What is so mysterious about the electronic states of SCI?

The 15 lowest lying doublet electronic states of the molecule SCI have been investigated theoretically at a high level of correlation treatment (MRCI). For the ground state (X ²II), spectroscopic constants were obtained from a set of eight vibrational intervals. This result extends our knowledge about this state beyond the experimentally known data that presently were derived from only two bands. Spin-orbit constants, transition probabilities and radiative lifetimes complement its spectroscopic characterization. For the excited electronic states, a global view of the doublet states is presented that can help us understand the scarcity of experimental data on electronic transitions for this system and also the difficulty of assigning the only two transitions so far recorded. Most of these states are repulsive, and for the few high lying bound ones, of Rydberg character, avoided crossings restrict the number of accessible vibrational states. Crossing by repulsive states and predissociation is also a factor that can prevent further emissions. Two new bound excited states, ²δ and ²Σ, predicted in this study, are of direct relevance to an interpretation of the limited experimental data available on electronic transitions.     

Cl2分子Rydberg态及混合Rydberg-价态多光子光谱

本工作结合多光子离化谱,激光诱导荧光及荧光激发谱技术,仔细研究Cl₂分子高激发Rydberg态和混合Rydbery-价态的结构及性质,定域了1¹∑_u⁺态内区的位置,证明2¹∑_u⁺态强的Rydberg-价混合特征,发现一新的u对称性Rydberg态并建议标识为¹∑_u态的激发,对三光子激发过程,2^{1关键词：}     

Electron spectroscopy of autoionizing states of nitrogen atoms

During excitation of N₂, NO and N₂O molecules by fast neutral 1¹S helium atoms, highly excited molecular states are formed which yield, through predissociation, autoionizing nitrogen atoms. The energy of electrons released in autoionization was measured and the energy and plausible spectroscopic assignment of autoionizing levels was determined. The excited levels belong to Rydberg series converging to the N⁺(¹D) series limit. Besides molecular states derived by correlation of the final atoms, highly excited molecular parent states are also discussed.     

Low-lying valence and Rydberg states of NS, obtained by configuration-interaction studies

Using double-ζ plus polarization basis sets with diffuse s and p functions on N and S, configuration-interaction calculations were carried out for low-lying valence and Rydberg states of NS. In general, there is good agreement with experimentally obtained spectroscopic constants, and with theoretical results obtained by other groups. The avoided crossing of 2²Σ⁺(C) and 3²Σ⁺(I), and the reported predissociation from low vibrational levels of the C state received particular attention.     

MRCI studies on ground and excited states of CBr

Potential curves and spectroscopic constants for a large number of doublet and quartet states of CBr were obtained by multireference configuration interaction calculations, using valence triple-zeta basis sets with polarization and diffuse functions. Besides the X²Π ground state, 1⁴Σ^?, 1²Δ and 2²Σ⁺ have been found to be stable. Spectroscopic constants calculated for 1²Δ are in excellent agreement with experimental values obtained by Dixon and Kroto in 1963. Their observed predissociation of one component of 1²Δ can be explained by the crossing of the 1²Δ potential near equilibrium by 1²Σ⁺. The 1²Σ⁺ state is calculated to have a shallow long-range minimum at 2.31?Å. The dissociation energy of X²Π is calculated to be 3.43?eV. An observed T _e of 4.97?eV for 2²Σ⁺ agrees with the theoretical value. Several Rydberg states of the 2π→Ryd and 3σ→Ryd series, starting at T _e ?=?5.25?eV, were identified. Photodissociation of CBr by sunlight, important in the ozone cycle, can occur via direct dissociation of the ground state, or by excitation to 1²Δ followed by predissociation. Most dissocative repulsive states lie at higher energies, and are not expected to participate in the photodisscociation of CBr.     

A theoretical study of the spectroscopic states of the CF molecule

LCAO-MO SCF calculations on the ground and excited states of CF are described. Close agreement with observed term values is obtained. The calculation of some molecular properties is discussed, and a very good result is obtained for the spin-orbit coupling in the ground state. The positive spin-orbit coupling in the ²Δ state is not explained. It is shown that the observed predissociation in the A state must be attributed to a curve crossing at a smaller internuclear distance than equilibrium, and that the ⁴Σ^- state from 5σ 2π² is responsible. Calculations show that a second-order treatment of the A ²Σ⁺-⁴∑^- interaction is necessary and sufficient to account for the predissociation.     

