Intracavity Laser Spectroscopy of NiCl System G: Identification of a [13.0] Π3/2 State

The (0,0) vibronic band of NiCl system G with a bandhead near 12 961 cm⁻¹ was recorded at high resolution in absorption using intracavity laser spectroscopy (ILS). For the ILS absorption spectra, the NiCl molecules were produced in a nickel hollow cathode, operated with a small amount of CCl₄, and line positions were referenced to iodine spectra. Fourier transform (FT) emission spectroscopy was used to record an extensive region of the spectrum used in a vibronic analysis of system G. For the FT spectra, excited NiCl molecules were produced in a high-temperature King-type carbon tube furnace. We show that this transition is the (0,0) vibronic band associated with a newly identified ²Π_3/2 excited state and the X²Π_3/2 ground state. The molecular constants for the new ²Π_3/2 electronic state are derived from the rotational analysis. Improved vibronic constants for the band are obtained from analysis of the FT spectra.     

Electron paramagnetic resonance and optical spectroscopy of K3Na(CrO4)2 ferroelastics activated by MnO 4 2− molecular impurity ions

Crystals of a proper ferroelastic K₃Na(CrO₄)₂ containing molecular impurity ions MnO ₄ ^2? are studied using electron paramagnetic resonance (EPR) and optical spectroscopy. The EPR spectrum of the Mn⁶⁺ ion contained in the molecular impurity ion MnO ₄ ^2? is identified at low temperatures (T ≤ 20 K). The intensity of this spectrum decreases unusually fast as the temperature increases. A broad IR luminescence band with a vibronic structure well resolved at a temperature of 8 K is revealed. Theoretical treatment of the Mn⁶⁺ ion involved in the molecular impurity ions MnO ₄ ^2? of the K₃Na(CrO₄)₂ ferroelastic crystal suggests that an important role in this case is played by the pseudo-Jahn-Teller. The pseudo-Jahn-Teller effect offers an explanation for the appearance of a fine structure in the vibronic replicas in the luminescence spectrum, on the one hand, and accounts for the fast decrease in the intensity of the EPR spectrum of K₃Na(CrO₄)₂: MnO ₄ ^2? with increasing temperature, on the other.     

Intensity and bandwidth of multiphonon vibronic transitions of rare-earth ions in crystals

The theory of multiphonon vibronic coupling to electronic transitions is applied in analysing fluorescence spectra of Eu²⁺ in BaFCI, which consist of the 4f⁷(⁶P_7/2,) → 4f⁷(⁸S_7/2) and 4f⁶5d → 4f⁷ transitions, and the 4f⁷-4f⁶5d excitation spectrum of Ce³⁺ in YPO⁴. The 4f electrons are weakly coupled to lattice vibration modes so that only weak one- and two-phonon sidebands are observable in the 4f-4f optical transitions, whereas the electron-phonon coupling is significantly stronger for a 5d electron. Accordingly, intensive multiphonon vibronic transitions overwhelmingly dominate the 4f⁶5d → 4f⁷ spectrum. It is shown that the extended Judd-Ofelt theory for weak vibronic coupling in the framework of the M-process is equivalent to the Huang-Rhys theory for the δ-process. In the analysis of experimental data, contributions from local ligand modes and lattice acoustic modes are separated, and the coupling strength is evaluated, in terms of the Huang-Rhys parameter S, for the 4f-4f and 5d-4f vibronic transitions.     

Computer Resolution and Franck-Condon Analysis of the Electronic Absorption Spectrum of KMnO4 in Water

Abstract

The electronic absorptíon spectrum of KMnO₄ in water solution was analyzed. The spectral contour was resolved into component bands and then Franck-Condon approach was applied. In the investigated range of 13000–48000 cm^?1 a presence of three structureless and of two vibronic strong bands was stated. The change in the Mn-O equilibrium bond length was found to be 10.5pm for 2e·1t₁ transition (vibronic band about 18000cm^?1) and to be 16pm for the 2e·3t₂ transition (vibronic band about. 30000cm_?1). The appropriate wavenumber of the vibrational mode in these excited electronic states was found to be 735cm^?1 and about 780cm^?1, respectively. The ground electronic state wavenumber of the totally symmetric vibrational mode was fitted to be equal to 828cm^?1. Details of the proposed method of computer elaboration of electronic spectra with vibrational structure were discussed.

Electronic absorption spectra of some inorganic comppunds consist of a number of strongly overlapped bands due to their vibronic structure.^1–5 A detailed analysis of spectral contours of such compounds provides some useful information about their structure in both ground excited electronic states.

