Pressure induced configuration demixing in the electronic spectrum of NO

Previous low resolution studies indicated that, in the absorption spectrum, transitions to Rydberg states are far more sensitive to pressure than transitions to valence states in accordance with the complete vanishing of Rydberg bands and the deperturbation of the valence bands in the spectrum of NO trapped in a solid rare gas matrix. The present study of NO is the first extensive investigation of medium and high resolution molecular electronic spectra subjected to pressure of foreign gases. It is observed that, at the highest pressure attained (～1000 bar), almost all of the Rydberg bands have vanished whereas the remaining valence bands stay relatively sharp. While high pressure medium resolution spectra give information about the deperturbation of intensities and of vibrational spacings of the valence bands, inspection of low pressure high resolution spectra reveals that the rotational lines react to pressure in a way reflecting closely the degree of configuration mixing between Rydberg and valence states.     

The spectrum of SiO in the vacuum ultraviolet region

The absorption spectrum of SiO has been photographed at high resolution in the region 1200–1500 Å. Several new electronic states have been observed, valence states as well as Rydberg states. Tables of the molecular constants of all the known states of SiO are given. Due to interactions between the electronic states, the constants of all states analyzed vary irregularly. From the Rydberg series a value of the ionization potential has been derived. It agrees with the value earlier reported, 11.6 ± 0.2 eV.     

An ab initio molecular orbital study of the electronically excited and cationic states of the ozone molecule and a comparison with spectral data

A number of valence and Rydberg, singlet and triplet excited states for ozone in the excitation energy range 1–12eV have been calculated by large scale CI methods preceded by MCSCF studies. A comparison of the theoretical intensity envelope with the VUV + EELS spectrum has been made. The present work supports the assignments for the Huggins + Hartley bands as having two electronic origins, 2 ¹A₁ and 1 ¹B₂. The experimental ～ 9.3eV and ～ 10.2eV bands of the VUV spectrum must have adventitious superposition of valence states on Rydberg transitions, because the high oscillator strengths of the valence states cannot be attributed to the 8.8eV broad band. A number of new valence and Rydberg states have been calculated, and these lead to the conclusion that the experimental 9–11 eV VUV spectral range in particular must yield more experimental states than the few so far identified. This suggests a major need for more sophisticated methods of experimental study for the excited state manifolds. The use of various MCSCF/CI studies of the vertical cationic states, supports the IP order as ²A₁ < ²B₂ < ²A₂. A re-analysis of the 12–13.4eV range of the UV-photoelectron band has been performed, with a view to determining the adiabatic IPs more accurately. The present work suggests that the adiabatic IP₂ lies at 12.86eV, slightly lower than has been assumed, with consequential effect on the analysis of the VUV spectrum near 9.4eV.     

铕原子奇宇称高激发态共振电离光谱的研究

采用光电离探测和自电离探测这两种不同的探测方法对铕原子的高激发态光谱进行了详细研究.一方面,采用光电离探测技术,系统测量了在第一电离限之下处于43927—45010 cm^-1能域内的奇宇称能级的光谱.通过光谱定标和误差估算等分析手段,获得了32个共振跃迁峰的位置和强度等光谱信息.并根据所用的激发路线和相关的选择定则等原理,进而确定了这些能级的总角动量. 通过与相关文献资料的对比和分析,研究发现了12个新能级.另一方面,精心设计了一种能够有效识别不同类型高激发态的鉴别方法.对同一能域中 关键词： Eu原子光谱 奇宇称高激发态 孤立实激发（ICE） 自电离探测     

The threshold electron impact spectrum of H2O

The threshold electron spectrum of H2 O was obtained using a high resolution electron impact spectrometer combined with the penetrating field method for scattered electrons with energies close to zero eV. The valence, triplet Rydberg states, as well as the resonances were identified and are discussed in the energy region 5.2–14.3 eV. The threshold spectrum confirms the influence of resonances on the enhancement of the intensity of some Rydberg states above 10 eV. The vibrational spacing of the observed transitions of the Rydberg states indicates that the water molecule is excited in the symmetric stretching mode.     

