Molecular structure, infrared spectrum, and photochemistry of squaric acid dimethyl ester in solid argon

Squaric acid dimethyl ester (C(6)O(4)H(6); 3,4-dimethoxycyclobut-3-ene-1,2-dione; DCD) was studied by matrix isolation infrared spectroscopy and by density functional theory (B3LYP) and ab initio (MP2) calculations with the 6-31++G(d,p) and 6-311++G(d,p) basis sets. Three conformers of the compound were theoretically predicted. The two most stable conformers were identified in low-temperature argon matrixes and the energy gap between them was determined. The trans-trans conformer (C(2)(v)) was found to be more stable than the cis-trans form (C(s)) by 4.2 kJ mol(-1), in consonance with the theoretical predictions (MP2 calcd = 3.9 kJ mol(-1)). In situ broadband UV irradiation (lambda > 337 nm) of the matrix-isolated compound was found to induce the ring-opening reaction leading to production of the bisketene, 2,3-dimethoxybuta-1,3-diene-1,4-dione as well as the trans-trans --> cis-trans conformational isomerization. The latter phototransformation allowed separation of the infrared spectra of the two conformers initially trapped into a low-temperature matrix. Upon higher energy irradiation (lambda > 235 nm), the main observed photoproducts were CO and deltic acid dimethyl ester (C(5)O(3)H(6); 2,3-dimethoxycycloprop-2-en-1-one), the latter being obtained in two different conformations (trans-trans and cis-trans). According to the experimental data, deltic acid dimethyl ester is produced by decarbonylation of the initially formed bisketene and not by direct CO extrusion from DCD.     

Spectral calibration of filters and detectors of solar telescope at a wavelength of 13.2 nm for the TESIS project

The telescope at a wavelength of 13.2 nm of the TESIS device of the CORONAS-PHOTON satellite is intended for imaging hot plasma (T ～ 10 MK) of the solar corona. In this paper, calibration of optical elements of the telescope is described. The transmittance of multilayer Zr/Si filters and the sensitivity and radiation resistance of the CCD-array-based detector were measured. The transmittance of filters in the operating wavelength range was 40–50% (for filters of various thicknesses); the spectral dependence of the transmittance was close to the calculated one. The transmittance of filters in the visible region was (1–2) × 10^?6. The detector sensitivity was 0.01–0.1 analog-to-digital units per photon (adu/photon), the radiation resistance was better than 10⁹ rad.     

Profile Monitor for Electron Beam in the High-Voltage Electron Cooling System of the COSY Synchrotron

Technical Physics - A high-voltage system for electron cooling of the COSY (Germany) synchrotron is featured by the presence of a profile monitor that is used for measurement of current density...     

Matrix isolation FTIR spectroscopic and theoretical study of 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243)

The molecular structure and infrared spectrum of the atmospheric pollutant 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243) were characterized experimentally and theoretically. The theoretical calculations show the existence of two conformers, with the gauche (G) and trans (T) orientation around the HCCC dihedral angle. Conformer G was calculated to be more stable than form T by more than 10 kJ mol (-1). In consonance with the large predicted relative energy of conformer T, only the G form was identified spectroscopically in cryogenic argon (10 K) and xenon (20 K) matrices prepared from room-temperature equilibrium vapor of the compound. The observed infrared spectra of the matrix-isolated HCFC-243 were interpreted with the aid of high-level density functional theory calculations and normal coordinate analysis. For experimental identification of the weakest IR absorption bands, the spectrum of HCFC-243 in the neat solid state at 145 K was obtained. This spectrum also confirmed the sole presence of the G conformer in the sample. Natural bond orbital and atomic charge analyses were carried out for the two conformers to shed light on the most important intramolecular interactions in the two conformers, in particular those responsible for their relative stability.     

Structure of Isolated 1,4-Butanediol: Combination of MP2 Calculations, NBO Analysis, and Matrix-Isolation Infrared Spectroscopy

Theoretical calculations at the MP2 level, NBO and AIM analysis, and matrix-isolation infrared spectroscopy have been used to investigate the structure of the isolated molecule of 1,4-butanediol (1,4-BDO). Sixty-five structures were found to be minima on the potential energy surface, and the three most stable forms are characterized by a folded backbone conformation leading to the formation of an intramolecular H-bond. To better characterize the intramolecular interactions and particularly the hydrogen bonds, natural bond orbital analysis (NBO) was performed for the four most stable conformers, and was further complemented with an atoms-in-molecules (AIM) topological analysis. Infrared spectra of 1,4-BDO isolated in low-temperature argon and xenon matrixes show a good agreement with a population-weighted mean theoretical spectrum, and the spectral features of the conformers expected to be trapped in the matrixes were observed experimentally. Annealing the xenon matrix from 20 to 60 K resulted in significant spectral changes, which were interpreted based on the barriers to intramolecular rotation. An estimation of the intramolecular hydrogen bond energy was carried out following three different methodologies.     

Coherent interaction of ion and electron beams in systems with electron cooling

A hydrodynamic approximation is used to study the behavior of dipole modes of the transverse oscillations of an ion beam in a storage ring with an electron cooling section. It is shown that in addition to the finite interaction time of the beams, instability may be caused by a specific interaction effect between the ion and electron beams in the magnetic field which leads to redistribution of energy between the various modes of the ion beam oscillations. In this case, the condition that the determinant of the transfer matrix for the cooling section does not exceed unity no longer guarantees the stability of the transverse coherent oscillations of the ion beam and all the eigenvalues of the complete matrix of the ion motion including the storage ring must be analyzed. Calculations of the stability of ion beam dipole oscillations are presented for the parameters of CELSIUS.