The molecular structure of N-methylsuccinimide studied by gas-phase electron diffraction (GED) and quantum-chemical methods

The molecular structure of N-methylsuccinimide was studied by the GED method at a nozzle temperature of 69–73°C. Anharmonic vibrational corrections to thermal-average r _a bond lengths, Δ(r _a − r _e), were calculated using the quadratic and cubic force constants from B3LYP/6-31G(df, p) calculations. The molecular skeleton was found to be planar within measurement errors. Some structural effects were likely caused by the conjugation of the N atom with two C=O bonds. The equilibrium geometric parameters derived from the experimental data and those from MP2/cc-pVTZ(seg-opt) calculations were in close agreement.     

Molecular structure of 1,5-diazabicyclo[3.1.0]hexane as determined by gas electron diffraction and quantum-chemical calculations

The equilibrium molecular structure and conformation of 1,5-diazabicyclo[3.1.0]hexane (DABH) has been studied by the gas-phase electron-diffraction method at 20 degrees C and quantum-chemical calculations. Three possible conformations of DABH were considered: boat, chair, and twist. According to the experimental and theoretical results, DABH exists exclusively as a boat conformation of C s symmetry at the temperature of the experiment. The MP2 calculations predict the stable chair and twist conformations to be 3.8 and 49.5 kcal mol(-1) above the boat form, respectively. The most important semi-experimental geometrical parameters of DABH (r(e), A and angle)e), deg) are (N1-N5) = 1.506(13), (N1-C6) = 1.442(2), (N1-C2) = 1.469(4), (C2-C3) = 1.524(7), (C6-N1-C2) = 114.8(8), (N5-N1-C2) = 107.7(4), (N1-C2-C3) = 106.5(9), and (C2-C3-C4) = 104.0(10). The natural bond orbital (NBO) analysis has shown that the most important stabilization factor in the boat conformation is the n(N) --> sigma*(C-C) anomeric effect. The geometry calculations and NBO analysis have been performed also for the bicyclohexane molecule.     

Interfacial interaction in a composite based on multi-walled carbon nanotubes and amorphous tin oxide

The specific features of changes in the electronic structure of multi-walled carbon nanotubes (MWCNTs) due to the interaction with an amorphous tin oxide in the SnO_x/MWCNT composite formed by magnetron sputtering have been investigated using X-ray spectroscopy. It has been shown that the formation of chemical bonds responsible for significant changes in the local and electronic structures of the outer layers of MWCNTs occurs at the boundaries of the “amorphous oxide/MWCNT” contacts. The vacuum annealing of the composite leads to the disturbance of the chemical interaction at interfaces of the composite and to a partial recovery of the local structure of the outer layers of MWCNTs. A decrease in the amount of oxygen in the tin oxide under vacuum annealing conditions causes an increase in the number of unpaired Sn 5s electrons, which, in turn, enhances the charge transfer through the interfaces in the composite and leads to a splitting of the π^*-subsystem of the outer layers of MWCNTs.     

Molecular structure and conformation of nitrobenzene reinvestigated by combined analysis of gas-phase electron diffraction,rotational constants,and theoretical calculations

The molecular structure and conformation of nitrobenzene has been reinvestigated by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) spectroscopic data, and quantum chemical calculations. The equilibrium r _e structure of nitrobenzene was determined by a joint analysis of the GED data and rotational constants taken from the literature. The necessary anharmonic vibrational corrections to the internuclear distances (r _e ? r _a) and to rotational constants (B _e ⁽ⁱ⁾  ? B ₀ ⁽ⁱ⁾ ) were calculated from the B3LYP/cc-pVTZ quadratic and cubic force fields. A combined analysis of GED and MW data led to following structural parameters (r _e) of planar nitrobenzene (the total estimated uncertainties are in parentheses): r(C–C)_av = 1.391(3) Å, r(C–N) = 1.468(4) Å, r(N–O) = 1.223(2) Å, r(C–H)_av = 1.071(3) Å, \({\angle}\)C2–C1–C6 = 123.5(6)°, \({\angle}\)C1–C2–C3 = 117.8(3)°, \({\angle}\)C2–C3–C4 = 120.3(3)°, \({\angle}\)C3–C4–C5 = 120.5(6)°, \({\angle}\)C–C–N = 118.2(3)°, \({\angle}\)C–N–O = 117.9(2)°, \({\angle}\)O–N–O = 124.2(4)°, \({\angle}\)(C–C–H)_av = 120.6(20)°. These structural parameters reproduce the experimental B ₀ ⁽ⁱ⁾ values within 0.05 MHz. The experimental results are in good agreement with the theoretical calculations. The barrier height to internal rotation of nitro group, 4.1±1.0 kcal/mol, was estimated from the GED analysis using a dynamic model. The equilibrium structure was also calculated using the experimental rotational constants for nitrobenzene isotopomers and theoretical rotation–vibration interaction constants.     

