Hydrogen bond studies

The deuteron magnetic resonance spectra from partially deuterated single crystals of NaHC₂O₄. H₂O have been studied. The quadrupole coupling tensors for stationary deuterons are determined at about 25°C. The quadrupole coupling constants and the assymmetry parameters η of the tensors for the two deuterons in the water molecule are, 235·2 ± 1·9 and 228·5 ± 1·6 kHz, and 0·09 ± 0·01 and 0·13 ± 0·01, respectively. The principal axes corresponding to the largest components both deviate by 0·9 ± 0·5° from their respective O-H directions. For one of the tensors this angular displacement is in the plane of the H₂O molecule and towards the other O-H direction. The displacement for the other tensor is out of the plane of the H₂O molecule.     

Electric dipole moments and nuclear hyperfine interactions for H2S,HDS, and D2S

Electric dipole moments and nuclear hyperfine coupling constants for several low-energy rotational states of the ground vibrational state of H₂S, HDS, and D₂S have been determined by molecular beam electric resonance spectroscopy. Analysis of the Stark effects for radiofrequency spectra of the lowest rotational levels gives dipole moments of 0.978325 (10) D for H₂S (J = 1, τ = 0), 0.977294 (20) D for D₂S (J = 1, τ = 0), and 0.977484 (60) D for HDS (J = 1, τ = 1 and J = 2, τ = 0). The electric field gradient tensor at the deuterium nucleus, the nuclear spin-spin tensor, and the spin-rotation tensor were evaluated from the hyperfine components of the radiofrequency spectra. The accuracy of these tensors was moderately improved over earlier measurements. From the H₂S spin-rotation tensor, the average paramagnetic shielding for the protons was found to be σ_av^p = ?104.84 (40) ppm. Combining this result with the proton NMR absolute chemical shift allowed the average diamagnetic shielding to be calculated as σ_av^d = 135.7 (5) ppm.     

GeTe和GeSe 分子在外电场下的特性研究

对Ge原子采用6-311++G^**基函数,Te和Se原子采用SDB-cc-pVTZ基函数,利用密度泛函理论的局域自旋密度近似方法优化得到了GeTe和GeSe分子的稳定构型,并计算了外电场作用下GeTe和GeSe基态分子的平衡核间距、总能量、最高已占据分子轨道能量E_H、最低未占分子轨道能量E_L、能隙、谐振频率和红外谱强度. 在上述计算的基础上利用单激发组态相互作用-局域自旋密度近似方法研究了GeTe和GeSe分子在外电场下的激发特性. 结果表明:随着正向电场强度的增大,分子核间距逐渐增大,分子总能量逐渐降低,谐振频率逐渐减小,红外谱强度则逐渐增大. 在0-2.0569×10¹⁰ V·m^-1的电场范围内,GeTe分子的E_H 均高于GeSe分子的E_H;随着正向电场的增大,GeTe与GeSe的E_H差逐渐变大,GeTe的E_L低于GeSe的E_L,它们的E_L均随正向电场的增大而增大. 无外场时,GeTe分子的能隙比GeSe分子的能隙要小;在外电场反向增大的过程中, GeTe和GeSe的分子能隙始终减小. 外电场的大小和方向对GeTe和GeSe分子的激发能、振子强度及跃迁的波长均有较大影响. 关键词： GeTe GeSe 外电场 激发态     

The microwave spectrum of cyanoformamide

The spectrum of cyanoformamide, NCCONH₂, has been measured between 18 and 40 GHz using a Hewlett-Packard spectrometer with Stark modulation. The molecule is somewhat unstable and could most conveniently be measured in a flow system. The quadrupole hyperfine structure due to the two nitrogen nuclei has been analyzed for the ground state, and quadrupole coupling constants, rotational constants, and centrifugal distortion constants have been determined for the ground state. A rough determination of the components of the electric dipole moment was possible from the Stark shifts of suitable transitions.     

FTMW spectroscopy of jet-cooled 9-cyanoanthracene

Rotational spectrum of jet-cooled 9-cyanoanthracene has been observed in the 4-8 GHz region with a Fourier-transform microwave spectrometer. The present observation of 25 low-J transitions with J^′′?11 has confirmed the previous results on the rotational constants of the ground state determined by rotational coherence spectroscopy [J. Phys. Chem. A. 105 (2001) 1131] and provided the values with significantly improved precision. An accurate set of hyperfine splitting constants is also reported for the ¹⁴N nuclear quadrupole coupling. The electric dipole moment was determined from Stark effect measurements on several split components: μ_b(=μ)=4.406(7) D.     