The electronic spectrum of permanganate ion is the typical example of vibronic spectra.¹ The main part of the past works based on the analysis of permanganate ion spectra in low temperatures and different polarizations. In such conditions the vibronic structure is rather good resolved and can be effectively studies.^1,3,6 Spectra of solutions as a rule are relatively poor resolved so their analysis has to be more sophisticated.

The main purpose of this work is a presentation of a new computer method for an effective study of vibronic spectra of solutions. This method has been applied to the electronic absorption spectrum of KMnO₄ in water. The method allowed us to fit the geometric parameters of spectral contour, to establish the origins and parameters of two progressions in the UV/VIS range as well as to calculate the changes in the Mn-0 equilibrium bond lengths and vibrational energy resulting from the electronic excitations of the soluted permanganate ion.     

Assignments of the nπ singlet states of p-benzoquinone

The vapor phase fluorescence spectra of p-benzoquinone-h₄ and d₄ are reported and discussed in relation to the assignment of the low lying singlet states. The low temperature, polarized single crystal electronic absorption spectra of p-benzoquinone and several of its isotopic derivatives are reported. From the isotope shifts and band polarizations of the various vibronic origins, a detailed vibronic analysis is offered of the electronic absorption spectrum of p-benzoquinone which indicates a near degeneracy of the ¹A_u and ¹B_1g electronic states.     

The laser-induced fluorescence spectroscopy of gold monoxide: B2Σ−－X2Π3/2 transition

The electronic spectrum of the gaseous gold monoxide molecule has been investigated in the range of 16000－18500?cm^?1 using laser induced fluorescence spectroscopy and single vibronic level emission spectra. Five rotationally resolved vibronic bands are observed and assigned to the transitions B²Σ^? (v'?=?0－4) －X²п_3/2 (v''?=?0), in which the 0－0 transition is observed for the first time. The molecular constants of the excited state B²Σ^? are obtained by a rotational analysis of the spectra. The spin-orbit coupling constant and the vibrational constants of the ground state X²п_i are determined with the accuracy improved by one order of magnitude. The lifetimes of most observed bands are also measured for the first time.     

Gas phase electronic spectrum of the HSCCS radical by laser-induced fluorescence spectroscopy

In a discharged supersonic jet of a CS₂ and C₂H₂ mixture, a vibronic band system of a new radical species was observed in the energy region 21 800-23 000 cm⁻¹ by laser-induced fluorescence (LIF) spectroscopy. The LIF excitation spectrum shows progressions with 490 and 80 cm⁻¹ separations. The vibronic structure of a dispersed fluorescence (DF) spectrum, obtained by tuning a probe laser to the vibronic origin band, also consists of progressions with 520 and 100 cm⁻¹ separations. A high-resolution laser scan provided a rotationally resolved LIF excitation spectrum for the vibronic origin band, showing the rotational structure of a-type transitions of a near-prolate top. Several chemical tests indicate that the spectral carrier contains sulfur atom(s), one hydrogen atom and more than one carbon atoms. Electronic transition energy, vibrational frequencies, and rotational constants of this species are similar to those of SCCS⁻ [M. Nakajima, Y. Yoneda, Y. Sumiyoshi, T. Nagata, Y. Endo, J. Chem. Phys. 119(2003)7805-7813.], and the spectral carrier was assigned as an isoelectronic radical, bent HSCCS. Ab initio geometrical optimizations supported the spectral carrier to be HSCCS. The observed electronic transition was assigned to be the transition, which corresponds to the Π-Π transition in the limit of linear geometry. The observed vibrations in the excitation and DF spectra were assigned as the symmetric CS stretching (ν₅) and SCC bending (ν₇) modes by comparing the results of theoretical calculations.     

Identification of the SO2 cold vibronic bands in the 32 200–33 300 cm−1 region

Summary The fluorescence excitation spectrum of SO₂ in the 32 200–33 300 cm⁻¹ energy region was recorded, at very low rotational temperature, in a pulsed supersonic jet. The band centres and relative intensities of about 60 well-resolved vibronic bands were determined in this region, which extends the previously available data by 800 cm⁻¹. Single vibronic level fluorescence spectra of two neighbouring vibronic bands in theD-band region along with a few filtered excitation spectra are also presented as an example of the resolution for the listed bands. The authors of this paper have agreed to not receive the proofs for correction.     

