English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

Comparison of experimental infrared (IR) spectra of the simplest carbocations (with the weakest carborane counterions in terms of basicity, CHB 11 Hal 11  - , Hal = F, Cl) with their calculated IR spectra revealed that they are completely inconsistent, as previously reported for the t-Bu + cation [Stoyanov E. S., et al. J. Phys. Chem. A, 2015, 119, 8619]. This means that the generally accepted explanation of hyperconjugative stabilization of the carbocations should be revised. According to the theory, one CH bond (denoted as ) from each CH 3 /CH 2 group transfers its σ-electron density to the empty 2p z orbital of the sp 2 C atom, whereas the σ-electron density on the other CH bonds of the CH 3 /CH 2 group slightly increases. From experimental IR spectra it follows that donation of the σ-electrons from the bond to the 2p z C-orbital is accompanied by equal withdrawal of the electron density from other CH bonds, that is, the electrons are supplied from each CH bond of the CH 3 /CH 2 group. As a result, all CH stretches of the group are red shifted, and IR spectra show typical CH 3 /CH 2 group vibrations. Experimental findings provided another clue to the electron distribution in the hydrocarbon cations and showed that the standard computational techniques do not allow researchers to explain a number of recently established features of the molecular state of hydrocarbon cations.

physical chemistry chemical physics/pccp. physical chemistry chemical physics

Stabilization of carbocations CH3+, C2H5+, i-C3H7+, tert-Bu+, and cyclo-pentyl+in solid phases: experimental data versus calculations