Computing UV-vis spectra of 1-bromo-1-propene: a comparison of model core potential and all-electron basis sets
Computing UV-vis spectra of 1-bromo-1-propene: a comparison of model core potential and all-electron basis sets
复制标题
计算 1-溴-1-丙烯的紫外可见光谱：模型核心势和全电子基组的比较
DOI：
10.1139/cjc-2016-0518
复制
发表时间：
2017
影响因子：
1.1
通讯作者：
M. Klobukowski
中科院分区：
文献类型：
--
作者：
Meagan S. Oakley;M. Klobukowski
真空紫外(VUV)光谱可用于识别复杂的多种分子混合物中的不同异构体。在这项工作中，计算的真空紫外光谱与实验混合物的光谱进行了比较，以确定合适的计算方法。由于基准分子1-溴-1-丙烯含有一个重原子，所以研究了全电子基组和模型核势基组。含时密度泛函理论(TD-DFT)可以精确计算低能激发下的电子激发态，并与对称适应团簇组态相互作用(SAC-CI)方法在高能下的计算结果进行了比较。TD-DFT在低能下是令人满意的，但在高能下，激发能可能偏离0.5 eV。采用全电子和模型芯势基组的TD-DFT对低激发态产生了令人满意的激发能。这种方法对实验产生的光谱的预测也是令人满意的，包括。
Vacuum ultraviolet (VUV) spectroscopy can be used to identify different isomers in complicated mixtures of many molecules. In this work, calculated VUV spectra are compared with spectra of experimental mixtures to benchmark appropriate computational methods. Because the benchmark molecule, 1-bromo-1-propene, contains a heavy atom, both all-electron and model core potential basis sets were investigated. Time-dependent density functional theory (TD-DFT) can accurately compute electronic excited states at low-energy excitations and was cross-checked at higher energies against results from the symmetry adapted cluster–configuration interaction (SAC–CI) method. TD-DFT was determined to be satisfactory at low energies; however, excitation energies can deviate by 0.5 eV at high energies. TD-DFT with both all-electron and model core potential basis sets produced satisfactory excitation energies for the lower excited states. This method is also satisfactory at predicting spectra produced experimentally, including ...