Millimeter- and submillimeter-wave spectra of AuCl and AuBr in the XΣ electronic ground states

The millimeter- and submillimeter-wave spectra of AuCl and AuBr in the X¹Σ⁺ states were observed by employing a source-modulated microwave spectrometer. The AuCl and AuBr molecules were, respectively, generated in a free space cell by a d.c. glow discharge in Cl₂ and Br₂ with Ar. The gold atoms were supplied by the sputtering reaction from a gold sheet placed on the inner surface of a stainless-steel cathode. Rotational transitions of , , , and in highly excited vibrational states as well as in the ground vibrational states were measured in the region between 189 and 314 GHz. The transition frequencies were analyzed by a least-squares method using a combined-isotopomer Dunham-type term energy expression. The potential constants of gold halides obtained were compared with those of copper and silver halides.     

Ab initio study of the spectroscopy of the XΠ electronic ground states of CNO and NCO

The X²Π electronic ground states of NCO and CNO have been investigated by complete ab initio methods. The dependence of the Renner-Teller parameters, ? and , on the ab initio method and on the basis set have been studied. These parameters have also been compared to experimental data for NCO. The potential energy surfaces of the X²Π state have been determined by the MRCI method and the cc-pVQZ basis set for NCO and CNO. The rovibronic levels of both isomers have been calculated variationally up to approximatively 4000 cm⁻¹ for J ? 5/2 and K ? 2, with the inclusion of the geometry dependence of the spin-orbit coupling. The agreement with experimental data obtained for NCO is remarkable. A similar accuracy for the ab initio rovibronic levels of CNO is expected since no experimental data exists for this isomer.     

The far-infrared and microwave spectra of the CH radical in the v = 1 level of the XΠ state

Transitions between the spin-rotational levels of the ¹²CH radical in the v = 1 level of the X²Π state have been studied by the technique of laser magnetic resonance at far-infrared wavelengths. The data have been combined with a measurement of lambda-doubling transition frequencies at 7 GHz to determine an improved set of molecular parameters for CH in the v = 1 level. The parameters provide information on the effects of vibrational excitation on the structural properties of CH. Accurate predictions of the transition frequencies between the low-lying levels of the radical in the absence of a magnetic field have also been made.Small inconsistencies in the least-squares fit of the laser magnetic resonance data prompted re-measurement of three far-infrared laser frequencies, the 122.5 μm line of CH₂F₂ pumped by 9R(22), the 122.5 μm line of CH₂F₂ pumped by 9P(8) and the 554.4 μm line of CH₂CF₂ pumped by 10P(14). The new measurements differ by as much as 3.8 MHz from those made previously and are more accurate; they also remove the inconsistencies in the fit. The re-measured frequencies of the two 122.5 μm lines are identical within experimental error which suggests that the far-infrared lasing transition is the same, namely the ^rR₂₃(32) transition in the v₉=1 level of CH₂F₂.     

Spectroscopy of AlO: Combined analysis of the AΠi → XΣ and BΣ → XΣ transitions

A combined analysis of the A²Π_i → X²Σ⁺ and B²Σ⁺ → X²Σ⁺ band systems of AlO, involving 21,500 line assignments, has been performed. The analysis indicates that the previously reported γ values of the B²Σ⁺ state are questionable. The present analysis shows that γ(B²Σ⁺) ≈ 0.014 cm⁻¹, essentially independent of the vibrational level. The positive sign is consistent with second order interaction with the higher-lying C²Π_r and lower-lying A²Π_i states. It also appears that many of the previously reported γ and γ_D values of X²Σ⁺ (v > 0) are doubtful. In fact, γ(X²Σ⁺) is observed to become increasingly negative for v″ > 1, due to second order interaction with the low-lying A²Π_i state. The present results are based on models where the hyperfine structure of the ²Σ⁺ states has been taken into account explicitly. Intensity patterns of the branches of the B²Σ⁺ → X²Σ⁺ system have been shown to be influenced by the case bβ_S coupling in the ground state v = 0,1 levels. This gives rise to intensity differences of around 10 percent in the R₁/R₂ and P₁/P₂ doublet components. The synthesized intensity patterns are fully in accord with the F₁/F₂ assignments of the present work.     

