The b-type rotational transitions of HNCO in the lowest excited vibrational state

In the microwave and millimeter wave spectra of HNCO, the b-type transitions between the K_a = 0 and 1 levels in the lowest excited vibrational state have been observed. Because of strong a-type Coriolis resonances among the three bending excited states the energy difference between the levels for K_a = 0 and 1 is much smaller in the lowest excited state than in the ground state. The subband origin of these b-type transitions has been found in the millimeter wave region at 275 697.309 MHz (9.1963 cm^?1). The effect of the Coriolis resonances is discussed in relation to the molecular quasi-linearity and is compared with the case of HNCS.     

Zeeman relaxation of N2 + (2Σ+) in collisions with 3He and 4He

We compare the cross sections for the transitions changing the projection of the total angular momentum of N₂ ⁺(²Σ) in collisions with ³He and ⁴He at very low collision energy. The fundamental states of the two nuclear spin isomers of N₂ ⁺ are considered as well as the two fine structure levels of the first excited para level N=2. It is shown that the two fundamental states of the two nuclear spin isomers behave differently. For the fundamental para level N=0 of N₂ ⁺, the projection changing cross section is always negligible compared to the elastic one for both He isotopes. For the fundamental ortho level N=1 of N₂ ⁺, the spin-rotation interaction couples the different spin levels directly so the spin relaxation becomes a first order process. The associated resonances increase the projection changing cross section which remains smaller but becomes comparable with the elastic one. This is in contrast with the excited rotational levels of N₂ ⁺, which for the rotational deactivation and elastic channels are found to be equal around the resonances for the collisions involving ³He. These two channels are always larger than the projection changing one. We also find that, for transitions involving the fundamental rotational state, the domain of validity of the threshold laws discussed by Krems and Dalgarno [Phys. Rev. A 67, 050704 (2003)] for a potential decreasing faster than 1/r2 is shortened, due to the long range charge induced dipole potential. This effect is illustrated for the collisions of ³He with the fundamental para state of N₂ ⁺.     

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.     

Excited state absorption and stimulated emission of Nd3+ in crystals. Part I: Y3Al5O12, YAlO3, and Y2O3

4 F_3/2 excited state of the Nd³⁺ ion in Y₃Al₅O₁₂, YAlO₃, and Y₂O₃ were measured in a continuous wave pump- and probe experiment in a wide spectral range from 850 nm (780 nm for Y₃Al₅O₁₂) to 1500 nm. The cross sections were determined from a comparison with the emission spectra and the simultaneously measured ground state absorption bleaching. The strongest excited state absorption transitions were found in the 1220–1400 nm spectral region due to transitions to the ²G_9/2 and ⁴G_7/2 levels. The spectral positions of the measured transitions are in good agreement with the theoretically expected transitions calculated from the known Stark-level splittings. Received: 4 December 1997/Revised version: 8 May 1998     

Photoinduced dynamics to photoluminescence in Ln3+ (Ln = Ce,Pr) doped β-NaYF4 nanocrystals computed in basis of non-collinear spin DFT with spin-orbit coupling

ABSTRACT

In this work, non-collinear spin DFT + U approaches with spin-orbit coupling (SOC) are applied to Ln³⁺ doped β-NaYF₄ (Ln = Ce, Pr) nanocrystals in Vienna ab initio Simulation Package taking into account unpaired spin configurations using the Perdew–Burke–Ernzerhof functional in a plane wave basis set. The calculated absorption spectra from non-collinear spin DFT + U approaches are compared with that from spin-polarised DFT + U approaches. The spectral difference indicates the importance of spin–flip transitions of Ln³⁺ ions. Suite of codes for nonadiabatic dynamics has been developed for 2-component spinor orbitals. On-the-fly nonadiabatic coupling calculations provide transition probabilities facilitated by nuclear motion. Relaxation rates of electrons and holes are calculated using Redfield theory in the reduced density matrix formalism cast in the basis of non-collinear spin DFT + U with SOC. The emission spectra are calculated using the time-integrated method along the excited state trajectories based on nonadiabatic couplings.     