The origin of non-planarity in ketyls

A series of one-electron properties, i.e. dipole, quadrupole, octupole moments, diamagnetic susceptibility, second moments and second moment anisotropies of charge distribution, electric field, electric field gradient, diamagnetic shielding, nuclear quadrupole coupling constant, have been obtained by ab initio S.C.F. calculations for the molecules COF₂, SO₂F₂ and SOF₂. The effect of the size of the gaussian basis sets, including d-type polarization functions, as well as the contraction schemes on the latter properties have been studied for the COF₂ molecule. This study enables us to determine the basis giving the best results as compared to experiment. With this basis the calculations have been extended to the properties of the molecules SO₂F₂ and SOF₂. Good overall agreement with experiment is obtained.     

Measurement of the electric dipole moment of NO (X2 Π ν = 0,1) by mid-infrared laser magnetic resonance spectroscopy

A pair of parallel Stark plates are added to a CO laser magnetic resonance spectrometer to apply electric field in the absorption cell. This apparatus is used to measure the molecular electric dipole moment via Zeeman and Stark effects simultaneously. The saturated absorption spectra of NO (X²Π_3/2, ν = 1 ← 0) was observed and the electric dipole moments of NO were directly measured in the presence of an electric field. The dipole moments are determined as μ₀(ν = 0) = 0.1595(15) D, μ₁ (ν = 1) = 0.1425(16) D. The electric dipole moment of the vibrationally excited state (ν = 1) is determined for the first time. The dependence of the electric dipole moments on its nuclear distances is interpreted.     

Determination of the helium-4 mass in a Penning trap

The determination of the rotational quadrupole alignment of diatomic molecules via REMPI detection is investigated. In this process a high focal intensity usually increases the detection probability. At high intensities the AC Stark effect may cause a splitting of the normally degenerate m_J sublevels of a rotational state J beyond the spectral width of the exciting radiation. This leads to a selective detection of only certain m_J states with the consequence that deduced alignment factors can be misleading. From the theoretical considerations line profiles are explicitly calculated for dynamic polarizabilities which represent the B ¹Σ⁺ _u←X ¹Σ⁺ _g transition of H₂, in order to fit an experimental (3+1) REMPI spectrum and to predict (1+1') line shapes as a function of laser intensity. It is further shown that the deduced quadrupole alignment factor A ₀ ⁽²⁾ is significantly changed by the second order AC Stark effect when the intensities are chosen high enough to observe asymmetric broadened line profiles. Different combinations of relative linear polarizations of the exciting and ionizing laser beams are discussed. Received 1st August 2000 and Received in final form 2 May 2001     

Die Abhängigkeit innerer und äußerer Wechselwirkungen des TlF-Moleküls von der Schwingung,Rotation und Isotopie

The hyperfinestructure, Stark effekt and Zeeman effect of the TlF molecule have been measured with a molecular beam resonance apparatus. The apparatus uses electric four poles as deflecting fields and a homogeneous electric field parallel to a super-imposed magnetic field in the transition region. Electric dipole transitions withΔm _J =±1,ΔJ=0 (J rotational quantum number) were measured in the following (v, J) states (v vibrational quantum number): (0,1), (1,1), (2,1) and (0,2) of the molecule²⁰⁵Tl¹⁹F and (0,1) of the molecule²⁰³Tl¹⁹F. For these five states the following interaction constants were determined: The magnetic (and the electric) dipolemoment of the molecule, the scalar and the tensor nuclear dipole-dipole interaction, the nuclear spin-rotational interactions, the anisotropy of the diamagnetic susceptibility ξ_⊥?ξ_∥, the anisotropy of the diamagnetic shielding of the external field by the electrons at the position of the nuclei σ_⊥?σ_∥. From these quantities it was possible to calculate the quadrupole-moment of the electronic charge distribution. Furthermore, the dependence of the ratio of the isotopic electric dipolemoments on vibrational state was measured. A new method for determining the nuclear magnetic moments is described. The method consists of a molecular beam resonance apparatus with combined magnetic and electric transition fields and was used to measure the magnetic moments of the nuclei²⁰⁵Tl and¹⁹F. — On page 293 will be found a table of results.     

