S2分子B″3Πu态的势能函数和光谱常数的理论研究

推导了S₂分子B″³Π_u态的合理离解极限.用Gaussian 94 QCISD(T)方法和6-311++G^**基组计算了S₂分子B″³Π_u以及X³Σ^-_g态的势能曲线.给出了S₂分子B″³Π_u态的Murrell-Sorbie势能函数和光谱常数.B″³Π_u与B³Σ^-_u态在排斥支重叠范围大；同时，B″³Π_u与X³Σ^-_g态有相同离解极限，因而，在吸引支有重叠.讨论了B″³Π_u与B³Σ^-_u和X³Σ^-_g态相互作用的特征. 关键词：     

The near-ultraviolet spectrum of diacetylene trapped in solid argon at 9 K

The absorption spectra of normal and deuterated diacetylene trapped in solid argon at 9 K were investigated in the near-ultraviolet region between 2000 and 3000 Å. The vibrational structure observed at low temperature for the band system at 2448 Å, which was previously reported by Haink and Jungen in the gas phase, and identified as a ¹Δ_u ← X¹Σ_g⁺ transition, was analyzed. A comparison between the spectra for C₄H₂ and C₄D₂ suggests some revisions in the upper-state vibrational assignments. The possibility that the upper state assumes a C_2htrans configuration of ¹A_u symmetry is examined. The matrix spectra also appear to indicate that the absorption spectrum observed at 2576 Å in the gas phase and which has been assigned to a ¹Σ_u^? ← X¹Σ_g⁺ transition may not originate in the ground state of C₄H₂.     

The ultraviolet absorption spectra of GeO in rare gas matrices

The absorption spectra of GeO isolated in rare gas matrices have been investigated in the wavelength region 1150–3000 Å using the 2.5-GeV synchrotron in Bonn as a continuum light source. Two vibrational progressions of bands have been found in each of the matrices, in neon, argon, krypton, and xenon. These progressions are situated in the regions 2400–2700 and 1800–2100 Å. They have been analyzed as corresponding to gas-phase bands of the A¹Π-X¹Σ⁺ and the E¹Σ⁺-X¹Σ⁺ systems, respectively. Absorption lines of matrix-isolated GeO were also found in the region 1180–1500 Å.     

Continuous wave optically pumped iodine laser: Spectroscopy and long range analysis of the X1Σg+ ground state of I2

Continuous wave oscillation is observed on transitions belonging to the I₂B 0_u⁺-X¹Σ_g⁺ system into highly excited vibrational levels of the ground state. The I₂ laser is optically pumped with a single longitudinal mode argon ion laser oscillating at either 514.5 or 501.7 nm resulting in some 752 assigned laser lines throughout the visible and near infrared. Of these, 44 transitions have 83 ≤ v″ ≤ 96 and are used here to obtain rotational and vibrational constants for levels of X¹Σ_g⁺ near the dissociation limit. A long range analysis applying the theory of LeRoy to the highest observed levels yields C₆ = 1.1 ± 0.1 × 10⁶ cm^?1 Å^?6 and indicates that the last bound vibrational level of X¹Σ_g⁺ has v = 114.     

The optical spectrum of the doubly charged molecular nitrogen ion: Rotational analysis of the (0-0) and (1-1) bands of the D1Σu+-X1Σg+ transition of N22+: Comparison of observations with Ab-initio calculation results

Emission spectra obtained in the 1550–1650 Å region with a 10-m vuv spectrograph are conclusively assigned to the N₂²⁺ ion. The 1589-Å band, previously observed by Carroll, and a new band of the same system, have been rotationally analyzed. Ab-initio calculations have been performed which support the assignment of these two bands to the D¹Σ_u⁺-X¹Σ_g⁺ system. The calculations also explain the observed breaking-off points in the branch structure as well as weakening and broadening of the other expected bands. These phenomena arise from electron configuration changes and perturbation effects in the ground state.     

The Hg2 (A3Ou− → X1Σg+) and (A31u → X1Σg+) fluorescence

The fine structure emission sepctrum near 5500 Å attributed to the Hg₂ (A³O_u^? → X¹Σ_g⁺) transition is shown to be strikingly similar to the HgCl (B²Σ⁺ → X²Σ⁺) emission spectrum sensitized by Hg(6³P_o) metastables. The correct Hg₂ (A³O_u^? → X¹Σ_g⁺) emission spectrum at 4850 Å was re-examined and confirmed to be a continuous one. It is suggested that the fine structure arose from the sensitization of a chlorine containing impurity.     

New Bands in the Shock Excited NbO Blue/Visible and Near Infrared Systems

Abstract

Band systems of the astrophysically important molecule Niobium Oxide (NbO) have been excited in helium-driven shock waves through argon containing powdered Nb₂O₅. Of the 25 bands of the Δv = +3, +2, +1,0, -1, -2 and -3 sequences of the C ⁴Σ^? – X ⁴Σ^? blue/visible system which were excited between 4220Å and 5608Å, 16 are newly reported here. The Δv = +3 and -3 sequences are completely new. 12 new bands were also excited in the near infrared region 7952Å - 8450Å.     