Magnetic interactions in Pr3+ : LiYF4 for quantum manipulation : search for an efficient three-level Λ system

The influence of an external magnetic field on the hyperfine structure of the ³ H₄(0) and ¹D₂(0) crystal field states of Pr³⁺ in LiYF₄ is studied in order to find an efficient three-level Λ system. Using an experimentally determined spin Hamiltonian, we show that three-level Λ systems can be obtained with equal strengths for the optically excited transitions under various magnetic field magnitudes and orientations. An analytical analysis based on two levels is proposed to find useful magnetic fields without extensive numerical calculations and to understand the general behaviour of the system. Pr³⁺ hyperfine structure has also been directly calculated using a complete Hamiltonian including free ion, crystal field and magnetic interactions. A good agreement with the spin Hamiltonian approach is found for the ground state whereas the excited state results poorly reproduce the experiment. This is attributed to the low accuracy of ¹D₂ crystal field wavefunctions. This suggests that transition strengths ratios could be calculated directly from the crystal field Hamiltonian with improved crystal field parameters.     

Proton radioactivity at non-collective prolate shape in high spin state of Ag

We predict proton radioactivity and structural transitions in high spin state of an excited exotic nucleus near proton drip line in a theoretical framework and investigate the nature and the consequences of the structural transitions on separation energy as a function of temperature and spin. It reveals that the rotation of the excited exotic nucleus ⁹⁴Ag at excitation energies around 6.7 MeV and angular momentum near 21? generates a rarely seen prolate non-collective shape and proton separation energy becomes negative which indicates proton radioactivity in agreement with the experimental results of Mukha et al. for ⁹⁴Ag.     

Lamb–Mössbauer factor of electronically excited molecular states measured by time‐differential Mössbauer emission spectroscopy

The Lamb-Mössbauer Factor (LMF) of molecular crystals is expected to depend on the electronic molecular states by their different intramolecular vibrational frequencies. Revisiting Mössbauer spectra obtained by time differential Mössbauer emission spectroscopy of the low spin compound [⁵⁷Co/Mn(bipy)₃](PF₆)₂ (bipy= 2,2'-bipyridine) a ratio of 1.25 for the LMFs of the low spin ground state and of an excited high spin state decaying in the Mössbauer time window could be evaluated. The difference found is in line with the change of LMF observed for spin crossover compounds where the excited high spin state is populated by the so‐called LIESST effect. The initial population of the high spin state is close to 100%.     

Spin relaxation of the8 S 7/2 ground state of europium in noble gases

Spin relaxation of the 4f ⁷ 6s ^{2 8} S _7/2 ground state of the Eu atom in noble gases was investigated by the direct, continuous optical pumping method. Transient signals could be observed by pulsed saturation of rf Zeeman transitions within theF= 6 hfs level of the stable Eu isotopes. The time constant of the transient signals can be related to the electronic spin depolarization cross section for Eu-noble gas collisions, yielding noble gas He Ne Ar Kr Xe σ₁in 10^?20 cm² 0.99(10) 5.1(5) 15(1.5) 43(4) 97(10) These cross sections exceed those measured forS-states of alkalies by three orders of magnitude. They can be explained by perturbations of theS-ground state configuration of Eu due to the admixture of excited state non-spherical wave functions.     

Radiative and non-radiative decays from the excited state of Ti3+ ions in oxide crystals

The fluorescence spectra of Ti³⁺ in Y₃Al₅O₁₂ (YAG), Al₂O₃ (sapphire), YAlO₃ (YAP) observed at 10 K are composed of zero-phonon lines accompanied by the broad vibronic sidebands. The temperature dependence of the fluorescence lifetime and of the total intensity of the broadband measured in YAG and Al₂O₃ indicate that the radiative decay times from the excited states are nearly constant in the range 10–300 K. This demonstrates that the broadband radiative emissions in Ti³⁺:YAG and Ti³⁺:Al₂O₃ are due to magnetic dipole transitions or to electric dipole transitions induced by static odd-parity distortion, respectively. The decrease of the fluorescence lifetime with increasing temperature in Ti³⁺:YAG and Ti³⁺:Al₂O₃ is due to non-radiative decay from the excited state which occurs through phonon-assisted tunnelling between the excited and ground states. The radiative decay of Ti³⁺:YAP is enhanced with increasing temperature, indicating that radiative decay rate contains a term associated with odd-parity phonons. Nevertheless, a non-radiative decay rate of 3.6 × 10⁴ s^–1 observed in the temperature range 10–300 K is due to excited state absorption, which depopulates the excited state and quenches the fluorescence at the laser wavelength.     