Laser excited fluorescence spectrum of nitrogen dioxide

The fluorescence spectrum of NO₂ excited by a single mode argon-ion laser was studied at a spectral resolution of 0.1 cm^?1. In particular the Stokes and the anti-Stokes ν₂ band excited by the 5145 Å line of an argon-ion laser were examined in detail. Some of the vibrational and rotational parameters of the ground electronic state and the rotational constants of the B₂ vibronic state were obtained.     

The potential barrier height for a Jahn-Teller center

The EPR spectrum of the Cu²⁺ ion in a ZnSiF₆·6H₂O crystal is studied in the temperature range T=5?300K. It is shown that the EPR spectrum can be represented in the form of a superposition of three contributions with essentially different properties. The first contribution is characterized by the maximal intensity at low temperatures and is described by a spin Hamiltonian with a large anisotropy of parameters. The second contribution has the maximal intensity at high temperatures and is described by a spin Hamiltonian with a low anisotropy of parameters. The third contribution cannot be described by a spin Hamiltonian and has the form of a partly orientationally averaged EPR spectrum. The reason for the emergence of these contributions is substantiated along with the form of the temperature dependence of their intensities on the basis of variation of the populations of vibronic states upon a change in temperature. The height (E₀=4±1cm_?1) of the potential barrier separating three equivalent Jahn-Teller potential wells of the Cu²⁺ ion is determined from analysis of the temperature dependence of the integrated intensity of the EPR spectrum. The obtained value of the barrier height substantially differs from the estimate (100 cm^?1) obtained earlier [2, 3] for the Cu²⁺ ion in ZnSiF₆·6H₂O on the basis of the tunneling model. It is shown that the forms of the temperature dependences of the linewidth of the low-and high-temperature EPR spectra are essentially different. This difference indicates that the contributions of the low-and high-temperature EPR spectra are associated with quantum-mechanical transitions between these states. It is proposed that the low-and high temperature contributions to the EPR spectrum are associated with the filling of under-the-barrier and above-the-barrier vibronic states, respectively.     

Jet Spectroscopy of theD12B1–D01B1Transition of thep-Cyanobenzyl Radical

We have generated thep-cyanobenzyl radical in supersonic free expansion, and measured the vibrationally and rotationally resolved laser induced fluorescence (LIF) excitation spectra and the LIF dispersed spectra from the single vibronic levels (SVL) in the green-blue region. The lowest energy band at 20 738 cm⁻¹with the strongest intensity in the excitation spectrum has been assigned to the 0⁰₀band of the visible spectrum, on the basis of the vibronic structures in the SVL dispersed spectra. Based on the band type of the 0⁰₀band,a-type, determined from the rotationally resolved LIF excitation spectrum, we have definitely assigned the visible band to theD₁2²B₁–D₀1²B₁electronic transition. We have found, on the grounds of the vibrational analysis of the dispersed spectra, that the vibronic structure of the 2²B₁–1²B₁electronic transition of the benzyl type is characterized by totally symmetric fundamental modes, 1, 8a, and 9a.     

Fourier Transform and Intracavity Laser Spectroscopy of NiCl System H: Identification of a [12.3] Σ State

The (0,0) vibronic band of NiCl system H near 12 259 cm⁻¹ was recorded at high resolution in absorption using intracavity laser spectroscopy (ILS) and in emission by Fourier transform (FT) spectroscopy. Though it was originally assigned in 1962 as the (1,1) vibronic band of ²Π_3/2-X²Δ_5/2, we have shown that this transition is the (0,0) vibronic band associated with a newly identified ²Σ⁺ excited state and the X²Π_3/2 ground state. The molecular constants for the new ²Σ⁺ electronic state were derived from the rotational analysis. For the ILS absorption spectra, the NiCl molecules were produced in a nickel hollow cathode, operated with a small amount of CCl₄. Line positions were referenced to iodine spectra observed from a heated extracavity cell using the intracavity laser as the light source. For the FT spectra, excited NiCl molecules were produced in a King-type carbon tube furnace.     

激光诱导NO2分子500—532nm区荧光激发谱的实验研究

用准分子激光抽运可调谐染料窄带激光测定了室温下NO₂分子500—532nm区高分辨荧光激发谱,在两个较强吸收区505—510nm和513—520nm范围内标识了25个振动带,并作了转动分析,得到了相应的带头位置、转动常数和旋-转偶合常数等分子光谱常数,在25个振动带中有5个谱带是新发现的,所有得到转动分析的谱线均属于平行跃迁X～ ² A₁—A～²Ｂ₂,对实验结果的分析表明电子激发态A～ 关键词： 激光诱导荧光激发谱 振动带 转动分析     

