Alternation of the spin–orbit coupling in the 2Π ground state of HC n S (n = 1–12) radicals

First-order calculations of spin–orbit constants, dipole moments and carbon–sulphur distances have been performed for HC _n S (n = 1–12) radicals in the ²Π electronic ground state. It is found that these molecular properties alternate with even or odd numbers of carbon atoms in the chains and the spin–orbit constant A _SO is around ?300 cm^?1 for n even and about +120 cm^?1 for n odd throughout the series. This agrees with the experimentally determined value of about ?270 cm^?1 for HC₂S, but the theoretically predicted A _SO values are much larger than the values given for HC₃S and HC₄S from a fit of their millimeter-wave spectra. Values that were too low were also assumed in the analysis of the rotational spectra of n = 4–8.     

Hyperfine splitting constants in the optical transition \boldsymbol{{4{f}^{7}} {6{s}^{2}} \;{^{8}{\rm S}_{7/2}} \to {4{f}^{7}} {6{s}6{p}}\; {^{6}{\rm P}_{5/2}} \ {\rm of} \ {^{151-155}{\rm Eu}}} isotopes and hyperfine anomaly

Using the method of laser-induced fluorescence in an atomic beam we have measured the hyperfine splitting constants, A and B, of the ground and excited states of the optical transition 4f ⁷6s ^{2 8}S $_{1/2}\to 4f^{7}$ 6s6p ⁶P_5/2 (564.58 nm) for ^151???155Eu isotopes. For all isotopes, the magnetic dipole constants of the ⁶P_5/2 atomic level are determined to a precision better than 0.04%. The A and B constants for the ground state ⁸S_7/2 of the radioactive ^152,154,155Eu were obtained for the first time with a precision better than 0.5%. Our data along with previous ground state hyperfine structure measurements for the stable europium isotopes allow us to determine the hyperfine anomaly for mentioned Eu isotopes.     

Accurate equilibrium structures for small polyatomic molecules,radicals and carbenes

The paper reports on recent efforts to establish accurate equilibrium structures for small polyatomic molecules, radicals and carbenes most of which are of relevance to interstellar cloud chemistry, combustion processes or atmospheric chemistry. Among these are the well–known interstellar cyanopolyynes HC₃N and HC₅N, members of the series NC_{2 n} N, HC_{2 n ?+?1}P and NC_{2 n} P, linear silicon carbides of type SiC_{2 n} and pure carbon chains up to C₁₄, the radicals HC₃O, HOCO and CH₂CHO as well as cumulene carbenes of type H₂C _n . Whenever possible, a mixed experimental/theoretical procedure is employed which makes use of accurate experimental values for the ground–state rotational constants of a sufficiently large number of different isotopomers plus the results of coupled cluster calculations (variant CCSD(T)). In less favourable cases, the transfer of well–established correction parameters as developed from related smaller molecules appears to be the method of choice.     

Microwave spectra of the Cl and Cl isotopomers of dichloromethylene: Nuclear quadrupole-, spin-rotation-, and nuclear shielding constants from the hyperfine structures of rotational lines

The rotational spectra of the isotopomers C³⁵Cl³⁷Cl and C³⁷Cl₂ of dichloromethylene in the ground vibronic state were recorded in the range 10-33 GHz using a molecular beam Fourier transform microwave spectrometer. CCl₂ was generated by flash pyrolysis using different precursors. The observed spectra were analyzed to yield rotational and centrifugal distortion constants, as well as the complete Cl nuclear quadrupole coupling tensors and the spin-rotation interaction constants from the hyperfine structure of the rotational lines. With inclusion of data from previous work on the most abundant species C³⁵Cl₂ [N. Hansen, H. Mäder, F. Temps, Phys. Chem. Chem. Phys. (3) (2001) 50-55.] a refined r₀ structure was determined. The spin-rotation interaction constants of all three isotopomers were used to derive ³⁵Cl and ³⁷Cl principal inertial axis nuclear magnetic shielding components which have not yet been determined by NMR spectroscopy.     

