scholarly journals Self-association of organic solutes in solution: a NEXAFS study of aqueous imidazole

2015 ◽  
Vol 179 ◽  
pp. 269-289 ◽  
Author(s):  
M. J. Thomason ◽  
C. R. Seabourne ◽  
B. M. Sattelle ◽  
G. A. Hembury ◽  
J. S. Stevens ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Solid State ◽  
Gas Phase ◽  
Computational Modelling ◽  
Organic Solutes ◽  
Nexafs Spectrum ◽  
Structural Environment ◽  
Self Association ◽  
X Ray Absorption ◽  
Complete Interpretation

N K-edge near-edge X-ray absorption fine-structure (NEXAFS) spectra of imidazole in concentrated aqueous solutions have been acquired. The NEXAFS spectra of the solution species differ significantly from those of imidazole monomers in the gas phase and in the solid state of imidazole, demonstrating the strong sensitivity of NEXAFS to the local chemical and structural environment. In a concentration range from 0.5 to 8.2 mol L−1 the NEXAFS spectrum of aqueous imidazole does not change strongly, confirming previous suggestions that imidazole self-associates are already present at concentrations more dilute than the range investigated here. We show that various types of electronic structure calculations (Gaussian, StoBe, CASTEP) provide a consistent and complete interpretation of all features in the gas phase and solid state spectra based on ground state electronic structure. This suggests that such computational modelling of experimental NEXAFS will permit an incisive analysis of the molecular interactions of organic solutes in solutions. It is confirmed that microhydrated clusters with a single imidazole molecule are poor models of imidazole in aqueous solution. Our analysis indicates that models including both a hydrogen-bonded network of hydrate molecules, and imidazole–imidazole interactions, are necessary to explain the electronic structure evident in the NEXAFS spectra.

Photoelectron spectra and electronic structure of cyanoguanidine in the gas phase and solid state

1981 ◽  
Vol 77 (4) ◽  
pp. 683 ◽  
Author(s):  
David Briggs ◽  
Martyn F. Guest ◽  
Ian H. Hillier ◽  
Michael J. Knight ◽  
Alastair A. MacDowell
Keyword(s):  
Electronic Structure ◽  
Solid State ◽  
Gas Phase ◽  
Photoelectron Spectra

scholarly journals Conclusively Addressing the CoPc Electronic Structure: A Joint Gas-Phase and Solid-State Photoemission and Absorption Spectroscopy Study

2017 ◽  
Vol 121 (47) ◽  
pp. 26372-26378 ◽  
Author(s):  
T. Zhang ◽  
I. E. Brumboiu ◽  
V. Lanzilotto ◽  
J. Lüder ◽  
C. Grazioli ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Solid State ◽  
Gas Phase ◽  
Absorption Spectroscopy ◽  
Spectroscopy Study

NEXAFS and XPS studies of nitrosyl chloride

2015 ◽  
Vol 17 (14) ◽  
pp. 9040-9048 ◽  
Author(s):  
Luca Schio ◽  
Cui Li ◽  
Susanna Monti ◽  
Peter Salén ◽  
Vasyl Yatsyna ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Fine Structure ◽  
Gas Phase ◽  
Theoretical Study ◽  
Nitrosyl Chloride ◽  
X Ray ◽  
Absorption Fine ◽  
Nexafs Spectroscopy ◽  
X Ray Absorption

The electronic structure of nitrosyl chloride (ClNO) has been investigated in the gas phase by X-ray Photoelectron (XPS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy at the Cl 2p, Cl 2s, N 1s and O 1s edges in a combined experimental and theoretical study.

scholarly journals Single-ion magnetism in the extended solid-state: insights from X-ray absorption and emission spectroscopy

2020 ◽  
Vol 11 (43) ◽  
pp. 11801-11810
Author(s):  
Myron S. Huzan ◽  
Manuel Fix ◽  
Matteo Aramini ◽  
Peter Bencok ◽  
J. Frederick W. Mosselmans ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Solid State ◽  
Light Source ◽  
Emission Spectroscopy ◽  
Lithium Nitride ◽  
Absorption And Emission ◽  
X Ray ◽  
Synchrotron Light ◽  
X Ray Absorption ◽  
Absorption And Emission Spectroscopy

Taking advantage of synchrotron light source methods, we present the geometric and electronic structure of iron doped in lithium nitride.

