Molecular Rydberg transitions: The lowest-energy Rydberg transitions of s-type in CH3X and CD3X,X = Cl,Br, and I

The absorption spectra associated with transitions to the lowest-energy s-type Rydberg states of CH₃X and CD₃X, X = Cl, Br, and I, have been measured and analyzed. The spectra of the bromides and iodides consist, individually, of four electronic origins of s-excitation type. The vibrational frequency of a given normal mode is more or less identical in all four excited states of any one molecule; and the excited state/ground state ratios of the frequencies of any given normal vibrational mode are essentially identical for all four molecules (i.e., for 16 states, four for each of two bromides and two iodides). The spectra of the chlorides are amenable to a number of different vibronic analyses, none of them unique; these analyses are discussed.     

Electronic photodissociation spectra of the Arn-C4H2 (n=1-4) weakly bound cationic complexes

Electronic spectra of a series of weakly bound clusters consisting of argon (Ar_n, n=1-4) bound to the butadiyne cation, C₄H₂⁺, have been recorded in the visible range from 440 to 520 nm by photodissociation. The C₄H₂⁺ fragment signal was recorded as a function of the laser wavelength during excitation of the A←X electronic transition. The observed transitions were assigned to the band origin of the cationic complexes and to vibronic bands involving excitation of the ν₃ and ν₇ vibrational modes of the C₄H₂⁺ moiety, as well as combination bands of these modes. Comparison of the photodissociation spectra of the various clusters reveals a small blue shift, 25 cm⁻¹ of the band maxima relative to the corresponding transitions reported from gas phase spectra of the bare C₄H₂⁺ cation. The magnitude of the blue shift of each band increases with successive Ar solvation up to n=3. Furthermore, each band becomes increasingly broadened towards the red with the addition of Ar atoms due to an increasing number of unresolved transitions involving excited intermolecular modes.     

Carbon K-shell excitation spectra of linear and branched alkanes

The electron energy loss spectra of ethane, propane, n-butane, n-pentane, n-hexane, isobutane, isopentane and neopentane in the region of carbon K-shell excitation have been recorded under dipole-dominated conditions (2.8 ke V impact energy, small angle). The spectra are dominated by transitions to unoccupied valence π¹(CH₂, CH₃) and σ¹(C-C) levels. Additional weak features are assigned to Rydberg transitions. The position of the main continuum feature in each spectrum is consistent with the predictions of an empirical relationship with bond length. Systematic variations of spectral intensities are observed which support our assignments. The dominant feature in the K-shell spectrum of ethane, which was previously assigned to C 1s → 3p Rydberg transitions, is reassigned to excitation to a 3p/π¹(CH₃ ), mixed Rydberg/valence orbital (of antibonding σ-¹(C-H) character), in comparison to the other alkane spectra. An improved calibration value of 290.74(5) eV for the energy of the C 1s → π¹ transition in CO₂ is also obtained.     

Inner-shell excitation and EXAFS-type phenomena in the chloromethanes

Small angle inelastic scattering of 2.5 keV electrons was used to study the inner-shell excitation of CH₄, CH₃Cl, CH₂Cl₂, CHCl₃, CCl₄ and C₂H₅Cl in the regions of carbon 1s, chlorine 2p and chlorine 2s excitation. Structure observed below the carbon 1s ionization threshold in each molecule is assigned to promotions of a carbon 1s electron to unoccupied valence and Rydberg orbitals. Trends in the distribution of spectral intensities through the series of chloromethane carbon 1s spectra are discussed in terms of the growth of a potential barrier. Broad features are observed in the chlorine 2p continua of CH₂Cl₂, CHCl₃ and CCl₄ and the carbon 1s continuum of CCl₄ which are assigned as the energy loss equivalent of extended X-ray absorption fine structure (EXAFS).     

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.     