Sub-millimeter spectroscopy of BaS (XΣ)

The pure rotational spectrum of BaS (X¹Σ⁺) has been recorded in the frequency range 355-396 GHz using direct absorption methods. Data were recorded for six isotopomers: ¹³⁸Ba³²S, ¹³⁷Ba³²S, ¹³⁶B³²S, ¹³⁵Ba³²S, ¹³⁴Ba³²S, and ¹³⁸Ba³⁴S, in vibrational states ranging from v = 0 to v = 6. This work is an extension of past microwave and millimeter studies. Revised spectroscopic constants have been established for the six species. The dissociation energy for ¹³⁸Ba³²S is estimated to be 42 392 cm⁻¹.     

Sub-Doppler laser absorption spectroscopy of the AΠi − XΣ (1, 0) band of CN: Measurement of the N hyperfine parameters in AΠ CN

Measurements of multiple rotational lines in the (1, 0) band of the A²Π_i − X²Σ⁺ “red” system of the cyanogen radical (CN) at sub-Doppler resolution are reported. The CN radical was produced by 193 nm photodissociation of NCCN (ethane dinitrile) and detected with a Ti:sapphire ring laser operating near 10 900 cm⁻¹. The sample was exposed to a weak, frequency-modulated probe beam and a strong, counterpropagating bleach laser beam. Demodulated probe laser signals display absorption and dispersion features derived from Doppler-free saturation of the hyperfine components as the laser scans across the central region of a Doppler-broadened rotational line spectrum. Hyperfine-resolved transition frequencies were combined with known ground-state X²Σ hyperfine term values to determine A²Π state hyperfine term values, which were analyzed in terms of an effective Hamiltonian for the A²Π state. All the expected hyperfine and ¹⁴N quadrupolar parameters were determined and their values analyzed in terms of a simple molecular orbital picture of the bonding in the radical. Higher sensitivity obtained with 400 kHz amplitude modulation of the bleach laser and additional phase-sensitive detection allowed hyperfine splittings in some rotational lines of ¹³C¹⁴N to be observed in natural abundance. Excited state hyperfine splittings were determined for a selection of rotational states, but not enough to determine the ¹³C hyperfine parameters.     

An ab Initio Study of the ÃΠ State and the ÃΠ←X?Σ Electronic Transition of MgNC

We use the RENNER program system (see, for example, P. Jensen, G. Osmann, and P. R. Bunker, in “Computational Molecular Spectroscopy” (P. Jensen and P. R. Bunker, Eds.), Wiley, Chichester, 2000, and references therein) to make a detailed calculation of the rovibronic energies in the first excited electronic state, òΠ, of the MgNC radical. This calculation is based on ab initio data (supplemented here with points for larger bending displacements from linearity) calculated at the level of MR-SDCI(+Q)/[TZ3P+f(Mg), aug-cc-pVQZ (N and C)] by T. E. Odaka, T. Taketsugu, T. Hirano, and U. Nagashima (J. Chem. Phys.115, 1349-1354 (2001)). These authors employed ab initio derived spectroscopic constants to calculate vibronic energies using perturbation expressions (J. T. Hougen and J. P. Jesson, J. Chem. Phys.38, 1524-1525 (1963)), and their results suggested that an observed vibronic band belonging to the òΠ←X?²Σ⁺ electronic transition (R. R. Wright and T. A. Miller, J. Mol. Spectrosc.194, 219-228 (1999)) should be reassigned. The present work confirms this conclusion, which is further substantiated by the rotational structures calculated in the vibronic states and by Franck-Condon theory predicting relative intensities.     

