Search results for "Matrix isolation"

2019

Molecular complexes between glycolic acid and nitrogen were studied in a low-temperature argon matrix with FTIR spectroscopy, and supported by MP2 and BLYPD3 calculations. The calculations indicate 11 and 10 stable complex structures at the MP2 and BLYPD3 levels of theories, respectively. However, only one hydrogen-bonded complex structure involving the most stable SSC conformer of glycolic acid was found experimentally, where the nitrogen molecule is bound with the carboxylic OH group of the SSC conformer. The complex shows a rich site structure variation upon deposition of the matrix in different temperatures and upon annealing experiments, which provide interesting prospects for site-sel…

Pencil Lead as a Matrix for MALDI-ToF Mass Spectrometry of Sensitive Functional Polymers

2007

With the increase in complexity of functional polymers in recent years, MALDI-ToF has become an important tool for gaining precise information on polymer functionality, end groups, and, in special cases, molecular weights. Here we describe how pencil lead, deposited by simply drawing with a regular pencil onto conventional MALDI-ToF targets, can be used as a very attractive matrix for MALDI-ToF mass spectrometry of synthetic polymers. Highly sensitive polymers such as silyl hydride functional poly(styrene), poly(butadiene), and poly(isoprene) have been investigated using conventional MALDI-ToF matrices as well as pencil lead. In all cases, the use of pencil lead prevented oxidation of the h…

Vibrational relaxation of matrix-isolated carboxylic acid dimers and monomers.

2009

Femtosecond mid-IR transient absorption spectroscopy was used to probe the vibrational dynamics of formic acid and acetic acid isolated in solid argon following excitation of the fundamental transition of the carbonyl stretching mode. Carboxylic acids form extremely stable H-bonded dimers, hindering the study of the monomeric species at equilibrium conditions. The low-temperature rare-gas matrix isolation technique allows for a unique control over aggregation enabling the study of the monomer vibrational dynamics, as well as the dynamics of two distinct dimer structures (cyclic and open chain). This study provides insight into the role of the methyl rotor and hydrogen bonding in the vibrati…

An Accurate Quartic Force Field and Fundamental Frequencies for the Ozonide Anion: A Rare Positive Anharmonicity for the Antisymmetric Stretch

2003

The CCSD(T) method has been used to compute a highly accurate quartic force field and fundamental frequencies for all 16O and 18O isotopomers of the ozonide anion. The CCSD and CASPT2 methods have also been used to verify the reliability of the CCSD(T) fundamental frequencies. The computed fundamental frequencies are in agreement with gas-phase experiments, but disagree with matrix isolation experiments for the antisymmetric stretch, ν3. CASPT2 calculations show that the antisymmetric part of the O3- potential surface is sensitive to the external environment. It is concluded that the antisymmetric stretch exhibits a significant matrix shift in the matrix isolation experiments and that the m…

A study of the atmospherically important reactions of dimethylsulfide (DMS) with I2 and ICl using infrared matrix isolation spectroscopy and electron…

2012

The reactions of dimethylsulfide (DMS) with molecular iodine (I(2)) and iodine monochloride (ICl) have been studied by infrared matrix isolation spectroscopy by co-condensation of the reagents in an inert gas matrix. Molecular adducts of DMS + I(2) and DMS + ICl have also been prepared using standard synthetic methods. The vapour above each of these adducts trapped in an inert gas matrix gave the same infrared spectrum as that recorded for the corresponding co-condensation reaction. In each case, the infrared spectrum has been interpreted in terms of a van der Waals adduct, DMS : I(2) and DMS : ICl, with the aid of infrared spectra computed for their minimum energy structures at the MP2 lev…

Complexes of Glycolic Acid with Nitrogen Isolated in Argon Matrices. I. Structures and Thermal Effects.

2019

Molecular complexes between glycolic acid and nitrogen were studied in a low-temperature argon matrix with FTIR spectroscopy, and supported by MP2 and BLYPD3 calculations. The calculations indicate 11 and 10 stable complex structures at the MP2 and BLYPD3 levels of theories, respectively. However, only one hydrogen-bonded complex structure involving the most stable SSC conformer of glycolic acid was found experimentally, where the nitrogen molecule is bound with the carboxylic OH group of the SSC conformer. The complex shows a rich site structure variation upon deposition of the matrix in different temperatures and upon annealing experiments, which provide interesting prospects for site-sel…

Experimental FTIR-MI and Theoretical Studies of Isocyanic Acid Aggregates

2023

Homoaggregates of isocyanic acid (HNCO) were studied using FTIR spectroscopy combined with a low-temperature matrix isolation technique and quantum chemical calculations. Computationally, the structures of the HNCO dimers and trimers were optimized at the MP2, B3LYPD3 and B2PLYPD3 levels of theory employing the 6-311++G(3df,3pd) basis set. Topological analysis of the electron density (AIM) was used to identify the type of non-covalent interactions in the studied aggregates. Five stable minima were located on the potential energy surface for (HNCO)2, and nine were located on the potential energy surface for (HNCO)3. The most stable dimer (D1) involves a weak, almost linear N-H⋯N hydrog…

Structure and IR Spectroscopic Properties of HNCO Complexes with SO

2021

FTIR spectroscopy was combined with the matrix isolation technique and quantum chemical calculations with the aim of studying complexes of isocyanic acid with sulfur dioxide. The structures of the HNCO⋯SO2 complexes of 1:1, 1:2 and 2:1 stoichiometry were optimized at the MP2, B3LYPD3, B2PLYPD3 levels of theory with the 6-311++G(3df,3pd) basis set. Five stable 1:1 HNCO⋯SO2 complexes were found. Three of them contain a weak N-H⋯O hydrogen bond, whereas two other structures are stabilized by van der Waals interactions. The analysis of the HNCO/SO2/Ar spectra after deposition indicates that mostly the 1:1 hydrogen-bonded complexes are present in argon matrices, with a small amount of the van de…

Complexes of Glycolic Acid with Nitrogen Isolated in Argon Matrices. II : Vibrational Overtone Excitations

2019

Structural changes of glycolic acid (GA) complex with nitrogen induced by selective overtone excitation of the νOH mode were followed in argon matrices using FTIR spectroscopy. For the most stable SSC1 complex present in different trapping sites directly upon deposition site, selective changes in the νOH region were achieved upon near-infrared irradiation. Simultaneously, new conformers of the GA…N2 complex were formed, giving rise to several sets of bands in the νOH and νC=O regions of the spectra. Both position and intensity of new absorptions appeared to be highly sensitive on the wavelength of radiation used, as well as on the annealing of the matrix. Based on theoretical calculations a…

Complexes of Glycolic Acid with Nitrogen Isolated in Argon Matrices. I : Structures and Thermal Effects

2019

Molecular complexes between glycolic acid and nitrogen were studied in a low-temperature argon matrix with FTIR spectroscopy, and supported by MP2 and BLYPD3 calculations. The calculations indicate 11 and 10 stable complex structures at the MP2 and BLYPD3 levels of theories, respectively. However, only one hydrogen-bonded complex structure involving the most stable SSC conformer of glycolic acid was found experimentally, where the nitrogen molecule is bound with the carboxylic OH group of the SSC conformer. The complex shows a rich site structure variation upon deposition of the matrix in different temperatures and upon annealing experiments, which provide interesting prospects for site-sel…