Although it has been widely recognized that hydrogen bonds play a significant role in the photophysics of molecules, this phenomenon has rarely been applied to the solvatochromic method for determination of dipole moments. The difference in the dipole moment between the ground and excited state was determined in protic and aprotic solvents using both the Lippert-Mataga equation and the Bilot-Kawski equation for bromocresol purple, a molecule capable of hydrogen-bond donation and acceptance. The dipole change in protic environments was determined to be 15.2 ± 1.0 D for the Lippert-Mataga method and 9.2 ± 1.0 D for the Bilot-Kawski method, while the change in aprotic environments was 10.4 ± 1.0 D and 6.7 ± 1.0 D, respectively. Both methods highlighted the importance of hydrogen bonding in stabilizing increased charge-separation of the excited state, allowing for larger changes in dipole moments in protic environments. This study further validates a simple, rational modification to the commonly used methods that allows access to dipole-moment data on dyes with hydrogen-bonding capabilities through solvatochromic experiments.
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http://dx.doi.org/10.1016/j.saa.2015.11.034 | DOI Listing |
J Chem Phys
January 2025
Department of Earth and Environmental Science, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6243, USA.
The detection of HC(S)CN in TMC-1 suggests that HC(S)NC may also exist. To aid in its possible detection, HC(S)NC and its deuterated isotopologue DC(S)NC were investigated via high-level ab initio methods, specifically CCSD(T) and CCSD(T)-F12. By utilizing multidimensional potential energy surfaces derived from explicitly correlated coupled-cluster calculations, we analyzed their geometrical parameters, vibrational frequencies, rotational constants, and a comprehensive set of spectroscopic constants generated via the vibrational second-order perturbation theory, vibrational self-consistent field, and vibrational configuration interaction theory(VCI) approaches.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Department of Chemistry, University of Washington, Seattle, Washington 98185, USA.
We derive a new expression for the strength of a hydrogen bond (VHB) in terms of the elongation of the covalent bond of the donor fragment participating in the hydrogen bond (ΔrHB) and the intermolecular coordinates R (separation between the heavy atoms) and θ (deviation of the hydrogen bond from linearity). The expression includes components describing the covalent D-H bond of the hydrogen bond donor via a Morse potential, the Pauli repulsion, and electrostatic interactions between the constituent fragments using a linear expansion of their dipole moment and a quadratic expansion of their polarizability tensor. We fitted the parameters of the model using ab initio electronic structure results for six hydrogen bonded dimers, namely, NH3-NH3, H2O-H2O, HF-HF, H2O-NH3, HF-H2O, and HF-NH3, and validated its performance for extended parts of their potential energy surfaces, resulting in a mean absolute error ranging from 0.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Ural Federal University, Ekaterinburg, Russia.
This work is devoted to the study of the static magnetization of immobilized multi-core particles (MCPs) and their ensembles. These objects model aggregates of superparamagnetic nanoparticles that are taken up by biological cells and subsequently used, for example, as magnetoactive agents for cell imaging. In this study, we derive an analytical formula that allows us to predict the static magnetization of MCPs consisting of immobilized granules, in which the magnetic moment rotates freely the Néel mechanism.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Nanjing University, Department of Physics, 22 Hankou Road, 210093, Nanjing, CHINA.
Amino acid crystals have emerged as promising piezoelectric materials for biodegradable and biocompatible sensors; however, their relatively low piezoelectric coefficients constrain practical applications. Here, we introduce a fluoro-substitution strategy to overcome this limitation and enhance the piezoelectric performance of amino acid crystals. Specifically, we substituted hydrogen atoms on the aromatic rings of L-tryptophan, L-phenylalanine, and N-Cbz-L-phenylalanine with fluorine, resulting in significantly elevated piezoelectric coefficients.
View Article and Find Full Text PDFMolecular junctions (MJs) are celebrated nanoelectronic devices for mimicking conventional electronic functions, including rectifiers, sensors, wires, switches, transistors, negative differential resistance, and memory, following an understanding of charge transport mechanisms. However, capacitive nanoscale molecular junctions are rarely seen. The present work describes electrochemically (E-Chem) grown covalently attached molecular thin films of 10, 14.
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