The recently developed (L. Song, W. Wu, Q. Zhang, S. Shaik, J. Phys. Chem. A 2004, 108, 6017) valence bond method coupled with a polarized continuum model (VBPCM) has been applied to the identity SN2 reaction of halides in the gas phase and in aqueous solution. The barriers computed at the level of the breathing orbital VB method (P. C. Hiberty, J. P. Flament, E. Noizet, Chem. Phys. Lett. 1992, 189, 259), BOVB and VBPCM//BOVB, are comparable to CCSD(T) and CCSD(T)//PCM results and to experimentally derived barriers in solution (W. J. Albery, M. M. Kreevoy, Adv. Phys. Org. Chem. 1978, 16, 85). The reactivity parameters needed to apply the valence bond state correlation diagram (VBSCD) method (S. Shaik, J. Am. Chem. Soc. 1984, 106, 1227), were also determined by VB calculations. It has been shown that the reactivity parameters along with their semiempirical derivations provide a satisfactory qualitative and quantitative account of the barriers.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/chem.200600372 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Demystifying Authenticity: Behavioral and Neurophysiological Signatures of Self-Positivity for Authentic and Presented Selves.
Neuroimage
January 2025
School of Psychology, University of Southampton, UK. Electronic address:
Authenticity has captivated scholars. But what is it? An emerging view considers it exaggerated favorability (self-enhancement), whereas traditional views regard it as self-accuracy and self-consistency. We tested these theoretical views by contrasting the authentic self with the presented self, a highly desirable representation.
View Article and Find Full Text PDFRevisiting the electrophysiological correlates of valence and expectancy in reward processing - A multi-lab replication.
Cortex
January 2025
Department of Experimental Clinical & Health Psychology, Ghent University, Ghent, Belgium.
Two event-related brain potential (ERP) components, the frontocentral feedback-related negativity (FRN) and the posterior P300, are key in feedback processing. The FRN typically exhibits greater amplitude in response to negative and unexpected outcomes, whereas the P300 is generally more pronounced for positive outcomes. In an influential ERP study, Hajcak et al.
View Article and Find Full Text PDFIntervalence Charge Transfer in an Osmium(IV) Tetra(ferrocenylaryl) Complex.
Inorg Chem
January 2025
Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States.
The functional properties of tetraaryl compounds, M(aryl) (M = transition metal or group 14 element), are dictated not only by their common tetrahedral geometry but also by their central atom. The identity of this atom may serve to modulate the reactivity, electrochemical, magnetic, and optical behavior of the molecular species, or of extended materials built from appropriate tetraaryl building blocks, but this has not yet been systematically evaluated. Toward this goal, here we probe the influence of Os(IV), C, and Si central atoms on the spectroelectrochemical properties of a series of redox-active tetra(ferrocenylaryl) complexes.
View Article and Find Full Text PDFExploring Singlet Carbyne Anions and Related Low-Valent Carbon Species Utilizing a Cyclic Phosphino Substituent.
Acc Chem Res
January 2025
Department of Chemistry and Research Center for Chemical Biology and Omics Analysis, College of Science, Southern University of Science and Technology, Shenzhen 518055, China.
ConspectusThe advancement of synthetic methodologies is fundamentally driven by a deeper understanding of the structure-reactivity relationships of reactive key intermediates. Carbyne anions are compounds featuring a monovalent anionic carbon possessing four nonbonding valence electrons, which were historically confined to theoretical constructs or observed solely within the environment of gas-phase studies. These species possess potential for applications across diverse domains of synthetic chemistry and ancillary fields.
View Article and Find Full Text PDFReconsideration of the P-clusters in VFe proteins using the bond-valence method: towards their electron transfer and protonation.
Acta Crystallogr D Struct Biol
February 2025
State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China.
P-clusters have been statistically analysed using the bond-valence sum (BVS) method together with weighting schemes. The crystallographic data come from the VFe proteins deposited in the Protein Data Bank (PDB) with high resolutions of better than 1.35 Å.
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!