Assignment and analysis of the rotational spectrum of bromoform enabled by broadband FTMW spectroscopy

The rotational spectrum of the bromoform molecule is complicated by overlap of extensive hyperfine splitting structure of three bromine nuclei belonging to four isotopic species of comparable abundance. We have been able to achieve an unambiguous assignment of this spectrum on the basis of complete hyperfine patterns of the lowest-J rotational transitions recorded at conditions of supersonic expansion with chirped-pulse, broadband Fourier transform microwave spectroscopy. The mm-wave rotational spectrum was then also studied up to J = 131 and 318 GHz, and extensive measurements are reported for four isotopic species of HCBr₃ and four DCBr₃ species. Precise values of many spectroscopic constants have been determined from global fits of all measurements for a given isotopic species and have been substantiated by comparisons among the various isotopic species and with results of ab initio calculations. The experimental measurements allowed determination of the axial rotational constant C for the symmetric top species, evaluation of nuclear quadrupole hyperfine splitting constants in the principal quadrupole axes of the bromine nucleus, and extension of the range of known values of the h₃ splitting constant. The r_z geometry of HCBr₃ was also determined.     

Rotational spectra, conformational structures, and dipole moments of thiodiglycol by jet-cooled FTMW and ab initio calculations

The rotational spectra of three low-energy conformers of thiodiglycol (TDG) (HOCH₂CH₂SCH₂CH₂OH) have been measured in a molecular beam using a pulsed-nozzle Fourier-transform microwave spectrometer. To determine the likely conformational structures with ab initio approach, conformational structures of 2-(ethylthio)ethanol (HOEES) (CH₃CH₂SCH₂CH₂OH) were used as starting points together with the consideration of possible intramolecular hydrogen bonding in TDG. Three lower-energy conformers have been found for TDG at the MP2=Full/6311G** level and ab initio results agree nicely with experimentally determined rotational constants. In addition, Stark measurements were performed for two of the three conformers for dipole moment determinations, adding to our confidence of the conformational structure matches between experimental observations and ab initio calculations. Of the three lower-energy conformers, one displays a compact folded-like structure with strong hydrogen bonding between the two hydroxyl groups and the central sulfide atom. Two other conformers have relatively open chain-like structures with hydrogen bonding between each of the hydroxyl groups to the central sulfur atom, of which one has pure b-type dipole moment according to the ab initio results.     

High-resolution FTIR measurement of the line parameters in the fundamental band of HI

The linestrengths and self-broadening coefficients are determined from high-resolution measurements for P(1)-P(10) and R(0)-R(15) lines in the fundamental vibration-rotation band of hydrogen iodide at different gas pressures in the range of 2-280 Torr. Dipole matrix elements are calculated from the linestrength data. New values of the Herman-Wallis coefficients obtained, C₁₀=0.1319, D₁₀=4.41×10^-3, are in a better agreement with theory than previously reported. A significant influence of the hyperfine splitting on the spectral line profiles is demonstrated.     

The high resolution infrared spectrum and laser Stark spectroscopy of thev8 band of propyne

The perpendicularv ₈ band lying in the 1000–1100 cm^–1 region has been studied from infrared and laser Stark, spectra. We were interested in the part of spectrum corresponding to the spectral range of the 9 m CO₂ laser lines. Assignments of rovibrational lines with J'<40 and K'<6 have been made. About 100 Stark resonances have been assigned to 12 rovibrational transitions. Effective molecular constants and dipole moment have been determined with high accuracy. A list of close resonances with CO₂ laser lines is given and may be used for optical pumping experiments.     

Microwave spectroscopy, Dunham analysis, and hyperfine splittings of the isotopomers of zinc monosulfide, ZnS

Two rotational transitions of the first six vibrational states of three isotopomers of zinc monosulfide, ⁶⁴Zn³²S, ⁶⁶Zn³²S, and ⁶⁸Zn³²S, have been observed in cavity Fourier transform microwave (FTMW) spectroscopy. In addition, the hyperfine splitting of the ⁶⁷Zn³²S due to the nuclear quadrupole coupling constant of the I = 5/2 ⁶⁷Zn nucleus was observed for two rotational transitions of v = 0. The zinc sulfide was produced by laser ablation of a zinc rod with the resulting zinc plasma reacting with 0.6% OCS in argon in a pulsed jet originating upstream of the ablation plasma. A Dunham expansion of the rotational constant is performed resulting in the determination of B_e, α_e, γ_e, δ_e, and ε_e (Y₀₁, −Y₁₁, Y₂₁, Y₃₁, and Y₄₁) for ZnS. There is no evidence of Born–Oppenheimer breakdown in the mass-scaling of these parameters to within our experimental accuracy. χ_aa(⁶⁷Zn) of ⁶⁷Zn³²S is also determined.     