Electric quadrupole moments and strong interaction effects in pionic atoms of 165Ho, 175Lu, 176Lu, 179Hf and 181Ta

The effective quadrupole moments Q_eff of the nuclei of ¹⁶⁵Ho, ¹⁷⁵Lu, ¹⁷⁶Lu, ¹⁷⁹Hf and ¹⁸¹Ta were accurately measured by detecting the pionic atom 5g-4f X-rays of the elements. The spectroscopic quadropole moments, Q_spec, were obtained by correcting Q_eff for nuclear finite size effect, distortion of the pion wave function by the pion-nucleus strong interaction, and contribution to the energy level splittings by the strong interaction. The intrinsic quadrupole moments, Q₀, were obtained by projecting Q_spec into the frame of reference fixed on the nucleus. The shift, ε₀, and broadening, Γ₀, of the 4f energy level due to the strong interaction between the pion and the nucleons for all the elements were also measured. Theoretical values of ε₀ and Γ₀ were calculated and compared to the experimental values. The measured values of Q₀ were compared with existing results in muonic and pionic atoms. The measured values of ε₀ and Γ₀ were also compared with existing values.     

Stable,metastable and unstable solutions of a spin-1 Ising system in the presence of magnetic fields due to the dipole and quadrupole moments

The spin-1 Ising model with bilinear (J) and biquadratic (K) interactions is studied for magnetic fields H_s and H_Q representing dipole and quadrupole moments, respectively, by using the lowest approximation of the cluster variation method. The influence of H_s, H_Q and α = J/K on metastable and unstable solutions, which are very important for many theoretical and experimental works, is investigated and it is found that metastable and unstable solutions occur at high temperatures when α and H_Q are increased. However if H_S is increased, metastable and unstable solutions can be found only at low temperatures.     

Measurement of the dipole moment of CF3CN

The Stark effect was observed for K = 0 and K = 1, J = 1 → 2 transitions in CF₃CN. Measurements were made in a Stark modulated microwave spectrometer. The dipole moment obtained was μ = 1.262 ± 0.010 D. An analysis of the effects of electric field inhomogeneities on the observed Stark shifts for K = 0 and K = 1 states is included. Appropriate corrections are given for measuring linear Stark effects in a standard waveguide cell calibrated using a molecule with second-order Stark effect.     

Der Einfluß eines elektrischen Feldes auf Level-Crossings des 6d 2 D 3/2-Zustands im TlI-Spektrum

The influence of an electric field on the energy levels of the 6d²D_3/2-state in the Tl I-spectrum was studied by measuring the shifts of level crossing signals relative to their magnetic field positions. The following values of the magnetic hyperfine constantA and the Stark parameterβ were deduced: ¦A¦=42(2) Mc/sec · g_J/0.8, ¦β¦=0.12(1) Mc/sec/(kV/cm)² · g_J/0.8 and A/β>0. Assuming that the main part of the energy shifts are caused by admixtures of the 7p²P-states the sign of the Stark parameterβ and —from the measured ratio A/β>0 —the sign of theA-factor should be negative. For electric field strength E?30 kV/cm the energy shifts of the 6d²D_3/2state are considerably greater than the hyperfine structure splitting. Therefore the case of decoupled hyperfine structure is considered.     

铯原子里德堡态Stark能量及电偶极矩的测量和理论计算

里德堡原子由于具有体积大、寿命长、易极化及在外电场中能级易于操控等特点, 已经成为了目前物理学领域研究的热点之一. 本文在磁光阱中实验测量了铯原子15P_3/2和16P_3/2态的Stark光谱,根据光谱给出了15P_3/2和16P_3/2|m|=1/2 Stark态在0-1400 V/cm场强范围适用的Stark 能量和偶极矩的经验性解析表达式; 用数值方法求解薛定谔方程获得了这些态的Stark能量、偶极矩和电子几率密度分布. 电子几率密度分布定性说明了计算的偶极矩矢量的方向是正确的. 计算的Stark能量、偶极矩与实验结果相一致.     

