Absolute Intensities Measurements in the nu(4) + nu(5) Band of (12)C(2)H(2): Analysis of Herman-Wallis Effects and Forbidden Transitions

We measured absolute line intensities in two bands of (12)C(2)H(2) near 7.5 μm, namely the nu(4) + nu(5)(Sigma(+)(u))-0(Sigma(+)(g)) and nu(4) + nu(5)(Delta(u))-0(Sigma(+)(g)) bands, using Fourier transform spectroscopy with an accuracy estimated to be better than 2%. Using theoretical predictions from Watson [J. K. G. Watson, J. Mol. Spectrosc. 188, 78 (1998)], the observation of the forbidden nu(4) + nu(5)(Delta(u))-0(Sigma(+)(g)) band and the Herman-Wallis behavior exhibited by its rotational lines were studied quantitatively in terms of two types of interactions affecting the levels involved by the band: l-type resonance and Coriolis interaction. In the case of the nu(4) + nu(5)(Sigma(+)(u))-0(Sigma(+)(g)) band, the influence of l-type resonance is also confirmed. We also attributed the intensity asymmetry observed between the R and P branches of that latter band to a Coriolis interaction with l = 1 levels. We did not observe the nu(4) + nu(5)(Sigma(-)(u))-0(Sigma(+)(g)) band, consisting only of a Q branch, in agreement with Watson's prediction. Copyright 2000 Academic Press.     

Characterization of the Ground State of Br(2) by Laser-Induced Fluorescence Fourier Transform Spectroscopy of the B(3)Pi(0(+))(u)-X(1)Sigma(+)(g) System

The laser-induced fluorescence (LIF) spectrum of the B(3)Pi(0(+))(u)-X(1)Sigma(+)(g) system of Br(2) was recorded by Fourier transform spectroscopy (FTS). The LIF spectra were obtained by using continuous-wave dye laser excitation in the spectral region 16 800-18 000 cm(-1). About 1800 rotationally resolved lines were recorded in 96 fluorescence progressions, originating from the 10 相似文献   

The Rotational Spectrum of SO(2) and the Determination of the Hyperfine Constants and Nuclear Magnetic Shielding Tensors of (33)SO(2) and SO(17)O

Rotational analyses of the B(2)Sigma(+)(u) --> X(2)Sigma(+)(g) system of the (14)N(+)(2) molecule have been extended to include the vibrational levels up to v' = 4. Spectral data from 20 bands obtained from high-resolution Fourier transform spectrometry of a hollow-cathode and a Pointolite lamp were included in the analysis. A global deperturbation yielded molecular parameters of the highly perturbed B(2)Sigma state and interaction parameters A(2)Pi(u) approximately B(2)Sigma(u) with a standard deviation of 0.011 cm(-1). Rotational term values of the B(2)Sigma(+) state were also determined. New perturbations in the B(2)Sigma(+) (v = 0) level have been observed at N approximately 85 and N approximately 96. Copyright 2000 Academic Press.     

Fourier Transform Spectroscopy of the A'(1)Pi-X(1)Sigma(+) System of CaO

The A'(1)Pi-X(1)Sigma(+) near-infrared system of CaO was observed for the first time at high resolution using a Fourier transform spectrometer. The A'(1)Pi-X(1)Sigma(+) chemiluminescence was excited in a Ca + N(2)O flame produced in a Broida-type oven. More than 3000 rotational lines, classified into 19 bands involving the A'(1)Pi 0 /= 2) levels with the nearby b(3)Sigma(+) (v-2) levels has been detected. An extended set of A'(1)Pi (v = 0-3) data has been obtained which is suitable for use in a future multistate deperturbation analysis of the a(3)Pi approximately A'(1)Pi approximately b(3)Sigma(+) approximately A(1)Sigma(+) complex of excited states. The new near-infrared spectra of the A'(1)Pi-X(1)Sigma(+) transition of CaO also permits the first direct high-resolution linkage between the orange and green systems and the near-infrared bands. Copyright 2000 Academic Press.     

