Computational Data for UV–Vis Absorption, Photolysis Thresholds, OH-Initiated Radical Formation, and Radical-Initiated Fragmentation in C5H12O6 Isoprene-Derived Oxidation Products

This dataset contains the computational data supporting the manuscript: "Computational Study of UV–Vis Absorption, Photolysis Thresholds, OH-Initiated Radical Formation, and Radical-Initiated Fragmentation in C5H12O6 Isoprene-Derived Oxidation Products." The dataset comprises Gaussian input and output files, optimized molecular geometries, transition-state structures, intrinsic reaction coordinate (IRC) calculations, TD-DFT excited-state calculations, natural transition orbital (NTO) analyses, charge-transfer diagnostics, bond dissociation energies, thermodynamic data, and transition-state theory (TST) kinetic calculations. The study investigates the electronic structure, UV–vis absorption properties, photolysis-relevant bond dissociation pathways, OH•-initiated hydrogen-atom abstraction (HAA), H•-induced O–H stripping reactions, oxygen-centered alkoxyl radical formation, and subsequent α C–C scission fragmentation pathways of C5H12O6, a highly oxygenated isoprene-derived secondary organic aerosol (SOA) constituent. Computational methods include: Geometry optimizations and frequency calculations at the M06-2X/def2-TZVP level of theory. Single-point energy calculations at the B3LYP-D3(BJ)/6-311+G(3df,3pd) level. TD-DFT calculations using CAM-B3LYP/6-311++G(3df,3pd). Implicit solvation using gas-phase, SMD MeCN, SMD water, and a custom SOA-like dielectric medium. Natural Bond Orbital (NBO), spin-density, and charge-transfer analyses. The data establish a mechanistic framework linking electronic excitation accessibility, radical formation, alkoxyl radical stability, low-barrier α-scission fragmentation, and volatility-altering degradation pathways relevant to the atmospheric aging of highly oxygenated isoprene-derived SOA constituents. Associated manuscript: Submitted to the Journal of Computational Chemistry (2026).本数据集包含支撑下述研究论文的计算数据：《C₅H₁₂O₆异戊二烯源氧化产物的紫外-可见吸收、光解阈值、OH引发自由基形成及自由基引发裂解的计算研究》。 本数据集涵盖高斯（Gaussian）计算软件的输入与输出文件、优化后的分子几何结构、过渡态结构、内禀反应坐标（Intrinsic Reaction Coordinate, IRC）计算结果、含时密度泛函理论（Time-Dependent Density Functional Theory, TD-DFT）激发态计算数据、自然跃迁轨道（Natural Transition Orbital, NTO）分析结果、电荷转移诊断参数、键解离能数据、热力学数据，以及过渡态理论（Transition-State Theory, TST）动力学计算结果。 本研究针对C₅H₁₂O₆——一种高含氧异戊二烯源二次有机气溶胶（Secondary Organic Aerosol, SOA）组分——展开多维度探究，涵盖其电子结构、紫外-可见吸收特性、与光解相关的键解离路径、羟基自由基（OH•）引发的氢原子夺取（Hydrogen-Atom Abstraction, HAA）反应、氢原子诱导的O-H剥离反应、氧中心烷氧基自由基的形成，以及后续的α位C-C键断裂裂解路径。 本研究采用的计算方法如下： 1. 在M06-2X/def2-TZVP理论水平下完成几何优化与频率计算； 2. 在B3LYP-D3(BJ)/6-311+G(3df,3pd)理论水平下完成单点能计算； 3. 使用CAM-B3LYP/6-311++G(3df,3pd)开展含时密度泛函理论计算； 4. 采用气相、SMD乙腈、SMD水以及定制类SOA介电介质进行隐式溶剂化模型计算； 5. 开展自然键轨道（Natural Bond Orbital, NBO）、自旋密度以及电荷转移分析。 本数据集提供的数据构建了一套机理框架，将电子激发可达性、自由基形成、烷氧基自由基稳定性、低能垒α裂解过程，以及与高含氧异戊二烯源SOA组分大气老化相关的挥发性改变降解路径关联起来。 相关研究论文已提交至《计算化学杂志》（Journal of Computational Chemistry，2026年）。