Lee In Seong, Min Seung Kyu
Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), 50 UNIST-gil, Ulju-gun, Ulsan 44919, South Korea.
J Chem Theory Comput. 2022 Jun 14;18(6):3391-3409. doi: 10.1021/acs.jctc.2c00037. Epub 2022 May 12.
We present a generalized formulation for the combination of the density functional tight binding (DFTB) approach and the state-interaction state-average spin-restricted ensemble-referenced Kohn-Sham (SI-SA-REKS or SSR) method by considering onsite correction (OC) as well as the long-range corrected (LC) functional. The OC contribution provides more accurate energies and analytic gradients for individual microstates, while the multireference character of the SSR provides the correct description for conical intersections. We benchmark the LC-OC-DFTB/SSR method against various DFTB calculation methods for excitation energies and conical intersection structures with π/π* or /π* characters. Furthermore, we perform excited-state molecular dynamics simulations with a molecular rotary motor with variations of LC-OC-DFTB/SSR approaches. We show that the OC contribution to the LC functional is crucial to obtain the correct geometry of conical intersections.
我们提出了一种广义公式，用于结合密度泛函紧束缚（DFTB）方法和态相互作用态平均自旋限制系综参考Kohn-Sham（SI-SA-REKS或SSR）方法，其中考虑了在位校正（OC）以及长程校正（LC）泛函。OC贡献为各个微观态提供了更准确的能量和解析梯度，而SSR的多参考特性为锥形交叉提供了正确描述。我们将LC-OC-DFTB/SSR方法与各种DFTB计算方法在具有π/π或/π特征的激发能和锥形交叉结构方面进行了基准测试。此外，我们使用分子旋转马达对不同的LC-OC-DFTB/SSR方法进行了激发态分子动力学模拟。我们表明，OC对LC泛函的贡献对于获得正确的锥形交叉几何结构至关重要。