The splitting of low-lying or low excited states for hydride molecules （cations） of the third period under spin-orbit coupling

This paper reports that the splitting of potential energy curves for the low-lying or low excited states for hydride molecules （cations） （MgH, AlH^＋, SiH, PH^＋, SH,ClH^＋） of the third period under Spin-Orbit Coupling has been calculated by using the Spin-Orbit Multi-Configuration Quasi-Degenerate Perturbation Theory （SO-MCQDPT） method. Then, spectroscopic constants of the split states have been derived from the Murrell-Sorbie function. The calculated dissociation energies for the spectrum branch terms have been given, respectively. The spectroscopic constants and dissociation energies for the spectrum branch terms are given for the first time in this paper.     

氢分子3pπ D1πu+和4pσ B″1Σu+态的预解离

运用量子亏损理论，并与参考系变换及本征通道R-矩阵法相结合，建立了描述氢分子里德伯态的预解离过程的理论方法．通过对氢分子的3pπD¹π_u⁺和4pσ B″¹Σ_u⁺电子态的预解离过程的研究，阐明其解离的机理，并给出预解离的线宽． 关键词：     

Resonant multiphoton dissociation of the NO molecule

The multiphoton dissociation of an unexcited NO molecule involving intermediate Rydberg states n?σ(²∑⁺), n?π(²П), and n?δ(²Δ), which are populated by a weak probe field and decay owing to nonadiabatic transitions in the predissociation states of valence configurations B′²Δ, L ²П, I ²∑⁺, and B ²П, has been studied. The role of the ponderomotive interaction that occurs under the simultaneous action of an intensive electromagnetic monochromatic radiation on the studied system has been analyzed. A theory to describe the dynamics of the process has been described. The possibilities of laser stimulation of this process, which consist in the search for ranges of variation in the frequencies and intensities of laser radiation that provide the highest efficiency of the resonant photostimulated process, have been discussed.     

Symmetric linewidth variations in the electron resonance spectra of biradicals

The infrared emission spectrum of the Rydberg molecule XeH was recorded with the Kitt Peak Fourier transform spectrometer. XeH was made in a hollow cathode discharge of 2·2 torr H₂ and 0·1 torr Xe. The 0-0 bands of the C ²Π-B ²Σ⁺ and the D ²Σ⁺-C ²Π transitions were observed near 3250 cm^?1 and 4420 cm^?1, respectively. A rotational analysis provides spectroscopic constants for these states.     

Rotational analyses of the A1Π-X1Σ+ and the a3Π-X1Σ+ systems of AlBr

The absorption spectrum of the A¹Π-X¹Σ⁺ system and the emission spectrum of the a³Π-X¹Σ⁺ system of AlBr have been examined at higher resolution than previously used. The present study has produced a significantly improved set of molecular constants for these excited states of AlBr. All data have been fitted in a self-consistent manner for an optimum set of constants. The broadening of features in the A-X system has been attributed to type c⁺ predissociation in the A¹Π state. Also, a comparison is made between the emission and absorption spectra of the A-X system.     

II: PROPERTIES OF DIATOMIC AND TRIATOMIC MOLECULES

Results are presented from a theoretical study of the × ⁶Σ⁺, A ⁶Σ⁺ and ⁶Δ electronic states of CrH using multiconfiguration second-order perturbation theory in the multi-state formalism (MS-CASPT2). It is shown that the results for the spectroscopic constants and radiative lifetimes for the A state are in agreement with experiment and an earlier multireference configuration interaction study only if the two close lying × and A states are allowed to interact at a level of approximation that includes dynamic correlation.     

Potential energy curves for the 48 lowest-lying molecular states of LiH+

The electronic energies of the 20 lowest lying ²Σ⁺ states, the 14 lowest lying ²Π states, and the 14 lowest lying ²Δ states of LiH⁺ have been calculated in the range 2 ≤ R ≤ 20 a.u. from a model potential approach and using truncated diatomic orbitals (TDO) as basis set. Results in very good agreement with the more recent literature were obtained for the spectroscopic constants, R_e and D_e, for the ground state X²Σ⁺.     