Low energy electron spectroscopy of CO in the 10.600–14.400 eV energy loss range

Excitation spectra of CO have been obtained at low electron impact energy in the 10.600–13.400 eV energy loss range for scattering angles from 10 to 120°, with a 35 meV experimental resolution. The angular behaviour of the observed peaks is used to discriminate singlet-singlet and singlet-triplet transitions. Previously calculated Rydberg states are observed, in particular the triplet analogue of the F¹Σ⁺ state. A new high energy valence triplet state is identified; the first observed vibrational level is at 11.595 eV and the vibrational spacing is 90 meV. Upper levels are strongly affected by predissociation.     

New valence and Rydberg states of the P18O molecule

The absorption spectrum of the P¹⁸O molecule has been studied in the region 1650–1800 Å. The upper levels of the transitions are shown to be levels of new ²Π valence, ²Π Rydberg and ²Δ Rydberg states of the PO molecule. Most of the levels are perturbed; some of them are predissociated. The new valence state P²Π corresponds to a regular state of the electronic configuration $\text{σ}{}^2\text{π}{}^3\text{π}{}^{12}$ and the ²Π and ²Δ Rydberg states belong to the 5p, 3d, 4d complex series. Perturbations of the P²Π state are shown to arise from Rydberg ～ Non Rydberg interactions with states of same or different symmetry. The complexity of the interactions does not allow to carry out a deperturbation but a comparison with the data of the P¹⁶O molecule allows to give a vibrational assignment to the levels of the P²Π state.     

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.     

Threshold electron impact excitation of Cl2

A high resolution electron impact threshold spectroscopy technique was used to examine the excitation of Cl₂ in the 2–14 eV region. This study complements previous photon absorption and emission measurements, because it is capable of detecting transitions which are optically forbidden. In the region up to 7.5 eV, broad dissociative structures are correlated with optically active valence states, although relative intensities in the threshold spectrum differ considerably and indicate a substantial contribution from the optically forbidden transitions. At 7.46 eV a series of 5 equidistant sharp peaks is detected and interpreted as arising from the² π _g Feshbach resonance, which differs from the ground state positive ion Cl ₂ ⁺ by a pair of Rydberg electrons: (4sσ)². The decay channels responsible for the appearance of the resonance in a threshold spectrum are discussed and it is suggested that they include several valence states of the (2431) and (2341) configurations, whose potential energy curves cross the Cl ₂ ^? ,²π_g curve in the region of energy at which the resonance state is formed. At higher incident electron energies and up to ionisation, Rydberg states predominate, starting with (2430) 4s^3,1 π _g states detected for the first time. The absence of broad peaks above 8 eV and the irregular appearance of Rydberg bands is consistent with the strong Rydberg-valence configuration mixing proposed by Peyerimhoff and Buenker. Where our resolution permits comparison, good general agreement is found with recent synchrotron radiation absorption measurements of optically allowed transitions.     

Ab initio study of the ground and excited states of hydrogen sulphide using SCF and CI calculations

Results from ab initio SCF and CI calculations on the ground state and low-lying valence and Rydberg states of H₂S are reported. A double ξ basis of contracted gaussian functions augmented by polarization and diffuse 3d, 4s and 4p functions is used for the calculations. The geometries of various excited states are studied by means of SCF calculations. The first observed band in the absorption spectrum is predicted to arise from the overlapping of transitions from the 2b₁ orbital to a Rydberg 4s and strongly bent valence upper state. The calculations support the assignment of other spectral features to transitions from the 2b₁ to components of the Rydberg 3d and 4p orbitals.     

Laser control of low-temperature reaction <Emphasis Type="Italic">e</Emphasis><Superscript>−</Superscript> + O<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>

A theory is developed to describe dissociative recombination of a slow electron with a ground-state molecular ion of oxygen driven by a strong monochromatic electromagnetic field. Mathematically, the theory is based on the time-independent formalism of radiative scattering matrix whose poles correspond to dressed intermediate states of the complex. The analysis embraces both transitions to dissociative states and laserinduced nonadiabatic transitions to intermediate bound states of valence configurations. Key reaction mechanisms are considered, and a classification is given of all allowed transitions to dissociative states. Partial and total reaction cross sections are calculated by taking into account the contributions from Rydberg, valence, and dissociative states of O₂^**. A detailed discussion of results is presented, and feasibility of laser control of the reaction is demonstrated.     