Atomic and molecular ions in intense ultra-fast laser fields

The interaction of a 60 fs 790 nm laser pulse with beams of Ar⁺, C⁺, H₂ ⁺, HD⁺ and D₂ ⁺ are discussed. Intensities up to 10¹⁶ Wcm^-2 are employed. An experimental z-scanning technique is used to resolve the intensity dependent processes in the confocal volume.Received: 6 January 2003, Published online: 15 July 2003PACS: 32.80.Fb Photoionization of atoms and ions - 33.80.Rv Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states) - 42.50.Hz Strong-field excitation of optical transitions in quantum systems; multiphoton processes; dynamic Stark shift     

Fast excited-state relaxation of Eu-Eu pairs in commercial Y2O3: Eu3+ phosphors

Low-temperature, dye-laser excitation spectroscopy of commercial Y₂O₃:Eu³⁺ phosphors reveals the presence of complex structure in the excitation lines of the ⁵D₀ and ⁵D₁ manifolds. The structure is associated with the presence of Eu³⁺ ion pairs. The kinetics of the emission decay are observed to be drastically different when excitation occurs either at the center or on the wings of the excitation lines, suggesting faster inter-level and/or inter-site energy transfer on exciting into the line wings. Low-temperature vibronic spectra are reported for the ⁷F₀→⁵D₀ transitions for both C₂ and C_3i sites. Evidence is presented for the detection of the highly forbidden ⁷F₀→⁵D₀ transition for the C_3i site.     

Excitation dynamics of Rydberg states in C<Subscript>60</Subscript>

The electron and nuclear dynamics of C₆₀ fullerenes irradiated with femtosecond laser pulses are investigated with photoelectron and photoion spectroscopy. The focus of this work is the detailed exploration of the population mechanism of Rydberg levels within the excitation process of neutral C₆₀. The effect of excitation wavelength, intensity, chirp, and polarization on the kinetic energy distribution of photoelectrons in single-pulse experiments gives first insight into the underlying processes. In combination with time-resolved two-color pump-probe spectroscopy depending on either pump, or probe pulse intensity, a more complete picture of the interaction can be drawn. The results point towards a very interesting but nevertheless complex behavior including four steps: (i) non-adiabatic multielectron excitation of the HOMO (h_u) → LUMO+1 (t_1g) transition; (ii) thermalization within the hot electron cloud on a time scale below 100 fs, followed by a coupling of energy to vibrational modes of the molecule via doorway state(s); (iii) population of electronically excited Rydberg states by multiphoton absorption, and (iv) single photon ionization from the excited Rydberg states. This excitation process results in a characteristic sequence of photoelectron lines in the photoemission spectra. The comparison of the experimental results with recent theoretical work gives convincing evidence that non-adiabatic multielectron dynamics (NMED) plays a key role for the understanding of the response of C₆₀ to short-pulse laser radiation.     

CASPT2 and CCSD(T) calculations of dipole moments and polarizabilities of acetone in excited states

The acetone molecule is investigated in its ground state and valence ^1,3n-π*, ^1,3π-π*, and ^1,3σ-π* excited states and Rydberg ^1,3n-3s, ^1,3π-3?, ^1,3n-3p_y and ^1,3π-3p_y states using the CASSCF, CASPT2, and CCSD(T) methods. Equilibrium geometries of excited states are obtained and their changes with respect to the ground state are discussed. For most excited states the C_2v symmetry of the ground state is lowered to the C_s symmetry. A series of valence vertical and adiabatic excitation energies is presented along with excitation energies for Rydberg states. The main body of the paper contains Finite-Field Perturbation Theory (FFPT) calculations of electric properties of the vertically as well as geometry relaxed excited states. Dipole moments of valence excited states decrease significantly upon excitation, being about one half of the ground state dipole moment. Polarizabilities usually change upon excitation much less (increase by about 30%) but hyperpolarizabilities are enhanced up to one or two orders of magnitude. The orientation of the dipole moment is reversed in some vertically excited Rydberg states. Properties of the ground and excited states are discussed considering alterations of the electronic structure and shifts in the geometry.     