Molecular structure and conformational composition of 1,3-dihydroxyacetone studied by combined analysis of gas-phase electron diffraction data, rotational constants, and results of theoretical calculations. Ideal gas thermodynamic properties of 1,3-dihydroxyacetone

The molecular structure of 1,3-dihydroxyacetone (DHA) has been studied by gas-phase electron diffraction (GED), combined analysis of GED and microwave (MW) data, ab initio, and density functional theory calculations. The equilibrium re structure of DHA was determined by a joint analysis of the GED data and rotational constants taken from the literature. The anharmonic vibrational corrections to the internuclear distances (re-ra) and to the rotational constants (B(i)e-B(i)0) needed for the estimation of the re structure were calculated from the B3LYP/cc-pVTZ cubic force field. It was found that the experimental data are well reproduced by assuming that DHA consists of a mixture of three conformers. The most stable conformer of C2v symmetry has two hydrogen bonds, whereas the next two lowest energy conformers (Cs and C1 symmetry) have one hydrogen bond and their abundance is about 30% in total. A combined analysis of GED and MW data led to the following equilibrium structural parameters (re) of the most abundant conformer of DHA (the uncertainties in parentheses are 3 times the standard deviations): r(C=O)=1.215(2) A, r(C-C)=1.516(2) A, r(C-O)=1.393(2) A, r(C-H)=1.096(4) A, r(O-H)=0.967(4) A, angleC-C=O=119.9(2) degrees, angleC-C-O=111.0(2) degrees, angleC-C-H=108.2(7) degrees, angleC-O-H=106.5(7) degrees. These structural parameters reproduce the experimental B(i)0 values within 0.05 MHz. The experimental structural parameters are in good agreement with those obtained from theoretical calculations. Ideal gas thermodynamic functions (S degrees (T), C degrees p(T), and H degrees (T)-H degrees (0)) of DHA were calculated on the basis of experimental and theoretical molecular parameters obtained in this work. The enthalpy of formation of DHA, -523+/-4 kJ/mol, was calculated by the atomization procedure using the G3X method.     

Detection and generation of submillimeter and terahertz modes in ferromagnet-antiferromagnet junctions

Spin-polarized current can tilt magnetic sublattices in an antiferromagnetic layer of a ferromagnet-antiferromagnet junction without imposing any external magnetic field. Thus, the current can induce magnetization in the antiferromagnetic layer. This effect seemingly took place in experiments on the observation of terahertz emission at the precession frequencies of current-induced magnetization. In this work, the mechanisms of motion of the induced magnetization, as well as the possibility of detection and generation of radiation emitted during such motion, are suggested and discussed. The notion of spin-injection antiferromagnetic resonance is introduced.     

Startup scenarios for an ultrashort pulse generator based on two coupled helical gyro-TWTS operating in the amplification and nonlinear absorption modes

Startup scenarios are studied for a high-power microwave ultrashort pulse (USP) generator with passive mode locking and consisting of two coupled helical gyro-TWTs operating in the amplification and nonlinear absorption modes. A startup scenario is proposed for a USP generator with a delay of switching on the absorbing section that allows the stability of generated pulses to be improved with a simultaneous increase in the efficiency of the device.