Simulation of the Electron Paramagnetic Resonance Spectrum of the Triplet Ground State Dimer Di-μ-(Pyridine N-Oxide)Bis[Bisnitrato(Pyridine N-Oxide)Copper(II)]

The EPR spectrum of the triplet ground state dimer di-μ-(pyridine N-oxide)bis[bisnitrato(pyridine N-oxide)copper(II)] has been reported recently¹. Of the very few triplet ground state copper(II) dimers with resolved metal hyperfine structure^2,3, the EPR spectrum of this complex is most complete. Previously, the analysis of the spectra of triplet ground state copper(II) complexes, in order to extract magnetic parameters, has been made using the equations reported by Wasserman et al.⁴ The best magnetic parameters should be obtained from a simulation of the experimental spectrum. We wish to report here the computer simulation of the EPR spectrum of a powdered sample of [Cu(II) (PYO)₂ (NO₃)₂]₂.     

Analysis of ν2 of H2Se

The infrared absorption spectrum of ν₂ of H₂Se in the region from 885 to 1347 cm^?1 was obtained with a resolution limit of 0.025 cm^?1 on the University of Denver 50-cm FTIR spectrometer system. We have assigned 1604 lines for the six isotopomers of H₂Se, including 25 lines for the H₂⁷⁴Se isotopomer, and have analyzed them using Watson's A-reduced Hamiltonian in the I^r rotational representation. Ground state constants for each of the five most abundant isotopomers were obtained from fits of microwave transitions combined with weighted averaged ground state combination differences formed from the infrared bands (010), (020), (100), and (001). Upper state constants for each of the five most abundant isotopomers were obtained from least-squares fits of the spectral lines of ν₂, keeping the ground state constants fixed to the values determined from our ground state fits. An alternate set of ground state constants together with isotopic mass adjustment constants for all six isotopomers was determined by simultaneously fitting all available microwave transitions and infrared ground state combination differences. Keeping this set of ground state constants fixed, a single set of upper state constants and isotopic mass adjustment constants for the ν₂ band was determined by a simultaneous fit of infrared spectral lines from all six isotopomers.     

Rotational Spectrum, Hyperfine Structure, and Internal Rotation of Methyl Carbamate

Methyl carbamate, an isomer of glycine, is a possible candidate for interstellar detection. It might be more abundant than glycine and its dipole moment is much larger. Furthermore, using high-level quantum chemical calculations, it is shown that syn methyl carbamate has a lower energy than glycine. The quadrupole hyperfine structure due to ¹⁴N has been measured using microwave Fourier transform spectroscopy. The rotational spectrum of the ground vibrational state has been measured from 8 to 240 GHz and accurate spectroscopic constants have been determined for the A internal rotation components of the rotational lines. Finally, the internal rotation splittings have been analyzed.     

The microwave spectrum of cyanohexatriyne,HCCCCCCCN

The detection of cyanobutadiyne, HC₅N, in various interstellar molecular clouds has prompted the laboratory synthesis and microwave study of the next member of the cyanopolyyne series in order to facilitate its detection by radio astronomy. In this study details of the synthesis and rotational analysis of cyanohexatriyne HC₇N are presented. The rotational constants B₀ = 564.00074 ± 0.00016 MHz and D₀ = 3.821 ± 0.087 Hz were the values used to identify HC₇N in the interstellar medium.     

Nuclear reactions as an example of the quantum theory of irreversible processes

A modification of the atomic beam magnetic resonance method for investigation of the hyperfine structure of excited atomic states will be described. Radiofrequency transitions between the hyperfine structure niveaus of the excited state, which are unequally populated by circularly polarized light, are detected by observing the resulting change in population number of the hyperfine structure niveaus of the ground state using magnetic deflection in an inhomogeneous field and additional radiofrequency transitions in the ground state as analyzers. As an application the hyperfine structure of the excited 4² P _3/2-state of K³⁹ has been investigated in an almost strong magnetic field of about 65 G with a constant frequency of the applied radiofrequency field of 125.50 Mc/s. The analysis of the radiofrequency signal of the excited state detected as a change in the amplitude of a radiofrequency transition in the ground state yielded the valuesA=(6.10±0.25) Mc/s andB=(1.8±1.2) Mc/s for the hyperfine structure constants of the 4² P _3/2-state of K³⁹. Further possibilities for observing signals of the excited state with the apparatus used in this experiment are also discussed.     

