Spectral Signatures of Hydrated Proton Vibrations in Water Clusters

Science ◽  
2005 ◽  
Vol 308 (5729) ◽  
pp. 1765-1769 ◽  
Author(s):  
J. M. Headrick
Keyword(s):  
Water Clusters ◽  
Spectral Signatures ◽  
Hydrated Proton

scholarly journals Towards complete assignment of the infrared spectrum of the protonated water cluster H+(H2O)21

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Jinfeng Liu ◽  
Jinrong Yang ◽  
Xiao Cheng Zeng ◽  
Sotiris S. Xantheas ◽  
Kiyoshi Yagi ◽  
...  
Keyword(s):  
Water Clusters ◽  
Model Systems ◽  
Cluster Method ◽  
Spectral Signature ◽  
Water Molecules ◽  
Vibrational Resonance ◽  
Spectral Signatures ◽  
Phase Water ◽  
Coordinated Water ◽  
Degenerate Perturbation Theory

AbstractThe spectroscopic features of protonated water species in dilute acid solutions have been long sought after for understanding the microscopic behavior of the proton in water with gas-phase water clusters H+(H2O)n extensively studied as bottom-up model systems. We present a new protocol for the calculation of the infrared (IR) spectra of complex systems, which combines the fragment-based Coupled Cluster method and anharmonic vibrational quasi-degenerate perturbation theory, and demonstrate its accuracy towards the complete and accurate assignment of the IR spectrum of the H+(H2O)21 cluster. The site-specific IR spectral signatures reveal two distinct structures for the internal and surface four-coordinated water molecules, which are ice-like and liquid-like, respectively. The effect of inter-molecular interaction between water molecules is addressed, and the vibrational resonance is found between the O-H stretching fundamental and the bending overtone of the nearest neighboring water molecule. The revelation of the spectral signature of the excess proton offers deeper insight into the nature of charge accommodation in the extended hydrogen-bonding network underpinning this aqueous cluster.

Spectral signatures of proton delocalization in H+(H2O)n=1−4 ions

2018 ◽  
Vol 212 ◽  
pp. 443-466 ◽  
Author(s):  
Laura C. Dzugan ◽  
Ryan J. DiRisio ◽  
Lindsey R. Madison ◽  
Anne B. McCoy
Keyword(s):  
Monte Carlo ◽  
Perturbation Theory ◽  
Harmonic Analysis ◽  
Water Clusters ◽  
Diffusion Monte Carlo ◽  
Spectral Signatures ◽  
And Diffusion

Vibrational couplings in protonated water clusters are described by harmonic analysis, vibrational perturbation theory (VPT2) and diffusion Monte Carlo (DMC) approaches.

Oriented Luminescent Nanostructures From Single Molecules Of Conjugated Polymers

2003 ◽  
Vol 771 ◽  
Author(s):  
Adosh Mehta ◽  
Pradeep Kumar ◽  
Jie Zheng ◽  
Robert M. Dickson ◽  
Bobby Sumpter ◽  
...  
Keyword(s):  
Conjugated Polymers ◽  
Polarization Anisotropy ◽  
Emission Pattern ◽  
Spectral Signatures ◽  
Dipole Emission ◽  
Ink Jet ◽  
Molecular Scale ◽  
Jet Printing ◽  
Photochemical Stability ◽  
Printing Techniques

AbstractDipole emission pattern imaging experiments on single chains of common conjugated polymers (solubilized poly phenylene vinylenes) isolated by ink-jet printing techniques have revealed surprising uniformity in transition moment orientation perpendicular to the support substrate. In addition to uniform orientation, these species show a number of striking differences in photochemical stability, polarization anisotropy,[1] and spectral signatures[2] with respect to similar (well-studied) molecules dispersed in dilute thin-films. Combined with molecular mechanics simulation, these results point to a structural picture of a folded macromolecule as a highly ordered cylindrical nanostructure whose long-axis (approximately collinear with the conjugation axis) is oriented, by an electrostatic interaction, perpendicular to the coverglass substrate. These results suggest a number of important applications in nanoscale photonics and molecular-scale optoelectronics.

Case Study of Autistic Subjects with Stable Water Clusters in Panama

2012 ◽  
Vol 3 (3-4) ◽  
pp. 267-280 ◽  
Author(s):  
Ricardo Velasquez ◽  
Holly Chu ◽  
Shui Yin Lo
Keyword(s):  
Water Clusters

Proton Acidity and Proton Mobility in ECR-40, a Silicoaluminophosphate That Violates Löwenstein’s Rule

2019 ◽  
Author(s):  
Michael Fischer
Keyword(s):  
Density Functional ◽  
Water Clusters ◽  
Computational Study ◽  
Acid Catalyst ◽  
Ab Initio Molecular Dynamics ◽  
Brønsted Acidity ◽  
Hydrothermal Route ◽  
Proton Mobility ◽  
Brönsted Acidity ◽  
A Minor

<p>The silicoaluminophosphate zeotype ECR-40, which has the MEI topology, contains linkages of AlO<sub>4</sub> tetrahedra via a common oxygen atom, thereby violating the famous “Löwenstein’s rule”. Due to the proven existence of Al-O-Al linkages in this material, it constitutes an ideal model system to study the acidity and mobility of protons associated with such unusual linkages. In addition, their properties can be directly compared to those of protons associated with more common Si-O-Al linkages, which are also present in ECR-40. In this work, static density functional theory (DFT) calculations including a dispersion correction were employed to study the preferred proton sites as well as the Brønsted acidity of the framework protons, followed by DFT-based ab-initio molecular dynamics (AIMD) to investigate the proton mobility in guest-free and hydrated ECR-40. Initially, two different proton arrangements were compared, one containing both H[O6] protons associated with Al-O-Al linkages and H[O10] protons at Si-O-Al linkages, the other one containing only H[O10] protons. The former model was found to be thermodynamically favoured, as a removal of protons from the Al-O-Al linkages causes a local accumulation of negative charge. Calculations of the deprotonation energy showed a moderately higher Brønsted acidity of the H[O10] protons, at variance with previous empirical explanations, which attributed the exceptional performance of ECR-40 as acid catalyst to the presence of Al‑O‑Al linkages. The AIMD simulations (<i>T</i> = 298 K) delivered no appreciable proton mobility for guest-free ECR-40 and for low levels of hydration (one H<sub>2</sub>O per framework proton). Under saturation conditions, framework deprotonation occurred, leading to the formation of protonated water clusters in the pores. Pronounced differences between the two types of framework protons were observed: While the H[O10] protons were always removed from the Si-O-Al linkages, the Al-O-Al linkages remained mostly protonated, but deprotonation did occur to a minor extent. The observation of a degree of framework deprotonation of Al-O-Al linkages differs from the findings reported in a recent computational study of hydrated aluminosilicate zeolites with such linkages (Heard et al., <i>Chem. Sci.</i> <b>2019</b>, <i>10</i>, 5705), pointing to an influence of the overall framework composition. Further inspection of the AIMD results showed that a coordination of water molecules to framework Al atoms occurred in many cases, especially in the vicinity of the Al-O-Al linkages, sometimes resulting in a pronounced modification of the linkages through additional bridging oxygen atoms. Given the changes in the local structure, it can be expected that such modified linkages are especially prone to break upon dehydration. Thus, in addition to elucidating the deprotonation behaviour of protons associated with different types of linkages, the calculations also provide insights into possible reasons for the instability of Al-O-Al linkages, clarifying why Löwenstein’s rule is mostly obeyed in materials that are formed via a hydrothermal route.</p>

Sign in / Sign up

Export Citation Format

Share Document