Critical evaluation of measured pure-rotation and rotation-vibration line positions and an experimental dataset of energy levels of CO in XΣ state

All available transitions from microwave to visible region (3.8-10 440 cm⁻¹) of the ¹²C¹⁶O molecule were collected from the literature and tested using the RITZ computer code. These data have been critically analyzed and used to obtain the most complete and precise set of 2247 experimental energy levels of this molecule covering the 0-67 000 cm⁻¹ interval. These levels together with calculated correlation matrix can be used to generate the most precise list of transitions with confidence intervals for astrophysical and atmospheric applications. Comparisons with the HITRAN and GEISA databanks as well as with Goorvitch high-temperature linelist are discussed. A set of corrected HITRAN ¹²C¹⁶O transition frequencies together with 99% confidence intervals is presented; it is proposed that this should be employed as a replacement for the current HITRAN database.     

Laser spectroscopy of VS: hyperfine and rotational structure of the CΣ-XΣ transition

The (0,0) and (0,1) bands of the C⁴Σ⁻-X⁴Σ⁻ electronic transition of VS (near 809 and 846 nm, respectively) have been recorded at high resolution by laser-induced fluorescence, following the reaction of laser-ablated vanadium atoms with CS₂ under supersonic free-jet conditions. A least squares fit to the resolved hyperfine components of the rotational lines gives the rotational constants and bond lengths as C⁴Σ⁻: , ; X⁴Σ⁻: , . The electron spin parameters for the two states show that there are some similarities between the states of VS and those of VO, but the hyperfine parameters show that the compositions of the partly filled molecular orbitals are by no means the same. The ground state Fermi contact parameter of VS, b(X⁴Σ⁻), is only 58% of that of the ground state of VO, which implies that the σ orbital of the ground σδ² electron configuration has less than 50% vanadium 4s character. Similarly, the excited state Fermi contact parameter, b(C⁴Σ⁻), is very much smaller than that of VO. No local rotational perturbations have been found in the C⁴Σ⁻ state of VS, though an internal hyperfine perturbation between the F₂ and F₃ electron components at low N confuses the hyperfine structure and induces some forbidden (ΔJ=±2) rotational branches.     

A Theoretical Study of MgNC and MgCN in the X?Σ Electronic State

The MgNC radical was the first Mg-containing species to be observed in interstellar space. This fact has stimulated considerable spectroscopic interest in this molecule, and in its isomer MgCN, but nevertheless the only rotationally resolved spectroscopic data presently available for X?²Σ⁺ MgNC comprise the rotational spectrum (K. Kawaguchi et al., 1993, Astrophys. J.406, L39-L42; K. Ishii et al., 1993, Astrophys. J.410, L43-L44; M. A. Anderson and L. M. Ziurys, 1994, Chem. Phys. Lett.231, 164-170; E. Kagi et al., 1996, J. Chem. Phys.104, 1263-1267; E. Kagi and K. Kawaguchi, J. Mol. Spectrosc. 2000, 199, 309-310) together with a few vibronic bands, all originating in the vibronic ground state and belonging to the òΠ←X?²Σ⁺ electronic transition (R. R. Wright and T. A. Miller, 1999, J. Mol. Spectrosc.194, 219-228). For MgCN, only the rotational spectrum in the vibrational ground state is known (M. A. Anderson, T. C. Steimle, and L. M. Ziurys, 1994, Astrophys. J.429, L41-L44). We report here potential energy surfaces calculated by the Averaged Coupled-Pair Functional (ACPF) method with TZ3P+f (Mg), TZ2P+f(N,C) basis sets including core-valence correlation due to the Mg 2s and 2p electrons. The ab initio results are used for determining the standard spectroscopic constants of X?²Σ⁺ MgNC and MgCN. Also, we report variational calculations of the rotation-vibration energies, and variational simulations of the lowest rotation-vibration bands, carried out with the MORBID program system (P. Jensen, 1988, J. Mol. Spectrosc.128, 478-501). We hope that our theoretical results will encourage and facilitate further characterization of X?²Σ⁺ MgNC and MgCN by high-resolution spectroscopy.     