Molecular beam electric resonance study of KCN,K13CN and KC15N

The microwave spectra of the isotopic species K¹³CN and KC¹⁵N have been investigated by molecular beam electric resonance spectroscopy, using the seeded beam technique. For both isotopic species about 20 rotational transitions originating in the ground vibrational state were observed in the frequency range 9–38 GHz. The observed transitions were fitted to an asymmetric rotor model to determine the three rotational, as well as the five quartic and three sextic centrifugal distortion constants. The hyperfine spectrum of KCN has been unravelled with the help of microwave-microwave double-resonance techniques. One hundred and forty hyperfine transitions in 11 rotational transitions have been assigned. The hyperfine structures of K¹³CN and KC¹⁵N were also studied. For all three isotopic species the quadrupole coupling constants and some spin-rotation coupling constants could be deduced. The rotational constants of the ¹³C and ¹⁵N isotopically substituted species of potassium cyanide, combined with those of the normal isotopic species (determined more accurately in this work), allowed an accurate and unambiguous evaluation of the structure, which was confirmed to be T shaped. Both the effective structure of the ground vibrational state and the substitution structure were evaluated. The results for the effective structural parameters are $\text{r}{}_{\mathrm{<mtext>CN</mtext>}}\text{= 1.169(3)}\text{A}\text{?}$, $\text{r}{}_{\mathrm{<mtext>KC</mtext>}}\text{= 2.716(9)}\text{A}\text{?}$, and $\text{r}{}_{\mathrm{<mtext>KN</mtext>}}\text{= 2.549(9)}\text{A}\text{?}$. The values obtained for the principal hyperfine coupling constant eQq_z(N), the angle between the CN axis and z_N, and the bond length r_CN indicate that in gaseous potassium cyanide the CN group can be considered as an almost unperturbed CN^? ion.     

Doppler-limited dye laser excitation spectroscopy of HCCl

The cw dye laser excitation spectrum of the $\text{A}\text{?}{}^1\text{A″(050) ←}\text{X}\text{?}{}^1\text{A′(000)}$ vibronic band of HCCl was observed between 16 539 and 16 656 cm^?1 with the Doppler-limited resolution, 0.03 cm^?1. The HCCl molecule was generated by the reaction of discharged CF₄ with CH₃Cl. The observed spectra were assigned to c-type transitions with ΔK_a = ±1 and also to axis-switching transitions with ΔK_a = 0 or ?2, but all with K′_a = 0, both for HC³⁵Cl and HC³⁷Cl. A rotational analysis yielded the rotational constants and quartic centrifugal distortion constants for the ground vibronic state and the band origin. A weak vibronic band, about one-third as intense as the main band, was found at about 57 cm^?1 to the violet of the main band for both isotopic species, and was ascribed to a transition from the ground vibronic state to a vibrational level, possibly (041), of the à state. The rotational levels of HC³⁵Cl in the à state showed a large perturbation; the J′ = 8, 9, and 10 levels were found to be split into two components. A normal coordinate analysis was carried out to calculate the centrifugal distortion constants and the inertia defect, which were in fair agreement with the observed values. The molecular structure of HCCl in the ground vibronic state was recalculated from the rotational constants of the two isotopic species combined with the 0.75B₀ + 0.25C₀ value previously reported for DC³⁵Cl.     