The permanent electric dipole moment of holmium monoxide, HoO

The high resolution molecular beam laser-induced fluorescence (LIF) spectrum of the (0, 0) band of the [17.6]7.5-X₁8.5 system of holmium monoxide, HoO, has been recorded field free and in the presence of a variable static electric field. The rotational constant, B₀, and magnetic hyperfine structure constant, h, for the v = 0 levels of the [17.6]7.5 and X₁8.5 states were obtained by assigning and fitting the field-free spectral features. The Stark shifts and splittings in the LIF spectra were analyzed to produce values for the magnitude of the permanent electric dipole moments, |μ|, of 3.96(6) and 4.80(5) D for [17.6]7.5, v = 0 and X₁8.5, v = 0, respectively.     

Laser spectroscopy of jet－cooled CuF in visible region

The laser-induced fluorescence excitation spectra of jet-cooled CuF have been recorded in the range of 19000－21470cm^{-1}, in which the CuF radicals were produced by the reaction of SF_6 with copper atoms from a dc discharge-sputtering source under supersonic jet conditions. Eight observed vibronic transition bands have been assigned as the transition from the ground state X(^1Σ^+) to B(^1Σ^+), C(^1Π) and an unreported upper state. The rotational structure of all observed bands has been analysed at the estimated rotational temperature 80K. We determined the newly observed band to be the (^1Π, v=1)－X(^1Σ^+v=0) transition according to the character of the rotational structure and the isotopic shift analysis. In addition, the lifetimes of the states involved in these bands were measured.     

Variation of Dipole Moment Function of O-H Bond of t-Butanol with the Nature of Solvent and Its Temperature

The intermolecular influence on dipole moment function is evaluated for O-H bond of t-butanol in different nonpolar solvents at temperatures ranging from 10° to 60°C employing IR band intensities of fundamental and first overtone bands. Two sets of dipole moment derivatives have been calculated corresponding to – and +- combinations of the transition moment matrix elements R₁₀ and R₂₀, the values for ++ and -+ combinations are equal in magnitude to those for - and +- combinations, respectively and opposite in signs. In general the dipole moment derivatives increase on lowering the temperature as well as with increasing molecular interactions with the solvent molecules. Dipole moment plots with dimensionless coordinate ξ [=(r-r_e)/r_e, where r and r_e are internuclear distances during vibration and at equilibrium, respectively] are reported for various systems considered. It is found that for +- combination the dipole moment maximum shifts to higher internuclear distances when polarisation of the solute molecules is increased by lowering of temperature or increase in molecular interactions between solute and solvent molecules. A reverse trend is observed for – combination.- The OH band of t-butanol vapor has been measured.     

类氢离子基态超精细结构的理论研究

利用相对论多组态Dirac-Fock方法,系统计算了类氢离子165Ho66+, 185Re74+,187Re74+,207Pb81+, 209Bi82+, 203TI80+和205TI80+的基态超精细结构分裂以及相应的基态跃迁波长,并与相关实验数据及其它理论结果进行了对比.     

LCAO-MO Calculation of Dipole Transition Moment of Some First-Row Transition Metal Tetroxy Anions

Abstract

Recently very encouraging results of semiempirical parameteric calculation of dipole transition moments of the lowest energy t₁ ? 2e (¹A₁ - ¹T₂) transition of permanganate and chromate ions have been reported. In the case of vanadate ion, which is isoelectronic with the permanganate and chromate ion, no such study of spectral intensities appears to have been reported so far. A parameteric calculation in terms of a single parameter β, the ligand mixing coefficient using Richardson's orbitals⁴ and both dipole velocity and dipole length operators have been reported in the present paper.     

The C hyperfine constants of HCS and HSC studied by microwave spectroscopy

The ¹³C hyperfine constants of the H¹³CS and HS¹³C radicals are determined by microwave spectroscopy. For H¹³CS, the 1₀₁-0₀₀ rotational transition is measured at 38.5 GHz with a Fourier transform microwave spectrometer, and two ¹³C hyperfine constants are determined. They are well interpreted in terms of a relatively large HCS bonding angle (132.8°). For HS¹³C, the N=7-6, 9-8, and 10-9 rotational transitions are measured in the 268-384 GHz region by using a source modulation spectrometer combined with a free-space discharge cell, and five ¹³C hyperfine constants including the nuclear spin-rotation constant, C_aa, are determined. From the ¹³C hyperfine constants, the p character of the unpaired electron orbital on the carbon atom is estimated to be 66.5%, supporting a classical resonance picture; .     

High resolution laser induced fluorescence excitation spectroscopy of jet-cooled terrylene

High resolution laser induced fluorescence excitation spectra upon absorption in the A¹B_3u ← X¹A_g band of jet-cooled terrylene have been recorded. Precise energies of three vibronic transitions are deduced. Low lying vibrations are found in both electronic states. Rotational constants in ground and excited state are determined by band contour analysis. Terrylene is a medium-size polycyclic aromatic hydrocarbon (PAH) and a possible carrier of diffuse interstellar bands (DIB). The results of the jet experiments are discussed regarding the PAH-DIB hypothesis.     