scholarly journals “Anti-Electrostatic” Halogen Bonding

2020 ◽  
Author(s):  
Jana Holthoff ◽  
Elric Engelage ◽  
Robert Weiss ◽  
Stefan Huber
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Gas Phase ◽  
Electrostatic Potential ◽  
Lewis Acids ◽  
Halogen Bonding ◽  
Halide Complexes ◽  
Self Association ◽  
Solid State Structures ◽  
Van Der Waals Radii

Halogen bonding (XB) is often described as being driven predominantly by electrostatics, and thus adducts between <i>anionic</i> XB donors (halogen-based Lewis acids) and anions seem counter­intuitive. Such “anti-electrostatic” XBs have been predicted theoretically, but there are currently no experimental examples based on organic XB donors. Herein, we report the synthesis of two negatively charged organoiodine derivatives, which were subsequently investigated towards their ability to form “anti-electrostatic” XBs with anions. Even though the electrostatic potential is universally negative across the surface of both compounds, DFT calculations indicate kinetic stabilization of their halide complexes in the gas phase and particularly in solution. Experimentally, self-association of the anionic XB donors was observed in solid-state structures, resulting in dimers, trimers and infinite chains. In addition, co-crystals with halides were obtained which featured XB adducts between two or even three anions. The bond-lengths of all observed interactions are 14-21% shorter than sum of the van-der-Waals radii.

scholarly journals The electronic structure and deexcitation pathways of an isolated metalloporphyrin ion resolved by metal L-edge spectroscopy

2021 ◽  
Vol 12 (11) ◽  
pp. 3966-3976
Author(s):  
Kaja Schubert ◽  
Meiyuan Guo ◽  
Kaan Atak ◽  
Simon Dörner ◽  
Christine Bülow ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Electronic Structure ◽  
Gas Phase ◽  
Quantum Mechanical ◽  
Quantum Mechanical Calculations ◽  
X Ray ◽  
Active Space ◽  
X Ray Absorption

Near-edge X-ray absorption mass spectrometry (NEXAMS) and restricted active space (RAS) quantum mechanical calculations at the metal L-edge reveal the electronic structure and orbital-specific deexcitation pathways of gas-phase metalloporphyrins.

SiL- andK-edge x-ray-absorption near-edge spectroscopy of gas-phase Si(CH3)x(OCH3)4−x: Models for solid-state analogs

1993 ◽  
Vol 48 (20) ◽  
pp. 14989-15001 ◽  
Author(s):  
D. G. J. Sutherland ◽  
M. Kasrai ◽  
G. M. Bancroft ◽  
Z. F. Liu ◽  
K. H. Tan
Keyword(s):  
Solid State ◽  
Gas Phase ◽  
X Ray ◽  
X Ray Absorption

scholarly journals “Anti-Electrostatic” Halogen Bonding

2020 ◽  
Author(s):  
Jana Holthoff ◽  
Elric Engelage ◽  
Robert Weiss ◽  
Stefan Huber
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Gas Phase ◽  
Electrostatic Potential ◽  
Lewis Acids ◽  
Halogen Bonding ◽  
Halide Complexes ◽  
Self Association ◽  
Solid State Structures ◽  
Van Der Waals Radii

Halogen bonding (XB) is often described as being driven predominantly by electrostatics, and thus adducts between <i>anionic</i> XB donors (halogen-based Lewis acids) and anions seem counter­intuitive. Such “anti-electrostatic” XBs have been predicted theoretically, but there are currently no experimental examples based on organic XB donors. Herein, we report the synthesis of two negatively charged organoiodine derivatives, which were subsequently investigated towards their ability to form “anti-electrostatic” XBs with anions. Even though the electrostatic potential is universally negative across the surface of both compounds, DFT calculations indicate kinetic stabilization of their halide complexes in the gas phase and particularly in solution. Experimentally, self-association of the anionic XB donors was observed in solid-state structures, resulting in dimers, trimers and infinite chains. In addition, co-crystals with halides were obtained which featured XB adducts between two or even three anions. The bond-lengths of all observed interactions are 14-21% shorter than sum of the van-der-Waals radii.

GAS PHASE X-RAY ABSORPTION SPECTROSCOPY WITH AN ELECTRON YIELD DETECTOR

1986 ◽  
Vol 47 (C8) ◽  
pp. C8-149-C8-151
Author(s):  
F. W. LYTLE ◽  
R. B. GREEGOR ◽  
G. H. VIA ◽  
J. M. BROWN ◽  
G. MEITZNER
Keyword(s):  
Gas Phase ◽  
Absorption Spectroscopy ◽  
X Ray ◽  
Electron Yield ◽  
X Ray Absorption
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