High-Resolution Visible Laser Spectroscopy of Cobalt Monochloride

The electronic spectrum of cobalt monochloride has been investigated from 415 to 725 nm using a laser-ablation/molecular-beam laser-induced fluorescence spectrometer. Two separate electronic systems with origins near 483.3 and 470.3 nm were observed. Data have been recorded for these two transitions at both low and high resolution. These transitions are now characterized as the [20.7]³Φ₄−X³Φ₄ and [21.3]³Φ₄−X³Φ₄ transitions. A low-resolution vibrational analysis and a high-resolution rotational analysis have been carried out for each system, resulting in accurate values for the ground and excited state vibrational spacings and effective rotational constants. In addition, the magnetic hyperfine structure resulting from the spin of the Co nucleus was resolved and the hyperfine constants were determined. Comparison of the CoCl spectrum with that of CoH and CoF has allowed the ground state electron configuration of (core)(10σ)²(4π)⁴(1δ)³(5π)³(11σ)² to be determined. The hyperfine constants support the electron promotion 11σ→12σ for the observed transitions.     

Excited-state absorption and energy output of laser ruby

The laser performance, luminescence intensity and absorption in excited state of rubies annealed in reducing or oxidizing atmosphere is given. Rubies doped with Mg, Ti or Fe were compared to those containing Cr only. The decrease of energy output is caused by the non-radiative transitions from the excited states to the ground⁴A₂ state. O^– centre developed by the presence of the large ions facilitate the transitions from the upper excited states only, whereas Fe and to a less extent Ti ions make the non-radiative transition from the metastable²E level to the⁴A₂ level possible. Ti³⁺ ions filter also the UV content of the flashlight and prevent the transition from the²E to the higher states.     

Synchrotron radiation from relativistic electrons in intense magnetic fields

The synchrotron radiation spectrum is calculated for relativistic electrons in the case where no restriction is placed on the strength of the magnetic field. It is shown that in intense fields H? H₀ = m²c³/e₀? =4.41 · 10¹³ G a major contribution to the total radiation intensity comes from transitions to the ground state and also to weakly excited levels. In particular, the contribution from transitions to the ground state (final electron energy E' =mc²) for electrons of initial energy E = 10 MeV in a field H = 2H₀ is 14% of the contribution from transitions to highly excited states (E'?mc²).     

The infrared spectrum of DCCF in the 320–850 cm−1 region: bending states up to υ4+υ5 = 3

Infrared spectra of deuterated monofluoroacetylene, DCCF, have been recorded in the region between 320 and 850 cm^?1 at an effective resolution ranging from 0.0024 to 0.0031 cm^?1. In total, 6650 rotation vibration transitions were assigned to 37 bands involving the bending states with v₄ + v₅ and |l₄+l₅|, respectively, up to 3, allowing the characterisation of the ground state and of 18 vibrationally excited states. The vν₅ bending fundamental has been studied for the first time. In addition, the difference band v₃ ← v₄ has been detected and analysed. All the assigned transitions have been fitted simultaneously by adopting a model Hamiltonian that takes into account the vibration and rotation l?type resonances. Rotational transitions in the ground and in bending excited states reported in the literature have been included in the global analysis. The set of 57 derived spectroscopic parameters reproduces 6130 infrared and 90 microwave and millimetre?wave transitions satisfactorily with root mean square values of 5.3 × 10^?4 cm^?1 and 77 kHz, respectively.     