High-K isomers as probes of octupole collectivity in heavy nuclei

The influence of the octupole deformation on the structure of high-K isomeric states in the region of heavy even–even actinide nuclei is studied through a reflection asymmetric deformed shell model (DSM). Two-quasiparticle states with high-K values are constructed by taking into account the pairing effect through a DSM + BCS procedure with constant pairing interaction. The behaviour of two-quasiparticle energies and magnetic dipole moments of Kπ=⁶⁺$K^{\pi }=6^{+}$, ⁶⁻$6^{-}$ and ⁸⁻$8^{-}$ configurations, applicable to mass numbers in the range A=234–252$A=234\text{–}252$, was examined over a wide range of quadrupole and octupole deformations. A pronounced sensitivity of the magnetic moments to the octupole deformation is found. The result suggests a possibly important role for high-K isomers in determining the degree of octupole deformation in heavy actinide nuclei.     

Measurements on polar liquids at a microwave frequency — evaluation of molecular parameters — a new method

A simple method of estimating the dipole moment (μ) and relaxation time (τ) of polar molecules in liquid state, from a single set of dielectric measurements at high frequency, is proposed by using the concept of dielectric virial coefficients and employing Onsager model. The proposed method is tested in a number of polar liquids and the results are discussed.     

Ultrasonic and DFT study of intermolecular association through hydrogen bonding in aqueous solutions of glycerol

The experimental measurements of density, viscosity and ultrasonic velocity of aqueous glycerol solutions were carried out as functions of concentration (0.1 ≤ m [mol kg^− 1] ≤ 1.0) and temperature (303.15 ≤ T [K] ≤323.15). The isentropic compressibility (β_s), acoustic impedance (Z), hydration number (H_n), intermolecular free length (L_f), classical sound absorption (α/f²)_class and shear relaxation time (τ) were calculated by using the measured data. These parameters have been interpreted in terms of solute–solvent interactions. The quantum chemical calculations were performed to study the hydrogen bonding in interacting complex formed between glycerol and water molecules. Computations have been done by using Density Functional Theory (DFT) method at B3LYP/6–31 + g(d) level of theory to study the equilibrium structure of glycerol, glycerol–water interacting complex and vibrational frequencies. The solution phase study was carried out using Onsager's reaction field model in water solvent. The computed vibrational frequencies are in good agreement with the main features of the experimental spectrum when four water molecules are considered explicitly with glycerol. The interaction energy (E_total), hydrogen bond lengths and dipole moment (µ_m) of the interacting complex are also presented and discussed with in the light of solute–solvent interactions.     

The rotational spectrum of HC8N, a linear molecule with a triplet ground state

By means of Fourier transform microwave spectroscopy of a supersonic molecular beam, we report here the laboratory detection of HC₈N, a carbon chain with a triplet electronic ground state. A total of 71 hyperfine components from six rotational transitions between 8 and 13 GHz were measured to an uncertainty of 5 kHz or better. Eight spectroscopic constants, including six fine and hyperfine coupling constants, were determined to high accuracy, despite a complex spectrum which consists of many closely spaced lines. Like the shorter HC_2nN chains, the linear triplet isomer detected here is highly polar and is almost certainly the ground state of HC₈N; in our molecular beam discharge source, it is 10 times less abundant than triplet HC₆N, but more than 100 times less abundant than the well-studied closed-shell cyanopolyyne HC₇N. Owing to the collapse of the hyperfine structure with increasing chain length, still longer chains may be detectable.     

Hyperfine structure and isotope shift studies of rhenium by laser optogalvanic spectroscopy

Doppler-limited high resolution laser optogalvanic spectra of six transitions of rhenium lying in the range 560–620 nm have been recorded. Isotope shifts between the two natural isotopes of rhenium,¹⁸⁵Re and¹⁸⁷Re, have been calculated in all the six transitions. Hyperfine coupling constants for eight levels belonging to the configurations 5d ⁵6s ², 5d ⁶6s, 5d ⁴6s ²6p and 5d ⁵6s6p are reported. Wherever possible our constants are compared with those given by others.     

The rotational spectrum of epifluorohydrin measured by chirped-pulse Fourier transform microwave spectroscopy

The rotational spectrum of epifluorohydrin measured by chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy is presented. A new CP-FTMW spectrometer capable of measuring the entire 7.5-18.5 GHz spectrum with a single polarizing pulse is described briefly. The CP-FTMW spectrometer takes advantage of recent advances in digital electronics by utilizing a 4.2 GS/s arbitrary waveform generator as a frequency source and a 12 GHz digital oscilloscope to digitize the down converted molecular free induction decay (FID). Signal averaging in the time domain is used to increase the signal-to-noise ratio. The rotational constants of three unique conformers of epifluorohydrin were measured, as well as the rotational constants of the three unique ¹³C isotopomers and the ¹⁸O isotopomer (in natural abundance) of the most stable conformer. The rotational constants of the two less stable conformers differ significantly from those previously reported [F.G. Fujiwara, J.L. Painter, H. Kim, J. Mol. Struct. 41 (1977) 169-175]. Ab initio calculations were performed for all three conformations and are compared to experimental values.