现出优异的性能。当使用激发态最优几何形状时,基于波函数的方法的相对性能与frank - condon区域观察到的趋势保持一致。然而,对于TD(A)-DFT,精度变化更大,因为不同交换相关函数的性能显著依赖于所选择的几何形状。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Excited-State Absorption: Reference Oscillator Strengths, Wave Function, and TDDFT Benchmarks

Excited-State Absorption: Reference Oscillator Strengths, Wave Function, and TDDFT Benchmarks

Excited-state absorption (ESA) corresponds to the transition between two electronic excited states and is a fundamental process for probing and understanding light-matter interactions. Accurate modeling of ESA is indeed often required to interpret time-resolved experiments. In this contribution, we present a dataset of 53 ESA oscillator strengths in three different gauges and the associated vertical transition energies between 71 excited states of 21 small- and medium-sized molecules from the QUEST database. In a few cases, we additionally investigated the effect of geometry relaxation on excited-state geometries. The reference values were obtained within the quadratic response (QR) CC3 formalism using eight different Dunning basis sets. We found that the d-aug-cc-pVTZ basis set is always adequate while its more compact double-ζ counterpart, d-aug-cc-pVDZ, performs well in most cases. These QR-CC3 data allow us to assess the performance of QR-TDDFT, with and without applying the Tamm-Dancoff approximation, using a panel of global and range-separated hybrids (B3LYP, BH&HLYP, CAM-B3LYP, LC-BLYP33, and LC-BLYP47), as well as several lower-order wave function methods, i.e., QR-CCSD, QR-CC2, EOM-CCSD, ISR-ADC(2), and ISR-ADC(3). We show that QR-TDDFT delivers acceptable errors for ESA oscillator strengths with CAM-B3LYP showing particular promise, especially for the largest molecules of our set, and in the Franck–Condon (FC) region. We also find that ISR-ADC(3) exhibits excellent performance in this region. When using excited-state optimal geometries, the relative performance of wave function-based approaches remains consistent with trends observed in the Franck–Condon region. However, for TD(A)-DFT, the accuracy varies more significantly, as the performance of different exchange-correlation functionals significantly depends on the chosen geometry.

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来源期刊
Journal of Chemical Theory and Computation
Journal of Chemical Theory and Computation 化学-物理:原子、分子和化学物理
CiteScore
9.90
自引率
16.40%
发文量
568
审稿时长
1 months
期刊介绍: The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.
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