Excitation spectrum of the lithium acceptor in CdTe and estimation of the valence band parameters

The infrared absorption of lithium doped CdTe shows sharp lines in the energy range 30–80 meV which are attributed to electronic transitions from the ground state to the excited states in the lithium acceptor and LO phonon assisted transitions. This excitation spectrum is analyzed using the theory of Baldereschi and Lipari what leads to a determination of the Luttinger valence band parameters.     

Vibrational transitions in Rydberg matter clusters from stimulated Raman and Rabi‐flopping phase delay in the infrared

Recently, rotational spectra of giant Rydberg matter (RM) clusters were studied in the radio frequency range (Mol. Phys. 105 (2007) 933–939), giving high‐precision bond distances in the nanometer range. However, the theoretical and experimental problem of vibrational motion or, rather, coupled electronic‐vibrational motion in the RM clusters is still unsolved; but it is expected that broad phonon bands will exist. Spectroscopic signatures from space make it likely that RM is a common form of matter in the Universe, and phonon bands in this spectroscopic range have not been taken into account so far. Spectroscopic results are now reported on transitions in the range 0.01–20 cm⁻¹, using primarily infrared (IR) lasers to probe the RM in a tunable open cavity with a Fabry–Perot interferometer to aid in the identification of the shifts. Stimulated Raman scattering from electronic transitions and Rabi‐flopping from electronic states in the clusters are observed. The broad stimulated Raman peaks are assigned to one and two consecutive vibrational (electronic‐vibrational) transitions. Theoretical values predicted for vibrations (phonon maxima) and electronic processes are in reasonable agreement with the experimental results. Improved calculations are needed to verify the assignments of the vibrational phonon distributions. Copyright © 2008 John Wiley & Sons, Ltd.     

Configuration interaction calculations of the satellite peaks observed in the core and valence photoelectron spectra of N2

Configuration interaction calculations are used to interpret satellite peaks observed in the X-ray and He (II) photoelectron spectra of N₂. Using a basis containing diffuse atomic functions, the X-ray peaks are assigned to states involving transitions to valence and Rydberg type orbitals. The three satellites in the He (II) spectrum are correlated with states involving occupancy of the 1π_g and 4σ_g molecular orbitals.     

Photoelectron and electron impact spectrum of HCN

The electronic structures of HCN and DCN have been determined by examining high resolution He(I) photelectron spectra of HCN and DCN, He(II) photoelectron spectrum of HCN, and the electron impact energy loss spectra of HCN and DCN. The present investigation supports an earlier assignment of the orbital sequence in HCN. New vibrational data are presented and the Rydberg series and valence transitions are reinvestigated. The adiabatic ionization energies for the 1π and 5σ orbitals in HCN are found to be 13.607 ± 0.002 eV and 14.011 ± 0.003 eV respectively.As mentioned above the investigation of the Rydberg series indicated that the first IP at 13.607 eV is the 1π ionization and the second IP at 14.011 eV is the 5σ ionization. A comparison of the experimental and theoretical intensity ratio between the two first PES progressions also supports this assignment. It is further supported by the fact that in the second IP the ν₃ vibration frequency is not changed as much as it is in the first IP, which is in agreement with the PES of N₂ and CO. The analysis of the bending vibrations also supports this ordering of the orbitals.The same orbital assignment has recently been proposed by Frost et al.⁵, using a comparison with the HCP photoelectron spectrum. The present paper supports their assignment of orbitals and (00⁰0)-(00⁰0) transitions. There are, however, some disagreements concerning the vibrational analysis. This is probably due to the fact that the HCN spectrum of Frost et al.⁵ revealed less structure than ours. As indicated by Figure 5 there is possibly still more structure to be revealed.     

Vibrational Analysis of the β System of 10B18O

Ten bands of the β system (B²Σ⁺ ? X²Σ⁺) of the ¹⁰B¹⁸O molecule have been observed for the first time. The spectrum was obtained by emission spectroscopy from a low‐pressure arc, at medium dispersion, and vibrationally analyzed using isotope shift measurements. Vibrational analysis gave the constants ω_e and ω_ex_e for both electronic states involved in the 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.