Intensity Measurements and Collision-Broadening Coefficients for the Oxygen A Band Measured by Intracavity Laser Absorption Spectroscopy

High-sensitivity, high-resolution intracavity laser absorption spectroscopy (ICLAS) has been used to measure line intensities, nitrogen-broadening coefficients, and self-broadening coefficients in the A band (b(1)Sigma(+)(g) <-- X(3)Sigma(-)(g)) of oxygen. Both linear cavity and ring cavity ICLAS configurations were used for these measurements, and the results were intercompared. The results were compared to values measured using long-path multiple-reflection cells by K. D. Ritter and T. D. Wilkinson [J. Mol. Spectrosc. 121, 1-19 (1987)] and L. Brown and C. Plymate, [J. Mol. Spectrosc. 199, 166-179 (2000)]. New results are included for weakly absorbing transitions, not observed in the earlier measurements, such as high rotational states (up to J = 39), hot-band transitions (v' = 1 <-- v" = 1), and isotopically substituted species ((18)O(2) and (16)O(18)O). Isotopic variants ((16)O(2), (18)O(2), and (16)O(18)O) have similar broadening coefficients for corresponding rotational levels, but the self-broadening coefficients are larger in the hot band (v' = v" = 1) as compared with v' = v" = 0 transitions. An ECS-EP scaling analysis of the v' = v" = 0 self-broadening data accurately represents the available data, with the exception of the N = 0 and N = 1 levels. Copyright 2000 Academic Press.     

The Perturbation between the G(1)Pi(g) and 2(1)Delta(g) States of (7)Li(2)

We have observed the rotational levels in the v = 2, 3, 5, 6, 7, and 8 vibrational manifolds of the 2(1)Delta(g) state of (7)Li(2) via the A(1)Sigma(+)(u) intermediate levels by DeltaLambda = 2 transitions. This violation of the DeltaLambda = 0, +/-1 selection rule is due to the interaction with the G(1)Pi(g) state. Band-by-band deperturbations of the G(1)Pi(g) approximately 2(1)Delta(g) (v(Pi), v(Delta)) = (11, 2), (12, 3), (15, 5), (16, 6), (18, 7), and (19, 8) bands have been performed. Deperturbed molecular constants and rotational-electronic interaction parameters are reported here. Copyright 2000 Academic Press.     

The Rotational Analysis of the A(2)Pi(r)-X(2)Sigma(+) Band System of MgBr

The A(2)Pi(r)-X(2)Sigma(+) emission spectrum of the magnesium monobromide radical, MgBr, has been recorded with a Fourier transform spectrometer modified to record double-sided interferograms. The emission spectra of the Deltav = -2, -1, 0, +1 bands were generated in a microwave discharge of a mixture of argon and vaporized MgBr(2). The Deltav = 0 and -1 bands were rotationally resolved, but the F(2) spin component (A(2)Pi(3/2)) in the (1, 1), (1, 2) and vibrational bands with v' > 1 were missing in our spectra because of a strong predissociation in the A state. The molecular constants in both electronic states were determined for the two bromine isotopomers. The r(0) bond length in the A state is about 2.327 ?, which is about 0.02 ? shorter than in the ground state. Franck-Condon factors were calculated from the Rydberg-Klein-Rees potentials, and they reproduce the observed relative intensities of the bandheads. An upper limit for the dissociation energy (D(0)(0)) was obtained as 26 268.4 cm(-1), based on the absence of the energy level with v = 1, A(2)Pi(3/2), J = 1.5 in our spectrum. Copyright 2000 Academic Press.     

Enhanced Access to the Dark Triplet States of (7)Li(2) through New Singlet-Triplet A(1)Sigma(+)(u) approximately b(3)Pi(u) Perturbation Window Levels: Perturbation-Facilitated Optical-Optical Double Resonance Study of the 2(3)Sigma(+)(g) State

