Investigation of the metastable structures of polyiodide in acetonitrile studied using global reaction route mapping and the reference interaction site model self-consistent field explicitly including constrained spatial electron density distribution.

In this study, we theoretically analyzed the metastable structures of polyiodide (I 7 - ) in the gas and acetonitrile phases using global reaction route mapping and the reference interaction site model self-consistent field explicitly including constrained spatial electron density distribution. From the chemical reaction pathways of I 7 - in acetonitrile, it was found that there would be 2 types of isomerization pathways. One proceeds with constant stoichiometry and the other takes place by breaking and forming I-I bonds. In addition, we discovered that I 7 - had various metastable structures within ∼10 kcal mol -1 . Comparing the most stable structure in the gas and acetonitrile phases, the tetrapot type is found to be the most stable structure in the gas phase; however, it is the zigzag type in acetonitrile. In order to understand this difference, we performed the decomposition analysis of the thermal correlation term in the gas and acetonitrile phases. It was found that thermal correction plays a key role in the stability and we could explain the difference in the population of the EQ states of I 7 - in each phase. Overall, we revealed that the solvation effect must be one of the crucial factors to stabilize the isomers of I 7 - and determine the chemical reaction pathways.