利用自电离探测技术研究Sm原子Rydberg态光谱

采用孤立实激发与自电离探测技术相结合的方法对Sm原子偶宇称高激发态进行了系统研究.按照不同的自电离通道将所测数据进行了分类和比较,并进行了详细讨论.不仅报道了许多收敛于不同电离限的Rydberg态的能级位置和跃迁的相对强度等信息,而且还把处于同一能域内的Rydberg态和价态进行了辨识.另外,不但提供了一种有效识别不同类型的高激发态的鉴别技术,而且还对处于41800 cm^-1到43800 cm^-1能域内的Rydberg态和价态的光谱特性进行了详细分析和讨论. 关键词： 自电离探测 Rydberg态 Sm原子     

Electronic states of SiF and SiF+: Configuration-interaction studies

For SiF, low-lying ²Π, ⁴Π, ²Σ⁺, ⁴Σ⁺, ²Σ⁻, ⁴Σ⁻, ²Δ, and ⁴Δ states were studied by configuration-interaction methods, using a double-zeta plus polarization basis set with 4s, 4pσ, 4pπ, and 5pπ Rydberg orbitals. Potential energy curves and spectroscopic constants for 17 stable valence and Rydberg states are given. The lowest ²Σ⁻ state is repulsive. There is good agreement with known spectroscopic constants. Besides A²Σ⁺, another semidiffuse state, 1⁴Π, is predicted. For the isoelectronic PO molecule, 2π → 3π valence excitations lie below Rydberg excitations, such that 2²Π of PO derives from 2π → 3π, whereas 2²Π of SiF derives from 3π → 4pπ. Dipole moments of X²Π and A²Σ⁺ at their respective R_e, and the radiative lifetime of A²Σ⁺ were calculated. For SiF⁺, many electronic states were investigated, but only two, the X¹Σ⁺ ground state and 1³Π are found to be stable. The ionization energy of SiF is calculated to be 6.87 eV (adiabatic) and 7.05 eV (vertical).     

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.     

Spectroscopic investigations on NO+(x1∑+,a3∑+,A1Ⅱ) ion using multi-reference configuration interaction method and correlation-consistent sextuple b

Three low-lying electronic states (x¹∑⁺,a³∑⁺,and A¹Ⅱ) of NO⁺ ion are studied using the complete active space self-consistent-field (CASSCF) method followed by highly accurate valence internally contracted multi-reference configuration interaction (MRCI) approach in combination of the correlation-consistent sextuple basis set augmented with diffuse functions, aug-cc-pV6Z. The potential energy curves (PECs) of the NO⁺(x¹∑⁺,a³∑⁺,A¹Ⅱ) are calculated. Based on the PECs, the spectroscopic parameters R_e, D_e, ω_e, ω_eχ_e, α _e, B_e, and D₀ are reproduced, which are in excellent agreement with the available measurements. By numerically solving the radial Schrödinger equation of nuclear motion using the Numerov method, the first 20 vibrational levels, inertial rotation and centrifugal distortion constants of NO⁺(x¹∑⁺,a³∑⁺,A¹Ⅱ) ion are derived when the rotational quantum number J is equal to zero (J = 0) for the first time, which accord well with the available measurements. Finally, the analytical potential energy functions of these states are fitted, which are used to accurately derive the first 20 classical turning points when J = 0. These results are compared in detail with those of previous investigations reported in the literature.     

(2 + 1) Resonance enhanced multiphoton ionization of hydrogen chloride in a pulsed supersonic jet: Vacuum wavenumbers of rotational lines with detailed band analysis for excited electronic states of HCl

A comprehensive study of the excited electronic states of HCl is reported. Using resonance enhanced multiphoton ionization ((2 + 1) REMPI) and time-of-flight mass spectrometry (TOFMS) over 120 band systems are analyzed. Supersonic jet techniques are used to prepare rotationally cold species for laser spectroscopy in the 77 000 to 96 000 cm⁻¹ region. At least 50 new electronic states are characterized as well as several features only tentatively assigned previously. A long vibrational progression consisting of 29 vibrational levels of the deeply bound V¹Σ⁺(0⁺) valence/ion-pair state is studied. We also extend the identification and analysis to high vibrational levels of low-lying Rydberg states. The assignments of [²Π_i] Rydberg state complexes are evaluated in terms of spin-orbit coupling and united-atom calculations. In several band systems, the spectra exhibit anomalous rotational line intensities and broadened linewidths which are consistent with predissociation. Multiphoton ionization with mass spectrometry permits the investigation of isotope effects as well as the appearance of fragment species associated with repulsive potential curves.