Deperturbation of the N2+ first negative group B2Σu+-X2Σg+

Twelve bands of the N₂⁺B²Σ_u⁺-X²Σ_g⁺ system, including v_B = 0–6 and v_X = 0–8, are reanalyzed. All effects of B²Σ_u⁺ ～ A²Π_u perturbations are explicitly considered. Despite the use of high precision (0.01 cm^?1) line measurements, no evidence for a perturber other than A²Π_u is obtained. Deperturbed constants for the B²Σ_u⁺ and X²Σ_g⁺ states are derived. The deperturbation is shown to be self-consistent and complete (excluding effects of the C²Σ_u⁺ state) by examining semiempirical relationships of the perturbation matrix elements with the spin-rotation constants of the B and X states and atomic spin-orbit parameters. A number of previous analyses of transitions involving the v_B = 3 and 5 levels are found to be incorrect.     

Predissociation linewidths and oscillator strengths for the (2-0) to (13-0) Schumann-Runge bands of O2

Analysis of the absorption spectrum of O₂ in the Schumann-Runge bands (B³Σ_u^?-X³Σ_g^?) from the 2-0 to the 13-0 band yields oscillator strengths which are in good agreement with past theoretical calculations. Predissociation linewidths deduced from the data tend to be larger than theoretical predictions for v′ ≤ 5 and are reasonably near theory for v′ > 5. The qualitative dependence of the linewidths on vibrational level is in accord with that expected for a repulsive potential intersecting the B³Σ state near v′ = 4. For a given band the predissociation linewidth deduced from the spectra tends to increase as the total angular momentum increases. The new linewidths are smaller than some past experimental results, and this will have an impact on future calculations of the photodissociation rates of O₂, NO, and H₂O in the earth's upper atmosphere.     

Microwave spectrum of γ-valerolactone

An Ar⁺ laser at 4579 Å is used to excite the B¹Π_u-X¹Σ_g⁺ fluorescence of the ⁶Li⁷Li molecule in a crossed heat pipe oven. The spectrum in the region 4400–6300 Å is recorded photoelectrically with an emphasis on the observation of higher vibrational levels in the ground state close to the dissociation limit. P and R doublets corresponding to v″ ≤ 26 originating from the (v′ = 13, J′ = 19) level are observed and identified using mass-reduced quantum numbers. Two additional ⁶Li⁷Li series, known from earlier work of Velasco, Ottinger, and Zare, are also analyzed. These data are used to construct effective Rydberg-Klein-Rees (RKR) potentials for specific J″ (=9, 19) quantum numbers of the ground state and from them the true (rotationless) potential energy curve (for X¹Σ_g⁺) is derived. This extends the previously known curve of Li₂ from 4.28 to 5.18 Å (outer turning point); this turning point corresponds to an energy which is approximately 88% of the dissociation energy, which is estimated here to be 8516 ± 18 cm^?1.     

Determination of the B1II-X1Σ and C1Σ-X1Σ electronic transitions strengths of CaO

The strengths S_e of the B¹II-X¹Σ electronic transitions of the CaO molecule have been determined by absorption measurements in a shock tube. Powdered calcium oxide and a gaseous mixture of oxygen and argon in the ratio of 1:5 or 1:9 were introduced into the shock channel. The CaO gas-phase concentration was determined by using the equilibrium constant for CaO?Ca + O; atomic oxygen concentration was calculated and that of calcium was measured spectroscopically. The values of S_e (in atomic units) are for B¹II-X¹Σ, 1.7 ± 0.5; for C¹Σ-X¹Σ, 2.1 ± 0.6.     

The electronic spectrum of bismuth monofluoride: An 0+ ← X10+ band system at 3838 Å

Emission bands of BiF (in the region of 3800 Å), formerly designated as belonging to the B-X₁0⁺ and A₃-X₁0⁺ transitions, have been photographed and rotationally analyzed under high resolution. These bands have been found to belong to an 0⁺ ← X0⁺ system. Extensive rotational and vibrational perturbations have been observed and the nature of the perturbing state is discussed.     

Intracavity laser absorption spectroscopy of AuO: Identification of the BΣ-XΠ3/2 transition

The visible electronic spectrum of AuO has been recorded at rotational resolution using intracavity laser absorption spectroscopy. Six vibrational bandheads have been identified, and three of the bands have been analyzed and assigned as bands of a newly identified B²Σ⁻-X²Π_3/2 transition of AuO. The molecular parameters for the newly identified B²Σ⁻ state are presented.     