Improved infrared and visible emission spectra of the H3 and D3 molecules

Better-resolved Rydberg-Rydberg emission spectra of the neutral H₃ and D₃ molecules in the infrared and visible regions, with less interference from H₂ and D₂ emission, have been obtained by using a Droege-Engelking type of corona discharge source. Using nl_λ notation, the lower electronic states are 3p₁ in the infrared and 2p₀ in the visible, and the upper electronic states are mixed (3s,3p₀,3d₀,3d₁,3d₂) states. In particular, a line near 16 842 cm⁻¹ in H₃, previously obscured by an H₂ line, reveals a (3s,3d) interaction that is confirmed by other lines. The spectra are analysed including this interaction. However, fits to effective Hamiltonians still have relatively large standard deviations, probably partly due to poor convergence of the rotational expansions and partly due to many small perturbations of the levels by background states.     

Inner shell electron energy loss spectra of the methyl amines and ammonia

Electron energy loss Spectroscopy has been used to obtain the inner shell excitation spectra of the methyl amines CH₃NH₂, (CH₃)₂NH and (CH₃)₃N for both the N 1s and C 1s regions. A spectrum of the N 1s region of NH₃ is also presented at higher resolution than previously published data. The C ls spectra are all very similar and the discrete portions may be assigned to Rydberg transitions. However, features attributable to a σ^* shape resonance are observed just above the N 1s and C ls ionization edges. The NH₃ spectrum is ascribed to Rydberg transitions. The N 1s spectra of the methyl amines, however, become increasingly dominated by a σ* resonance in the continuum with increased methylation. The features in the inner-shell spectra are compared with the reported valence-shell optical absorption spectra and support the Rydberg assignment. The inner-shell spectra of (CH₃)₃N and NH₃ are also compared with previously published inner shell electron energy loss spectra of NF₃ and the third row phosphorus analogues PF₃,P(CH₃)₃andPH₃.     

332—362nm范围内CF2Cl自由基的共振增强多光子电离研究

用CF₂Cl₂分子直流脉冲放电的方法产生CF₂Cl自由基，结合共振增强多光子电离(REMPI)技术，测量了332—362nm波长范围内CF₂Cl自由基的(2+1)REMPI光谱，分析并标识了4s Rydberg态带源位于(ν_0—0=55371cm^-1)，两个被激活振动模ω′₃(CF₂剪式振动模)和ω₄′(OPL 关键词：     

Observation of the 5pΠu Rydberg state of Li2

Some weak, collisionally induced transitions in ⁷Li₂ have been recorded by Fourier transform spectrometry in the near infrared, following excitation of the 5d¹Π_g state by optical-optical double resonance. They have been assigned as transitions to the 1 ¹Δ_g state from levels v=0 and 1 of a new ungerade Rydberg state, 5p¹Π_u. Quantum defect considerations indicate that the principal quantum number for this new state is 5, and that the assignment to 5p is compatible with a Rydberg series of which the lowest members would be the B¹Π_u and C¹Π_u states.     

Resonant electron impact excitation of highly charged Fe ions studied with a compact electron beam ion trap

We present extreme ultraviolet spectra of 3s3p–3s3d transitions in Fe¹⁴⁺ observed with a compact electron beam ion trap. The contributions of indirect excitation via a metastable state and resonant excitation are studied by observing the electron energy dependence of the spectra for the energy range of 60–210 eV. The results indicate that the 3s3d ¹D₂ level is directly excited from the 3s² ground state whereas the 3s3d ³D₃ level has a large contribution of the indirect excitation via the 3s3p ³P₂ metastable state. Comparisons with the theoretical excitation cross sections including MNn resonant excitations show good qualitative agreement with the experimental results for the electron energy dependent features.     