Calculation of interaction of the stretching and bending vibrations of HF in the hydrogen-bonded complex [F(HF)2]?

Vibrations of the [F(HF)₂]^? complex are calculated with allowance for the anharmonic interactions of the stretching vibrations of HF monomers and their rotations about the centers of gravity of HF in the plane of the complex. A four-dimensional vibrational Schr?dinger equation is solved using a potential energy surface calculated in the MP2/6-311++G(3df,3pd) approximation with the superposition of atomic functions of the monomers taken into account. The equilibrium and vibrationally averaged structures of the complex are determined. The frequencies and intensities for spectral transitions from the ground state to a number of excited vibrational states are calculated. It is shown that, due to resonances between the excited states of the stretching modes and doubly excited states of the bending modes, the overtone transitions associated with the bending modes borrow a significant part of the intensity of fundamental stretching transitions.     

Electronic states and spectroscopic properties of MgH in absence and presence of spin–orbit coupling − a configuration interaction study

Electronic spectrum of astrophysically important molecule magnesium hydride (MgH) has been studied using configuration interaction methodology excluding and including spin–orbit coupling. Potential energy curves of several spin-independent (Λ?S) electronic states have been constructed and spectroscopic constants of low-lying bound Λ?S states within 8.2 eV of term energy are reported in the first stage of calculations. The X²Σ⁺ is identified as the ground state in the Λ?S level. In the subsequent stage, the spin–orbit interaction has been incorporated and its effects on the potential energy curves and spectroscopic features of different electronic states of the species have been investigated. The X²Σ⁺_1/2 is identified as the spin–orbit (Ω) ground state of the species. Transition moments of several dipole-allowed transitions are computed in both the stages and radiative lifetimes of the corresponding excited states are computed. Electric dipole moments (µ) for a number of low-lying bound Λ?S states as well as several low-lying Ω-states are also calculated in the present study.     

Luminescence channels of manganese-doped spinel

Two independent luminescence channels are observed from manganese-doped spinel Mn:MgAl₂O₄. The luminescence around 520 nm is assigned to transition from the lowest electronic excited state ⁴T₁ to the ground state ⁶A₁ of Mn²⁺ (3d)⁵ ion by analyzing the excitation spectrum and electron spin resonance measurement. The emission at 650 nm is triggered by the band edge excitation and is assigned similarly to the charge-transfer process associated with the manganese ion.     

Non-yrast states of 132Ce polutated in β-decay

Non-yrast low spin states of the nucleus ¹³²Ce were studied by means of γ-spectroscopy following the β-decay of the ground and medium spin isomeric states of ¹³²Pr. The activity was produced with the reaction ¹¹⁷Sn(¹⁹F,4n) ¹³²Pr at the Cologne FN TANDEM accelerator. The γγ coincidences and singles spectra were measured with the OSIRIS cube spectrometer. The β-decay of ¹³²Pr populates states with spins up to 6ħ and excitation energies up to 4.4 MeV in ¹³²Ce. Besides ground and quasi-gamma bands, an excited band based on the 0₂⁺ state and many other low-lying states were observed. The γγ angular correlations were analyzed to assign spins and parities to the excited states, and to determine the multipolarities of the γ-transitions. We found dominant E2 transitions in the quasi-gamma band and from the quasi-gamma band to the ground band. The experimental data are compared with calculations using the Interacting Boson Model (IBM). Good agreement is reached in the vicinity of the O(6) limit.     

A theoretical analysis of the excited states in 2-benzoylthiophene

The lower excited states of 2-benzoylthiophene have been studied using ab initio quantum chemical methods based on multiconfigurational wave functions. Six singlet and six triplet excited states have been characterized. The geometry has been optimized for the two lowest triplet states, which are responsible for the photoreactivity of the chromophore in the photosensitizing drug tiaprofenic acid. The T¹(π → π?) and T₂(n → π?) states have been found to be close in energy with the π → π? state slightly lower. The excited states have been characterized using density difference and spin density plots. The different photochemical behaviour of the two triplet states can be rationalized from the theoretical data.