Two new pairs of singlet-triplet A(1)Sigma(+)(u) approximately b(3)Pi(u) mixed levels of (7)Li(2) have been observed and used here as "window" levels in cw perturbation-facilitated optical-optical double-resonance (PFOODR) experiments. Previously, only one b(3)Pi(u) vibrational level, v = 19, was known to mix with the singlet A(1)Sigma(+)(u) v = 13 level, resulting in three perturbed A approximately b pairs [L. Li, T. An, T.-J. Whang, A. M. Lyyra, W. C. Stwalley, R. W. Field, and R. A. Bernheim, J. Chem. Phys. 96, 3342 (1992)]. The scarcity of window levels and the resulting difficulty in accessing the dark triplet states of Li(2) is caused by the weak spin-orbit interaction of Li(2). The two new mixed b(3)Pi(u) v = 15 and 22 levels reported here enhance access to the dark triplet state manifold through expansion of the Franck-Condon overlap factor range. Furthermore, the earlier range of accessible rotational levels, N = 5, 7, and 10, is now expanded to include N = 8 and N = 16, thereby allowing for more reliable determination of the excited triplet states rotational structure. To demonstrate the importance of the new A(1)Sigma(+)(u) approximately b(3)Pi(u) mixed levels, we have studied the 2(3)Sigma(+)(g) state by cw PFOODR fluorescence excitation spectroscopy. New molecular constants and RKR potential curve have been determined. As previously reported [L. Li, G. Lazarov, and A. M. Lyyra, J. Mol. Spectrosc. 191, 387 (1998)], the 2(3)Sigma(+)(g) state interacts with the repulsive 1(3)Pi(g) state by L-uncoupling and predissociates. We show that some 2(3)Pi(g) levels predissociate accidentally by the 1(3)Pi(g) state via the 2(3)Sigma(+)(g) state through L-uncoupling. Copyright 2001 Academic Press.     

Fourier Transform Emission Spectroscopy of CuCl

The electronic spectra of CuCl were observed in the 18 000 cm(-1) to 25 000 cm(-1) spectral region using a Bruker IFS 120 HR Fourier transform spectrometer (FTS) and with the FTS associated with the McMath-Pierce Solar Telescope at Kitt Peak. On the basis of ab initio calculations, the labels for the electronic states were revised, and the a(3)Sigma(+)(1)-X(1)Sigma(+) 0-0 band, the b(3)Pi(0)-X(1)Sigma(+) 0-0, 1-0, and 0-1 bands, the b(3)Pi(1)-X(1)Sigma(+) 0-0, 1-0, and 0-1 bands, the A(1)Pi-X(1)Sigma(+) 0-0, 1-0, and 0-2 bands, and the B(1)Sigma(+)-X(1)Sigma(+) 0-0 and 1-0 bands were measured. Improved spectroscopic constants were obtained for the excited and ground states. Copyright 2001 Academic Press.     

Determination of Interatomic Potentials for the X0(+), A0(+), and B1 States of HgKr from Fluorescence and Excitation Spectra

We present an analysis of the A0(+)(6(3)P(1))-->X0(+)(6(1)S(0)) bound-bound and bound-free fluorescence spectrum, and of the A0(+)(6(3)P(1))<--X0(+)(6(1)S(0)) and B1(6(3)P(1))<--X0(+)(6(1)S(0)) bound-bound excitation spectrum of the HgKr van der Waals molecule. The A-->X fluorescence spectrum, which was observed for the first time, as well as the excitation spectra were recorded using a pulsed supersonic molecular beam crossed with a pulsed dye laser beam. An analysis of the A(v')<--X(v"), B(v')<--X(v"), and A(v'=8)-->X(v") bound-bound bands indicates that a Morse function combined with a long-range approximation represents the interatomic potential energy curve of the A, B, and X states below the dissociation limit. In the simulation of the A(v'=8)-->X bound-free spectrum the Morse, Lennard-Jones (n-6), and Maitland-Smith (n(0), n(1)) functions were tested, and the Maitland-Smith (11.39, 10.50) potential was found to be a good representation of the repulsive part of the X-state PE curve above the dissociation limit, over the internuclear separation range R=2.85-3.55 ?. The spectroscopic characteristics for the A, B, and X states obtained in this work are compared with other available experimental and theoretical results. Copyright 2001 Academic Press.     

Observation of direct dissociative ionization in molecular hydrogen

Direct dissociative ionization is the simplest three-body breakup process in H2. We describe the experimental verification of direct dissociative ionization to the repulsive A2Sigma(+)(u) state by resolving the kinetic energy and angular distributions of the formed protons. A (2+1) resonant enhanced multiphoton ionization process via the isotropic E,F (1)Sigma(+)(g)(v = 6,J = 0) level is employed. The structure in the kinetic energy spectrum is well described by a projection of the vibrational wave function of the E,F (1)Sigma(+)(g)(v = 6,J = 0) state onto the repulsive ionic state. The electronic character of the ionization continuum is revealed by the proton angular distribution.     

