Published November 2005
| Version v1
Journal article
Solvation effects on the stability of diiodohalogen anions: a quantum-chemical study
Creators
- 1. Rostovskij Gosudarstvennyj Univ., Rostov-na-Donu (Russian Federation)
Description
DFT-B3PW91 nonempirical calculations with the HW+(3d) and 6-31G++(d,p) basis sets were performed to study the electronic structure and relative stability of X- · Bn, X- · BnI2 · By, and Bn · XI2- · By (n = 1-4, y = 0, 1) clusters, where B stands for H2O, CH3OH, CH3CN, and CHCl3 and X = Cl, Br, and I. The formation of solvated iodohalogen anions was shown to occur as a result of the displacement of solvent clusters from the solvation shells of X- and I2; that is, the Cl- and Br- anions most screened by solvents were least prone to form XI2-. Taking solvation effects into account gives the series of increasing relative stability of iodohalides (ClI2- < BrI2- < I3-) that is opposite to the stability series of gas-phase species
Abstract (Russian)
С помощью ab initio метода DFT-B3PW91 в базисах HW+(3d), 6-31G++(d,p) изучено электронное строение и относительная устойчивость кластеров состава Х- · Вn, Х- · ВnI2 · By, Вn · ХI2- · By, (n = 1-4, у = 0, 1), где В = Н2О, СН3ОН, CH3CN, СНСl3, а Х = Сl, Вг, I. Показано, что образование сольватированных иодогалогенид-анионов происходит в результате вытеснения кластеров растворителей из сольватных оболочек Х- и I2, т.е. наиболее экранированные со стороны растворителей анионы Сl- и Вг- менее склонны к образованию XI2-. Установлено, что учет сольватационных эффектов приводит к ряду возрастающей относительной устойчивости иодогалогенидов: ClI2- < BrI2- < I3-, противоположному газофазномуAdditional details
Additional titles
- Original title (Russian)
- Квантово-химическое изучение влияния сольватации на устойчивост' дииодгалогенид-анионов
Publishing Information
- Journal Title
- Zhurnal Fizicheskoj Khimii
- Journal Volume
- 79
- Journal Issue
- 11
- Journal Page Range
- p. 2014-2021
- ISSN
- 0044-4537
- CODEN
- ZFKHA9
INIS
- Country of Publication
- Russian Federation
- Country of Input or Organization
- Russian Federation
- INIS RN
- 37037024
- Subject category
- S37: INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY;
- Descriptors DEI
- ACETONITRILE; ANIONS; BROMINE COMPOUNDS; CHEMICAL COMPOSITION; CHLORINE COMPOUNDS; CHLOROFORM; ELECTRONIC STRUCTURE; HYDRATES; IODIDES; IODINE; METHANOL; MOLECULAR CLUSTERS; MOLECULAR STRUCTURE; SOLVATION; STABILITY
- Descriptors DEC
- ALCOHOLS; CHARGED PARTICLES; CHLORINATED ALIPHATIC HYDROCARBONS; ELEMENTS; HALIDES; HALOGEN COMPOUNDS; HALOGENATED ALIPHATIC HYDROCARBONS; HALOGENS; HYDROXY COMPOUNDS; IODINE COMPOUNDS; IONS; NITRILES; NONMETALS; ORGANIC CHLORINE COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC HALOGEN COMPOUNDS; ORGANIC NITROGEN COMPOUNDS
Optional Information
- Notes
- 33 refs., 3 figs., 3 tabs.