Absorption spectrum of the (2, 1) band in the AПi-XΣ system of CS cation

The spectrum of CS⁺ cation was recorded in the 12,235-12,600 cm⁻¹ region by employing optical heterodyne velocity modulation absorption spectroscopy. In combination with simultaneous measurement of optical heterodyne concentration modulation absorption spectroscopy, the spectral lines of CS⁺ blended with the neutral CS lines were identified and extracted from the observed spectra. One hundred and eighty-two spectral lines of CS⁺ were assigned to the (2, 1) band in the A²П_i-X²Σ⁺ system and the improved molecular constants of the upper level (υ = 2) in the A²П_i state were derived by nonlinear least squares fitting.     

The 1-v″ bands progression of the BΣ → XΣ system of CO

The B²Σ⁺ → X²Σ⁺ (0-1, 2, 3, 4 progression) electronic transition of ¹²C¹⁷O⁺ was first observed and analyzed by Szajna and Ke¸pa [Spectrochim. Acta A 65 (2006) 1014-1020]. We have now extended our previous studies. The use of high resolution conventional spectroscopic techniques has allowed first rotational analysis of the 1-2, 1-3, 1-4 and 1-5 bands of the first negative system in the 37,000-43,000 cm⁻¹ spectral region. Approximately 500 transition wavenumbers were measured with an estimated accuracy of 0.005 cm⁻¹. The present data were combined with the previous measurements to yield an improved set of molecular constants for the B²Σ⁺(v′ = 0, 1) and X²Σ⁺(v″ = 1, 2, 3, 4, 5). The v′ = 1 and v″ = 5 vibrational levels were observed for the first time and the main molecular constants are (in cm⁻¹, one standard deviation in parentheses)

B2Σ+		X2Σ+
B1 = 1.710792(20)		B5 = 1.825694(23)
D1 = 7.799(15) × 10−6		D5 = 6.085(21) × 10−6
γ1 = 1.9491(37) × 10−2		γ5 = [8.381] × 10−3

Full-size table

     

Doppler-limited spectroscopy of the AΠ1 ← XΣ system of ICl in the 0.8 μm region using a Ti:sapphire ring laser

Doppler-limited vib-rotational absorption spectra of the A ← X electronic transition of I^35/37Cl are measured in the range 11,352-13,507 cm⁻¹ using a Ti:sapphire ring laser. The P-, Q-, and R-branch lines belonging to the v ← v″ = (0-7) ← (0-7) transition in I³⁵Cl and the v ← v″ = (0-6) ← (2-6) transition in I³⁷Cl are assigned. Under Doppler-limited conditions, the P- and R-branch lines are split into doublets by the nuclear quadrupole coupling effect of the I atom. The unperturbed positions of these lines are correctly calculated, whereas splitting in the Q-branch lines was not observed. The mass-reduced Dunham expansion coefficients U_l,m of the A and X states and the spectroscopic constants , and H_v^′ of the A state are determined using a global least-squares fitting procedure.     

New spectroscopic investigations of the fourth-positive (AΠ → XΣ) system bands in the CO molecule

The present work puts forward the results of the recordings carried out under high resolution by conventional, photographic spectroscopy and modern analysis of thirteen bands with v′ = 7-12 and v″ = 16-24 of the fourth-positive (A¹Π → X¹Σ⁺) band system. The current investigations include the region of the observed ¹³C¹⁶O molecule spectrum, much greater now than before. Especially, new transitions connected with not hitherto observed v′ = 12 vibrational level of the A¹Π state, were recorded and studied. Moreover, the region of perturbations observed in the upper state of the fourth-positive system was significantly enlarged. The observed perturbations were confronted with those predicted from theoretical calculations.     

