Symmetry-Adapted Perturbation Theory (SAPT) is one of the most popular approaches to energy component analysis of non-covalent interactions between closed-shell systems, yielding both accurate interaction energies and meaningful interaction energy components. In recent years, the full open-shell equations for SAPT up to second-order in the intermolecular interaction and zeroth-order in the intramolecular correlation (SAPT0) were published [P. S. Zuchowski et al., J. Chem. Phys. 129, 084101 (2008); M. Hapka et al., ibid. 137, 164104 (2012)]. Here, we utilize density-fitted electron repulsion integrals to produce an efficient computational implementation. This approach is used to examine the effect of ionization on π-π interactions. For the benzene dimer radical cation, comparison against reference values indicates a good performance for open-shell SAPT0, except in cases with substantial charge transfer. For π stacking between hydrogen-bonded pairs of nucleobases, dispersion interactions still dominate binding, in spite of the creation of a positive charge.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1063/1.4963385 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Substituent and Heteroatom Effects on π-π Interactions: Evidence That Parallel-Displaced π-Stacking is Not Driven by Quadrupolar Electrostatics.
J Am Chem Soc
January 2025
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Stacking interactions are a recurring motif in supramolecular chemistry and biochemistry, where a persistent theme is a preference for parallel-displaced aromatic rings rather than face-to-face π-stacking. This is typically explained in terms of quadrupole-quadrupole interactions between the arene moieties but that interpretation is inconsistent with accurate calculations, which reveal that the quadrupolar picture is qualitatively wrong. At typical π-stacking distances, quadrupolar electrostatics may differ in sign from an exact calculation based on charge densities of the interacting arenes.
View Article and Find Full Text PDFFrom Molecule to Aggregate: Understanding AIE through Multiscale Experimental and Computational Techniques.
J Phys Chem B
December 2024
Department of Chemistry, Indian Institute of Technology Gandhinagar, Palaj, Gandhinagar 382055, India.
Article Synopsis
- Aggregation-induced emission (AIE) is gaining importance in fields like materials science and biomedicine, but the mechanisms behind it are not fully understood.
- This study utilizes a combination of experimental and theoretical methods, including the synthesis of four organic molecules and modeling simulations, to explore what influences AIE activity.
- The research finds that AIE-active molecules form J-type aggregates with enhanced emission, while AIE-inactive molecules form H-type aggregates with restricted emission, and the molecules localize within lipid droplets, potentially guiding future material design for advanced applications.
Crystal structure predictions for molecules with soft degrees of freedom using intermonomer force fields derived from first principles.
Acta Crystallogr B Struct Sci Cryst Eng Mater
December 2024
Department of Physics and Astronomy, University of Delaware, Newark, DE 19716, USA.
Article Synopsis
- - The seventh blind test for molecular crystal structure prediction (CSP) involved two stages with seven diverse crystal targets, including cocrystals and a salt, analyzed using a CSP protocol that started with finding optimal molecule conformations.
- - An ab initio two-body rigid-monomer six-dimensional force field (aiFF) was developed to assist with packing and energy minimization in CSPs, incorporating flexible-monomer techniques for specific targets.
- - The results highlighted a success rate of 15% in structure generation and 33% in structure rating during the submission phase, improving significantly post-submission to 54% and 89%, respectively; the study suggests a conformer-based CSP approach is effective for crystals with flexible
The C-H···S-S hydrogen bonding in diethyl disulfide⋯difluoromethane: a combined microwave spectroscopic and computational study.
Phys Chem Chem Phys
December 2024
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 401331, China.
The C-H⋯S weak interaction is crucial for comprehending the stability in biological macromolecules and their interactions with smaller molecules. Despite its prevalence, an in-depth understanding and recognition of such interaction remain elusive. Herein, the rotational spectra of a binary complex formed by diethyl disulfide and difluoromethane were investigated using Fourier transform microwave spectroscopy combined with theoretical calculations to examine the C-H⋯S-S interaction.
View Article and Find Full Text PDFIn Silico Screening of CO-Dipeptide Interactions for Bioinspired Carbon Capture.
Chemphyschem
November 2024
Department of Chemistry, University of Tennessee, 37996, Knoxville, Tennessee, United States.
Carbon capture, sequestration and utilization offers a viable solution for reducing the total amount of atmospheric CO concentrations. On an industrial scale, amine-based solvents are extensively employed for CO capture through chemisorption. Nevertheless, this method is marked by the high cost associated with solvent regeneration, high vapor pressure, and the corrosive and toxic attributes of by-products, such as nitrosamines.
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!