The applicability of the resonance model to explain the evolution of electron density was tested for a set of 15 nitriles whose protonation processes were studied by means of the quantum theory of atoms in molecules (QTAIM). The electron densities were obtained at the B3LYP/6-31++G**//B3LYP/6-31++G** and HF/6-31++G**//HF/6-31++G** levels. QTAIM atomic and bond properties do not follow the trends that should be expected according to the resonance model and our results are more in line with a H(+)-N[triple bond]C-R Lewis structure than with the H-N(+)[triple bond]C-R and H-N[triple bond]C(+)-R ones. Also, reasonable agreement between experimental and calculated PA values as well as good correlations between variations in atomic energies and populations as a result of protonation were found.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jp811023x | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Proton-Controlled Electron Injection in MoS During Hydrogen Evolution Revealed by Time-Resolved Spectroelectrochemistry.
J Am Chem Soc
January 2025
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Monolayer MoS is an effective electrocatalyst for the hydrogen evolution reaction (HER). Despite significant efforts to optimize the active sites, its catalytic performance still falls short of theoretical predictions. One key factor that has often been overlooked is the electron injection from the conductive substrate into the MoS.
View Article and Find Full Text PDFImpact of Ligand Structure on Biological Activity and Photophysical Properties of NHC-Protected Au Nanoclusters.
J Am Chem Soc
January 2025
Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6, Canada.
N-heterocyclic carbene (NHC)-protected gold nanoclusters display high stability and high photoluminescence, making them well-suited for fluorescence imaging and photodynamic therapeutic applications. We report herein the synthesis of two bisNHC-protected Au nanoclusters with π-extended aromatic systems. Depending on the position of the π-extended aromatic system, changes to the structure of the ligand shell in the cluster are observed, with the ability to correlate increases in rigidity with increases in fluorescence quantum yield.
View Article and Find Full Text PDFHydrogen Tunneling and Conformational Motions in Nonadiabatic Proton-Coupled Electron Transfer between Interfacial Tyrosines in Ribonucleotide Reductase.
J Am Chem Soc
January 2025
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Ribonucleotide reductase (RNR) is essential for DNA synthesis and repair in all living organisms. The mechanism of RNR requires long-range radical transport through a proton-coupled electron transfer (PCET) pathway spanning two different protein subunits. Herein, the direct PCET reaction between the interfacial tyrosine residues, Y356 and Y731, is investigated with a vibronically nonadiabatic theory that treats the transferring proton and all electrons quantum mechanically.
View Article and Find Full Text PDFTernary NASICON-Type NaVMnFe(PO)/NC@CNTs Cathode with Reversible Multielectron Reaction and Long Life for Na-Ion Batteries.
ACS Appl Mater Interfaces
January 2025
Key Laboratory of Low Carbon Energy and Chemical Engineering of Gansu Province, Lanzhou 730050, China.
Na superionic conductor (NASICON)-structure NaMnV(PO) (NVMP) electrode materials reveal highly attractive application prospects due to ultrahigh energy density originating from two-electron reactions. Nevertheless, NVMP also encounters challenges with its poor electronic conductivity, Mn dissolution, and Jahn-Teller distortion. To address this issue, utilizing N-doped carbon layers and carbon nanotubes (CNTs) for dual encapsulation enhances the material's electronic conductivity, creating an effective electron transport network that promotes the rapid diffusion and storage of Na.
View Article and Find Full Text PDFNanoscale Manipulation of Single-Molecule Conformational Transition through Vibrational Excitation.
J Am Chem Soc
January 2025
Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0309, United States.
Controlling molecular actions on demand is a critical step toward developing single-molecule functional devices. Such control can be achieved by manipulating the interactions between individual molecules and their nanoscale environment. In this study, we demonstrate the conformational transition of a single pyrrolidine molecule adsorbed on a Cu(100) surface, driven by vibrational excitation through tunneling electrons using scanning tunneling microscopy.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!