Investigation of highly excited states of calcium by three-photon ionization

The three-photon ionization in Ca from S₀ ground state is studied. The two-photon process is a near -- resonance process with one of the following bound states: 4s4d ¹D₂, 4p P₂, 4s6s ¹S₀, 4 D₂ and 4 S₀ while the third photon reach either directly the continuum or one of the autoionizing states. The succession of bound states as well as the transitions above the ionization limit are discussed. The dynamics of the multiphoton excitation processes is also discussed and radiative decay of 4 S₀ Ca state with two-photon excitation as well as (the measured) decay times of the Ca autoionizing states using the proper line profiles for different quantum numbers has been determined.Received: 29 September 2003, Published online: 18 May 2004PACS: 32.70.-n Intensities and shapes of atomic spectral lines - 32.70.Cs Oscillator strengths, lifetimes, transition moments - 32.80.Fb Photoionization of atoms and ions - 32.80.Rm Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states)     

Electron-energy-loss spectroscopy of KxC60 and K-halides: comparison in the K3p excitation region

We have investigated the electronic structure of K_xC₆₀ (x=0–6) using low-energy electron energy loss spectroscopy (LEELS), especially focusing on the K_3p core-electron excitation spectra. It is found that the structure of the K_3p-excitation spectrum of K_xC₆₀ quite differs from that of KCl. Furthermore, the K_3p-excitation LEELS of K₃C₆₀ has been revealed to be different from that of K₆C₆₀. K_3p electrons are excited into K_4s- and K_3d-derived empty states in both K_xC₆₀ and KCl, but in the case of K_xC₆₀ the K_3d-derived empty states have a rather complicated structure where several levels are not well separated. Consequently, K_3p-excitation LEEL spectra of K_xC₆₀ show wide-spread plateau-like structures. The difference in the K_3p-excitation spectra of K₃C₆₀ and K₆C₆₀ is considered to originate from the different crystal field around K⁺ cations in the C₆₀ molecular crystal.     

Predicting intense-field photoionization of atoms and molecules from their linear photoabsorption spectra in the ionization continuum

We report a new approach to intense-field photoionization that is based on the ad hoc assumption that m photons of energy arriving within a typical electronic response time are effectively equivalent to a single photon of energy . The heuristic model contains no adjustable parameters and unifies apparent multiphoton and field aspects. Moreover, nonsequential, suppressed and above-threshold ionization phenomena become readily understandable. Predicted ionization intensities are in satisfactory agreement with available experimental data ranging from C₆H₆ to Ne^{3 +} , from femtosecond to nanosecond laser pulses, and from ultraviolet to infrared laser radiation.Received: 20 January 2004, Published online: 17 August 2004PACS: 32.80.Rm Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states) - 32.80.Wr Other multiphoton processes - 42.50.Hz Strong-field excitation of optical transitions in quantum systems; multiphoton processes; dynamic Stark shift     

High resolution laser spectroscopy of Ba Rydberg atoms

The purpose of the present paper is to illustrate some selected aspects of high resolution laser spectroscopy of Rydberg atoms, rather than giving an extensive review of the state of the art. The following topics will be discussed: (i) Excitation and detection of Ba Rydberg atoms with principal quantum numbers up ton≲300; (ii) Stark effect and atomic diamagnetism of high-n Ba Rydberg states in thel-mixing region, (iii) Resonance in singlet-triplet mixing of 6snp¹P₁ and 6snd¹D₂ Ba Rydberg states deduced from hyperfine structure measurements.     

Two-photon spectroscopy of ytterbium

Two-photon laser spectra of the Yb vapor have been obtained. Transitions to highly excited 4f¹⁴ 6sns¹S₀ and 4f¹⁴ 6snd ¹D₂ states are seen in direct two-photon excitation. Hybrid resonances involving 4f¹⁴ 6s6p ¹P⁰₁ and 4f¹⁴ 5d6s ³D₂ intermediate states lead to transitions to 4f¹⁴ 6sns¹S₀, 4f¹⁴ 6snp ³P⁰_2,1 and 4f¹⁴ 6snd ¹D₂ levels.