Nuclear quadrupole hyperfine quantum beats in HCl and pyrimidine measured by the pump-probe method using REMPI/LIF detection

Coherent time resolved IR-UV double resonance spectroscopy with REMPI and/or LIF detection has been used to measure the nuclear hyperfine structure of a diatomic and a polyatomic molecule. The pump-probe technique was applied and the experimental set up was optimized to achieve highest spectral resolution. Following excitation of the HCl fundamental vibrational transition by a nanosecond IR laser pulse, the nuclear quadrupole coupling constants were determined to be eQq = −69.51(22) MHz for H³⁵Cl and eQq = −54.40(16) MHz for H³⁷Cl in the J = 1 and J = 2 states of the υ = 1 level. Nuclear (Cl) spin-rotation interaction was shown to be active with the corresponding coupling constant being C _I = 0.068(10) MHz for H³⁵Cl and C _I = 0.049(8) MHz for H³⁷Cl. For pyrimidine a C-H stretch vibration ν ₁₃ was excited and the quadrupole tensor elements for the rovibronic states J _{K a} ,K _c = 1₁₀ and 1₀₁ of the υ ₁₃ = 1 level were found to be χ _aa = −3.095(10) MHz, χ _bb = 0.227(10) MHz and χ _cc = 3.322(10) MHz. In this case the residual frequency error was reduced to 8 kHz. The results of these jet experiments independently confirm those from millimeter wave and microwave measurements on static gas samples.     

Back-bending in182,184,186osmium

The high spin yrast states uptoJ=22⁺ in^182,184,186Os are studied in a microscopic variational approach with number-conserved projected states. The energy spectra, quadrupole, moments andB (E2) values are calculated by employing the Hamiltonian with quadrupole plus pairing interactions. The results of the calculations are in fair agreement with the available experimental data.     

Electric quadrupole interaction of210Po(6+) in Bi single crystal

The electric quadrupole coupling constant of the²¹⁰Po(6⁺) isomer in a Bi single crystal was measured as a function of the temperature using the time-differential perturbed angular correlations technique. The electric field gradient (EFG) for Po in Bi is found to be temperature independent in the range 77–477 K. Using a calculated value of the nuclear quadrupole moment, the magnitude of the EFG is derived, and in turn serves to re-examine the systematics of quadrupole moments of λh ₉ ^2/2 configurations in the lead region.     

The argon nuclear quadrupole moments

New standard values -116(2) mb and 76(3) mb are suggested for the nuclear quadrupole moments (Q) of the ³⁹Ar and ³⁷Ar nuclei, respectively. The Q values were obtained by combining optical measurements of the quadrupole coupling constant (B or eqQ/h) of the 3s²3p⁵4s[3/2]₂ (³P^o) and 3s²3p⁵4p[5/2]₃ (³D^e) states of argon with large scale numerical complete active space self-consistent field and restricted active space self-consistent field calculations of the electric field gradient at the nucleus (q) using the LUCAS code, which is a finite-element based multiconfiguration Hartree–Fock program for atomic structure calculations.     

The microwave spectrum and centrifugal distortion constants of difluoroborane,HBF2

The microwave spectra of two isotopic species of the unstable molecule difluoroborane have been measured between 8 and 36 GHz. Transitions have been measured up to J = 56 and K_a = 9 for H¹⁰BF₂, and up to J = 66 and K_a = 11 for H¹¹BF₂. Improved values for the rotational constants, boron nuclear quadrupole coupling constants, and quartic and sextic centrifugal distortion constants have been evaluated for both species.     

Molecular beam electric resonance without A- and B-fields

We report on a novel phenomenon observed during the passage of a pulsed NO beam seeded in He through a combined homogeneous, static electric and RF field, denoted as C-field in a standard molecular beam electric resonance (MBER) experiment. Although we refrain from the state selective A- and B-fields, which are considered crucial for a MBER experiment, the transmitted intensity exhibits as a function of the RF frequency conspicuous dips at resonance frequencies that depend strictly linearly on the static field strength E ₀. Their spectral width is by a factor of 4 smaller than the time of flight broadening. Both, the resonance frequencies and their linear field dependence can be precisely predicted applying a simple expression for the Stark effect to a transition of a single rotational state (J = 3/2) of the electronic ground state . However, this formula is valid only in the high field limit (E ₀ > 1000 kV/m) while the employed field (E ₀ = 1.47 kV/m) was in the extreme low field domain where the large type doubling and hyperfine coupling lead to a purely quadratic Stark effect. We assume that the phenomenon is due to a yet unknown collective rather than to an isolated particle process.Received: 9 May 2003, Published online: 12 August 2003PACS: 33.20.Bx Radio-frequency and microwave spectra - 32.60. + i Zeeman and Stark effects Author for correspondence: A. González Ureña