Nuclear spin induced collapse and revival shape of Rabi oscillations of a single electron spin in diamond

A collapse and revival shape of Rabi oscillations in an electron spin of a single nitrogen-vacancy centre has been observed in diamond at room temperature. Because of hyperfine interaction between the host ¹⁴N nuclear spin and the nitrogen-vacancy centre electron spin, different orientations of the ¹⁴N nuclear spins lead to a triplet splitting of the transition between ground state (m_s =0) and excited state (m_s =1). The manipulation of the single electron spin of nitrogen-vacancy centre is achieved by using a combination of selective microwave excitation and optical pumping at 532 nm. Microwaves can excite three transitions equally to induce three independent nutations and the shape of Rabi oscillations is a combination of the three nutations.     

Hyperfeinanomalie im151Eu und153Eu

Using the Mössbauer effect, the ratios of theg factors and the hyperfine splitting constants for the 21.6 keV state and the ground state in¹⁵¹Eu and of the 103 keV state and the ground state in¹⁵³Eu have been measured. From these results values for the hyperfine anomaly of⁰Δ ₁₅₁ ²² =?0.81(8)% and⁰Δ ₁₅₃ ¹⁰³ =+ 1.8(8)% have been derived for¹⁵¹Eu and¹⁵³Eu, respectively.     

Fine and hyperfine structure in three low-lying 3Σ+ states of molecular hydrogen

The fine structure constant (electron spin-spin coupling) and the hyperfine structure parameters (electron-nuclear spin coupling, including spin-rotation and electron-nuclear quadrupole coupling) in the low-lying triplet states b³Σ⁺ _u, a³Σ⁺ _g and e³Σ⁺ _u of molecular hydrogen and deuterium are calculated using a recently developed technique with full configuration interaction and multiconfiguration self-consistent field wave functions. The second-order spin-orbit coupling contribution to the ³Σ⁺ states splitting is negligible, and the calculations therefore provide a good estimate of the zero-field splitting based only on the electron spin-spin coupling values. For the bound a³Σ⁺ _g state a negligible zero-field splitting is found, in qualitative agreement with the e-a spectrum. The zero-field splitting parameter is considerable for the repulsive b³Σ⁺ _u state (?1 cm^?1) and of intermediate size for the bound e³Σ⁺ _u state. The isotropic hyperfine coupling constant is very large not only for the valence b³Σ⁺ _u state (1580 MHz) but also for the Rydberg a and e triplet states (?1400 MHz). The quadrupole coupling constants for the deuterium isotopes are negligible (0.04–0.07 MHz) for all studied triplet states. The electric dipole activity of the spin sublevels in the triplet-singlet transitions to the ground state is estimated by means of the quadratic response technique.     

Hyperfine interactions in the alkaline-earth Sr ions by collinear fast beam laser spectroscopy

The magnetic dipole hyperfine structure constants of the⁸⁷SrII 5s²S_1/2 ground state and the 5p²P_1/2 excited state, and the isotope shifts of the ionic 5s²S_1/2 → 5p²P_1/2 resonance transition for all stable Sr isotopes, measured by collinear fast beam laser spectroscopy, are reported.     

The Lamb-dip spectrum of methylcyanide: Precise rotational transition frequencies and improved ground-state rotational parameters

Methylcyanide, CH₃CN, is an important interstellar species, and therefore the accurate knowledge of precise rest frequencies for rotational transitions as well as ground-state rotational and hyperfine constants is needed. In this work the hyperfine structure of the millimeter- and submillimeter-wave spectra of CH₃CN has been further investigated. In addition, accurate THz measurements have been carried out for the first time. Consequently, the present investigation allowed us to provide the most accurate ground state rotational and hyperfine parameters known at the moment for CH₃C¹⁴N. To resolve the hyperfine structure of the rotational transitions observed, the Lamb-dip technique has been exploited. Both frequency-modulated and video-type detections have been employed.     