Rotational analysis of the a3Π-X1Σ+ bands of GaD

A new method of producing strong and clean emission spectra of the gallium hydride/deuteride molecule has been developed. Five bands belonging to the gallium deuteride molecule (GaD) have been photographed under high resolution. The rotational analyses of the bands lying at 5669.14 Å (0-0) and 5675.10 Å (1-1) in the a³Π₁-X¹Σ⁺ transition, 5761.0 Å (0-0) and 5766.20 Å (1-1) in the a³Π_0⁺-X¹Σ⁺ transition, and 5760.85 Å (0-0) in the a³Π_0⁻-X¹Σ⁺ transition have been performed. Accurate rotational constants (B, D) have been determined for the X¹Σ⁺, a³Π_0^± and a³Π_1^± states. The Λ doubling in the a³Π₀ (v = 0) and a³Π₁ (v = 0 and 1) states are obtained.     

Studies of labile molecules with a tunable dye laser: Laser excitation spectrum of BrF (B3Π(0+)-X1Σ+)

The B³Π(0⁺) ← X¹Σ⁺ absorption spectrum of BrF (4850–5200 Å) has been observed by the technique of laser emission spectroscopy. Fluorescence was excited by a pulsed, scannable dye laser with a 0.1 Å bandwidth. Rotational analysis has been carried out for six bands of the v″ = 0 progression (8 ≥ v′ ≥ 3) of ⁷⁹BrF and ⁸¹BrF. Rotational constants for the B³Π(0⁺) state are reported for the first time. RKR potential energy curves for both states, and an array of Franck-Condon factors and r-centroids for the transition, have been calculated. Bands with v′ > 8 were not observed in fluorescence owing to the onset of predissociation near J′ = 28 of the v′ = 8 level. An upper limit for the ground state dissociation energy is D₀″ (BrF, X¹Σ⁺) ≤ 20 880 cm^?1.     

On the non-BoltzmannA-X emission in Na2 following laser excitation of theB state

A ¹Σ _u ⁺ -X ¹Σ _g ⁺ emission in Na₂ is observed following excitation ofB ¹π _u by various lines of an argon ion laser. The excitation energy ofB ¹π _u is collisionally transferred to the (2)¹Σ _g ⁺ which then radiatively populates theA ¹Σ _u ⁺ state. The Na vapour is contained in a stainless steel crossed heat pipe with Ar buffer gas and temperature around 600°C. For all laser lines except 4579 Å, the coarse features ofA-X emission are independent of the laser wavelength. However, at high resolution the finer differences between different laser line excitation are explained. Variousv′-v″ transitions in this emission are identified. Computer simulation is presented to help explain some features of this emission.     

The electronic spectrum of silicon monotelluride radical

In the electronic spectrum of silicon monotelluride which has been produced in microwave discharges through sealed tubes, a large number of new bands belonging to theA ¹Π-X ¹Σ⁺ system (3100–3900 Å) and theE ¹Σ⁺-X ¹Σ⁺ system (2800–3100 Å) of Si¹³⁰Te has been observed. The vibrational structure analyses of these band systems have resulted in the determination of improved vibrational constants in all the three electronic states involved in these transitions. An error in the previous determination of the vibrational constants of theE ¹Σ⁺ state has been corrected. An upper limit for the dissociation energy of the silicon monotelluride has been determined to be 40,000 cm^?1.     

High resolution Fourier transform spectrum of GaCl

The electronic emission spectrum of the A³Π₀-X¹Σ⁺ and B³Π₁-X¹Σ⁺ transitions of Gallium monochloride molecule (⁶⁹GaCl) has been recorded on BOMEM DA8 Fourier transform spectrometer at an apodized resolution of 0.035 cm⁻¹. The rotational structure of the 0-0, 1-0, 2-1, and 3-2, bands belonging to A-X and 0-0, 0-1, 1-2, and 0-2 bands belonging to B-X transitions has been analyzed and equilibrium rotational constants for the X¹Σ⁺ and A³Π₀ states have been obtained. For the first time we are able to determine the Λ-doubling constants in the v = 0 and 1 levels of the B³Π₁ state.     

Inelastic scattering and satellite fine structure in the high-resolution uv photoelectron spectrum of CS2

The outer valence region in CS₂ has been studied by high-resolution UV photpelectron Spectroscopy. The spectra reveal detailed vibrational structure in the X$\text{\$}\text{?}$²Π_g, A$\text{\$}\text{?}$²Π_u, B$\text{\$}\text{?}$²Σ⁺_u and C$\text{\$}\text{?}$²Σ⁺_g bands. Some of the fine-structure peaks in the X$\text{,}\text{?}$B$\text{\$}\text{?}$and C$\text{\$}\text{?}$bands are shown to be pressure-dependent. The reason for the pressure dependence is assumed to be inelastic scattering of electrons emitted in the adiabatic transitions. It is established that the two CI satellite bands present in the He(I)-excited spectrum contain vibrational structure.