Feshbach resonances of the C3H− anion: laser autodetachment spectroscopy and ab initio calculations

The electronic spectra of the C₃H^? and C₃D^? anions have been studied above the lowest electron detachment threshold. On the basis of the vibrational, rotational analysis and ab initio calculations, the photodetachment spectrum is assigned to the d³ A″←a³ A″ Feshbach resonance in the bent chain C₃H(D)^? anion. The vibronic system is characterized by a long vibrational progression involving the CCH in plane bending mode ν₄. The potential curves along this coordinate obtained from the spectral analysis and theoretical calculations reveal the importance of vibronic coupling in the electronic excited states. A strong Renner–Teller effect is thought to be the reason for the existence of the Feshbach resonance because the ⁴Σ^? neutral parent and the ³Π anion excited states are close in energy. As for the neutral, ν₄ appears to be the active mode and drives the interaction between the Feshbach and the dipole bound states.     

On the theory of vibronic superradiance

The Dicke superradiance on vibronic transitions of impurity crystals is considered. It is shown that parameters of the superradiance (duration and intensity of the superradiance pulse and delay times) on each vibronic transition depend on the strength of coupling of electronic states with the intramolecular impurity vibration (responsible for the vibronic structure of the optical spectrum in the form of vibrational replicas of the pure electronic line) and on the crystal temperature through the Debye-Waller factor of the lattice vibrations. Theoretical estimates of the ratios of the time delays, as well as of the superradiance pulse intensities for different vibronic transitions well agree with the results of experimental observations of two-color superradiance in the polar dielectric KCl:O ₂ ^? . In addition, the theory describes qualitatively correctly the critical temperature dependence of the superradiance effect.     

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.     

Investigation of the luminescence spectrum of UO2MoO4

By time-resolved spectroscopy the intrinsic emission spectrum of UO₂MoO₄ at 4.2 K is obtained. The main progressions in the vibronic structure are identified as couplings with the A_g correlation field components of the symmetric and asymmetric UO₂ stretching modes. The intrinsic zero-phonon line in the emission and excitation spectrum is shown to be split both by the crystal field and correlation field. The steady-state emission spectrum at 4.2 K is dominated by emission from traps. The vibronic structure of the trap emission reveals that all traps are distorted uranyl groups.     

The origin of the isotropic EPR spectrum of a Jahn-Teller impurity in crystals

The motional narrowing processes and their contribution to the origine of the isotropic EPR spectrum of a cubic ²E — term in the cases of strong linear and both weak and strong second-order vibronic interaction, are investigated. It is shown that these relaxation processes are nonefficient at low temperature, and the isotropic spectrum is associated with the nearest exited vibronic singlet level.     

Laser Raman Spectrum of Triglycine Sulfate

Abstract

The laser Raman spectrum of ferroelectric triglycine sulfate has been determined by the use of an argon ion gas laser. The observed Raman lines are compared with reported assignments in the literature by Taurel¹ and Krishnan², Determination of depolarization ratio of the sulfate line at 980 cm^?1 shows that the Raman band is highly polarizable and the molecular vibration is totally symmetrical v₁.

The role played by the glycine groups in the spontaneous polarization and its reversal can be indirectly confirmed by Raman spectrum of TGS. Interpretation of the Raman spectrum indicates that the SO₄ groups do not have tetrahedral symmetry at roan temperature. Ferroelectric behavior of TGS is attributed to the glycine groups.     

Two-photon vibronic spectroscopy of allene at 7.0–10.5 eV: experiment and theory

2?+?1 resonance-enhanced multiphoton ionization (REMPI) spectra of allene at 7.0–10.5?eV have been observed. The excited vibronic symmetry has been determined from polarization-ratio measurements. Based on the vibronic energies and peak intensities calculated using ab initio MO and time-dependent density functional theory, the very congested REMPI spectra have been assigned as due to π*?←?π, 3p?←?π, 4s?←?π, 4p?←?π, and 4d?←?π transitions. Vibrational progressions related to the CH₂ twisting (ν₄ ～770?cm^?1) have been observed for several excited electronic states. Calculated Franck–Condon factors also confirm that CH₂ twisting is the most active mode in the vibronic spectra of allene. In this study, theoretical calculations of two-photon intensities and polarization ratios have been made through the ab initio computed one-photon transition dipole moments to various electronic states as intermediates. As a starting point to interpret the complicated vibronic spectrum of allene, the theoretical approach, without vibronic couplings, has been applied to predict the peak positions, spectral intensities, and polarization ratios of Rydberg states, and qualitatively shows a considerable agreement with experimental observations.