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1,2-二氧杂环丁烷衍生物中SA-CASSCF和MS-CASPT2的自旋-轨道耦合与混合系数，以及通过轨迹表面跳跃模拟并经校准的SA-CASSCF得到的三线态激发产率

Spin-Orbit Coupling and Admixture Coefficients in SA-CASSCF and MS-CASPT2, and Triplet Excitation Yield Simulated via Trajectory Surface Hopping and Calibrated SA-CASSCF in 1,2-Dioxetane Derivatives.

作者信息

Zhou Jian-Ge, Shu Yinan

机构信息

Interdisciplinary Nanotoxicity Center, Department of Chemistry, Physics and Atmospheric Sciences, Jackson State University, Jackson, Mississippi 39217, United States.

Department of Chemistry and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States.

出版信息

J Phys Chem A. 2025 Feb 6;129(5):1195-1206. doi: 10.1021/acs.jpca.4c04639. Epub 2025 Jan 26.

DOI:10.1021/acs.jpca.4c04639
PMID:39863993
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11808776/
Abstract

The energy gaps, spin-orbit coupling (SOC), and admixture coefficients over a series of the configurations are evaluated by the SA-CASSCF/6-31G, SA-CASSCF/6-31G*, SA-CASSCF/ANO-RCC-VDZP, and MS-CASPT2/ANO-RCC-VDZP to reveal the extent of the inaccuracy of the SA-CASSCF. By comparing the mean absolute errors for the energy gaps and the admixture coefficient magnitudes (ACMs) measured between the SA-CASSCF/6-31G, SA-CASSCF/6-31G*, or SA-CASSCF/ANO-RCC-VDZP and the MS-CASPT2/ANO-RCC-VDZP, the SA-CASSCF/6-31G is selected as the electronic structure method in the nonadiabatic molecular dynamics simulation. The major components of the ACMs of the SA-CASSCF/6-31G and MS-CASPT2/ANO-RCC-VDZP are identified and compared; we find that the ACMs are underestimated by the SA-CASSCF/6-31G, which is verified by the reasonable triplet quantum yield simulated by the trajectory surface hopping and the calibrated SA-CASSCF/6-31G. The magnitude of the singlet-triplet mixing positively correlates to the hopping probability between the mixed singlet and triplet states, which is confirmed by the computed S-T transition probability.

摘要

通过SA - CASSCF/6 - 31G、SA - CASSCF/6 - 31G*、SA - CASSCF/ANO - RCC - VDZP和MS - CASPT2/ANO - RCC - VDZP评估了一系列构型的能隙、自旋 - 轨道耦合（SOC）和混合系数，以揭示SA - CASSCF的不精确程度。通过比较SA - CASSCF/6 - 31G、SA - CASSCF/6 - 31G*或SA - CASSCF/ANO - RCC - VDZP与MS - CASPT2/ANO - RCC - VDZP之间测量的能隙平均绝对误差和混合系数大小（ACM），选择SA - CASSCF/6 - 31G作为非绝热分子动力学模拟中的电子结构方法。确定并比较了SA - CASSCF/6 - 31G和MS - CASPT2/ANO - RCC - VDZP的ACM的主要成分；我们发现SA - CASSCF/6 - 31G低估了ACM，这通过轨迹表面跳跃和校准的SA - CASSCF/6 - 31G模拟的合理三线态量子产率得到验证。单重态 - 三重态混合的大小与混合的单重态和三重态之间的跳跃概率呈正相关，这通过计算的S - T跃迁概率得到证实。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/7cfbd997f2d5/jp4c04639_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/8d90a2c6e8bc/jp4c04639_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/1085f4b3eb2e/jp4c04639_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/15e6c6c60893/jp4c04639_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/0c09d6f3ead6/jp4c04639_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/872d3a6bf826/jp4c04639_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/7cfbd997f2d5/jp4c04639_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/8d90a2c6e8bc/jp4c04639_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/1085f4b3eb2e/jp4c04639_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/15e6c6c60893/jp4c04639_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/0c09d6f3ead6/jp4c04639_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/872d3a6bf826/jp4c04639_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5479/11808776/7cfbd997f2d5/jp4c04639_0006.jpg

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