The pure rotational spectrum of ZnO in the XΣ and aΠi states

The pure rotational spectrum of ZnO has been measured in its ground X¹Σ⁺ and excited a³Π_i states using direct-absorption methods in the frequency range 239-514 GHz. This molecule was synthesized by reacting zinc vapor, generated in a Broida-type oven, with N₂O under DC discharge conditions. In the X¹Σ⁺ state, five to eight rotational transitions were recorded for each of the five isotopologues of this species (⁶⁴ZnO, ⁶⁶ZnO, ⁶⁷ZnO, ⁶⁸ZnO, and ⁷⁰ZnO) in the ground and several vibrational states (v = 1-4). Transitions for three isotopologues (⁶⁴ZnO, ⁶⁶ZnO, and ⁶⁸ZnO) were measured in the a³Π_i state for the v = 0 level, as well as from the v = 1 state of the main isotopologue. All three spin-orbit components were observed in the a³Π_i state, each exhibiting splittings due to lambda-doubling. Rotational constants were determined for the X¹Σ⁺ state of zinc oxide. The a³Π_i state data were fit with a Hund’s case (a) Hamiltonian, and rotational, spin-orbit, spin-spin, and lambda-doubling constants were established. Equilibrium parameters were also determined for both states. The equilibrium bond length determined for ZnO in the X¹Σ⁺ state is 1.7047 Å, and it increases to 1.8436 Å for the a excited state, consistent with a change from a π⁴ to a π³σ¹ configuration. The estimated vibrational constants of ω_e ∼ 738 and 562 cm⁻¹ for the ground and a state agreed well with prior theoretical and experimental investigations; however, the estimated dissociation energy of 2.02 eV for the a³Π_i state is significantly higher than previous predictions. The lambda-doubling constants suggest a low-lying ³Σ state.     

Axis-Switching and Coriolis Coupling in the Ã(010)-X?(000) Transitions of DCCl and HCCl

The rotationally resolved Ã(010)-X?(000) spectrum of DCCl between 12 880 and 12 964 cm⁻¹ was measured using frequency-modulated laser absorption spectroscopy of jet-cooled and ambient temperature samples. Transitions to levels with K_a′=0 and 1 were assigned, and their analysis leads to improved accuracy of both the ground state rotational constants of DCCl and, when combined with existing data for HCCl, the geometry of the radical. In addition to the expected perpendicular band structure, a number of parallel (Δ K_a=0) subbands were observed. Their intensity derives from a combination of c-type Coriolis coupling and axis-switching (J. T. Hougen and J. K. G. Watson, 1965, Can. J. Phys.43, 298) resulting from the change in geometry between the two states. The two contributions have been calculated for the (010)-(000) band of DCCl and previously recorded data for HCCl. Satisfactory agreement with experimental measurements was obtained. The Coriolis contributions are small for these transitions, but may add to or subtract from the axis-switching. For higher bending excitation in the upper state, Coriolis coupling is predicted to make larger contributions to the parallel subband intensities.     

Magnetocaloric properties of the spin-S (S ≥ 1) Ising model on a honeycomb lattice

Using effective field theory, we have investigated magnetocaloric features of the spin-S Ising model for some spin values $S=1,3/2,2,5/2,3$ and 7/2 on a honeycomb lattice. Effects of the external magnetic field on the isothermal entropy change, its half-width and also cooling capacity have been determined and discussed in detail. The numerical results show that the isothermal entropy change decreases whereas its half-width and cooling capacity tends to increase when the spin magnitude of the system is increased starting from $S=1$ to 7/2 for a fixed value of the external field. Finally, we have also performed some calculations to check the applicability of magnetocaloric scaling procedure for the present system. It is found that the rescaled numerical data collapse onto the same universal curve for all considered values of spin component S.