Microwave spectrum,quadrupole coupling constant,and conformation of 1-cyanocyclohexene

The microwave spectrum of 1-cyanocyclohexene has been investigated in the frequency regions 8–12.4 and 18–26.5 GHz. A-Type transitions in the ground state and three excited states have been assigned. The rotational constants in the ground state were determined to be A = 4565.98 ± 0.46, B = 1423.44 ± 0.01, and C = 1136.17 ± 0.01 MHz. From the experimental data, it was suggested that the molecule has an equilibrium half-chair conformation similar to those of cyclohexene and 1-fluorocyclohexene. From the hyperfine splittings of the ¹⁴N nucleus, the quadrupole coupling constant, X_aa, was found to be 4.2 MHz.     

An investigation of the structure of free-base porphycene by time-resolved electron nuclear double resonance and density functional theory on the photoexcited triplet state

The photoexcited triplet state of free-base porphycene has been investigated by time-resolved electron nuclear double resonance spectroscopy at 10 K. In order to determine whether porphycene is cis or trans configured, experimentally determined A_zz hyperfine coupling tensor components are compared with those predicted from density functional theory. The structures of cis and trans porphycene, in both the singlet ground state and lowest excited triplet state were calculated using the Becke3-Lee-Yang-Parr composite exchange correlation functional and the 6–31G* basis set. Hyperfine couplings for these structures were then calculated using the same functional but with the extended EPR-II basis set. From the results it can be concluded that porphycene has a trans configuration in both the ground singlet and lowest excited triplet state. Additionally, the significant differences in structure between the singlet and triplet states are reflected in the calculated hyperfine couplings, with those for the trans conformation in the triplet state in reasonable agreement with the experimental values.     

Microwave rotational spectra of the Kr-NH3 van der Waals complex

Rotational spectra of the Kr-NH₃ van der Waals complex were measured in the frequency range between 4 and 24 GHz using a pulsed jet cavity Fourier transform microwave spectrometer. The isotopomers studied included those of NH₃, ¹⁵NH₃, ND₃, NHD₂, and NH₂D with the five most abundant isotopes of Kr. Tunnelling splittings due to the inversion of the ammonia subunit within the ground state of the complex were observed for all three deuterium containing isotopomers. In the NH₃ and ¹⁵NH₃ isotopomers, one of the tunnelling states has a spin statistical weight of zero and the splitting can therefore not be measured in these species. Nuclear quadrupole hyperfine structure arising from the ¹⁴N and ⁸³Kr nuclei was measured and the corresponding nuclear quadrupole coupling constants were determined. These were used to estimate structural parameters and derive information about the intermolecular dynamics. Smaller nuclear quadrupole splittings arising from the deuterium nuclei were observed but could not be resolved. The ground state spectroscopic constants were compared with experimental and theoretical data previously reported for Ar-NH₃ and its isotopomers. For the Kr-ND₃ isotopomers, additional transitions were observed and assigned to the two inversion components of an excited internal rotor state. A fit of the spectroscopic constants revealed the presence of a Coriolis perturbation, similar to that reported for this state in Ar-ND₃ and Ar-NH₃.     

The phosphorescent triplet state of p-xylene in an isotopically mixed crystal at 1·2K: an investigation by E.S.R. and MIDP

The phosphorescence spectrum of p-xylene-h ₁₀ in a p-xylene-d ₁₀ host is first presented. Secondly we report E.S.R. experiments performed on p-xylene-α,α′-d ₆ in p-xylene-d ₁₀; from an analysis of the orientations of the principal axes in combination with the crystal structure and of the hyperfine splittings it is concluded that the in-plane principal axes of the zfs tensor make an angle of 68° with the molecular axes. Thirdly we discuss Microwave-Induced Delayed Phosphorescence (MIDP) experiments on p-xylene-h ₁₀ in p-xylene-d ₁₀ in which the relative radiative rate constants for decay from the zero-field spin components of the triplet state to single vibronic bands of the ground state have been obtained.

The results of the MIDP and E.S.R. measurements are shown to be mutually consistent in terms of a model in which the effect of the crystal field and the methyl substituents on the pseudo-Jahn-Teller unstable electronic structure of the triplet state of benzene is described.