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Related Concept Videos

Ionic Crystal Structures02:42

Ionic Crystal Structures

Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
¹H NMR: Complex Splitting01:13

¹H NMR: Complex Splitting

A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.
IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations01:08

IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations

Identical bonds within a polyatomic group can stretch symmetrically (in-phase) or asymmetrically (out-of-phase). Similar to hydrogen bonding, these vibrations also influence the shape of the IR peak. Generally, asymmetric stretching frequencies are higher than symmetric stretching frequencies. For example, primary amines exhibit two distinct IR peaks between 3300–3500 cm−1 corresponding to the symmetric and asymmetric N-H stretching, while secondary amines exhibit a single stretching vibration...
Structure of Amines01:19

Structure of Amines

The hybridized nitrogen atom in amines possesses a lone pair of electrons and is bound to three substituents with a bond angle of around 108°, which is less than the tetrahedral angle of 109.5°. However, the C–N–H bond angle is slightly larger at 112°, with a carbon–nitrogen bond length of 147 pm. This carbon–nitrogen bond length of of amines is longer than the carbon–oxygen bond of alcohols (143 pm) but shorter than alkanes’ carbon–carbon bond (154 pm). These aspects are illustrated in Figure...
Mass Spectrum: Interpretation01:24

Mass Spectrum: Interpretation

An unknown compound can be established by identifying the molecular ion peak in the mass spectrum. The molecular ion peak is often weak or absent due to the predominance of fragmentation in high-energy electron beams. In such cases, a soft-energy electron beam can be used to scan the spectrum to enhance the intensity of the molecular ion peak. Additionally, chemical ionization, field ionization, and desorption ionization spectra are used to obtain a relatively intense molecular ion peak.To...
Raman Spectroscopy: Overview01:20

Raman Spectroscopy: Overview

The underlying principle of Raman spectroscopy is based on the interaction between light and matter, specifically molecules' inelastic scattering of photons. When a monochromatic beam of light, typically from a laser source, interacts with a sample, most scattered light has the same frequency as the incident light. This is known as Rayleigh scattering.
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Related Experiment Video

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Low Pressure Vapor-assisted Solution Process for Tunable Band Gap Pinhole-free Methylammonium Lead Halide Perovskite Films
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Raman spectra of the double-anion salts M3ZnCl4NO3 (M+ = K+, Rb+, NH4).

R L Carter1

  • 1Department of Chemistry, University of Massachusetts Boston, 02125, USA. robert.carter@umb.edu

Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy
|November 15, 2000
PubMed
Summary

This study analyzes Raman spectra of isomorphous double-anion salts, K3ZnCl4NO3, (NH4)3ZnCl4NO3, and Rb3ZnCl4NO3. Findings reveal distinct vibrational modes for the zinc tetrachloridometallate(2-) and nitrate ions, influenced by crystal site symmetry.

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Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid

Published on: January 25, 2020

Area of Science:

  • Solid-state chemistry
  • Vibrational spectroscopy
  • Crystallography

Background:

  • Isomorphous double-anion salts, including K3ZnCl4NO3, (NH4)3ZnCl4NO3, and Rb3ZnCl4NO3, share the Pnma space group and Z=4.
  • Understanding the vibrational behavior of these salts provides insights into their structural and bonding characteristics.

Purpose of the Study:

  • To investigate and interpret the room-temperature Raman spectra of K3ZnCl4NO3, (NH4)3ZnCl4NO3, and Rb3ZnCl4NO3.
  • To compare the spectral features of these double-anion salts with their single-anion counterparts.
  • To elucidate the influence of crystallographic site symmetry on the vibrational modes of the zinc tetrachloridometallate(2-) and nitrate ions.

Main Methods:

  • Room-temperature (295 K) Raman spectroscopy was performed on polycrystalline samples.
  • Spectra were analyzed based on Cs site symmetry for the ions and D2h factor group of the unit cell.
  • Comparisons were made with Raman spectra of M2ZnCl4 and MNO3 single-anion salts.

Main Results:

  • Despite isomorphism, ZnCl4(2-) modes varied significantly among the M3ZnCl4NO3 compounds.
  • NO3- modes exhibited greater similarity across the studied salts.
  • Splitting of NO3- v3 and v4 modes was observed due to reduced site symmetry (Cs) from the free ion (D3h).
  • The Raman-inactive v2 mode of NO3- was detected, often with lower intensity than its overtone (2v2).
  • Distinctive features, including potential hot bands or disorder, were noted in the spectra of K3ZnCl4NO3 and Rb3ZnCl4NO3 but not in (NH4)3ZnCl4NO3.
  • Broad bands from NH4+ ions in (NH4)3ZnCl4NO3 obscured some spectral regions but allowed observation of the NO3- overtone 2v2.

Conclusions:

  • The vibrational spectra confirm the isomorphism of the studied double-anion salts.
  • Site symmetry plays a crucial role in the observed splitting and intensity patterns of the nitrate ion modes.
  • The presence of ammonium ions significantly impacts the overall spectral profile due to their broad vibrational bands.