Fourier Transform Emission Spectroscopy of the Low-Lying Electronic States of NbN

The high-resolution spectrum of NbN has been investigated in emission in the 3000-15 000 cm(-1) region using a Fourier transform spectrometer. The bands were excited in a microwave discharge through a mixture of NbCl(5) vapor, approximately 5 mTorr of N(2), and 3 Torr of He. Numerous bands observed in the near-infrared region have been classified into the following transitions: f(1)Phi-c(1)Gamma, e(1)Pi-a(1)Delta, C(3)Pi(0+)-A(3)Sigma(-)(1), C(3)Pi(0-)-A(3)Sigma(-)(1), C(3)Pi(1)-a(1)Delta, C(3)Pi(1)-A(3)Sigma(-)(0), d(1)Sigma(+)-A(3)Sigma(-)(0), and d(1)Sigma(+)-b(1)Sigma(+). These observations are consistent with the energy level diagram provided by laser excitation and emission spectroscopy [Y. Azuma, G. Huang, M. P. J. Lyne, A. J. Merer, and V. I. Srdanov, J. Chem. Phys. 100, 4138-4155 (1993)]. The missing d(1)Sigma(+) state has been observed for the first time and its spectroscopic parameters are consistent with the theoretical predictions of S. R. Langhoff and W. Bauschlicher, Jr. [J. Mol. Spectrosc. 143, 169-179 (1990)]. Rotational analysis of a number of bands has been obtained and improved spectroscopic parameters have been extracted for the low-lying electronic states. The observation of several vibrational bands with v = 1 has enabled us to determine the vibrational intervals and equilibrium bond lengths for the A(3)Sigma(-)(0), a(1)Delta, b(1)Sigma(+), d(1)Sigma(+), and C(3)Pi(1) states. Copyright 2000 Academic Press.     

Ab Initio Investigation of the ellipsis pi(2)(g) (X(3)Sigma(-)(g), 1(1)Delta(g), 1(1)Sigma(+)(g)) Electronic States of NCN. Study of the Renner-Teller Effect in the 1(1)Delta(g) State

Large-scale CI calculations are carried out to obtain accurate potential energy surfaces for the ellipsis pi(2)(g) manifold (X(3)Sigma(-)(g), 1(1)Delta(g), 1(1)Sigma(+)(g)) of electronic states of NCN. Separation of the low-lying singlet states from the triplet ground state is computed in close agreement with the results of a recent photoelectron study by T. R. Taylor, R. T. Bise, K. R. Asmis, and D. M. Neumark [Chem. Phys. Lett. 301, 413-416 (1999)]. Vibronic coupling (Renner-Teller effect) in the 1(1)Delta(g) state is studied by means of a perturbative and a variational approach. Results of the present ab initio study confirm explicitly the rho(4) dependence postulated for the splitting of bending potential curves in Delta electronic states at small deviations from linearity. Copyright 2000 Academic Press.     

First Observation of Hyperfine Structure in K(2)

The hyperfine structure of the (v'-v") = (27-0) band of the b(3)Pi(u0(+)) <-- X(1)Sigma(+)(g) transition has been observed by laser excitation spectroscopy in a highly collimated molecular beam. Hyperfine parameters for magnetic dipole and electric quadrupole interaction are derived from least-squares fitting of the hyperfine pattern and deperturbation between A(1)Sigma(+)(u) and b(3)Pi(u0(+)). Copyright 2000 Academic Press.     

Characterization of Electronic Spectra of Rhodium Monohydride and Monodeuteride

Emission spectra of two new electronic transitions of Pb(2) have been measured with a Fourier transform spectrometer in the 5200-8500 cm(-1) range. The emissions were observed from the afterglow of a microwave discharge in a mixture of Pb(x) vapor with hydrogen and argon carrier gas. By comparison with the results of ab initio calculations, the spectra are assigned to transitions from the lowest 1(g) and 1(u) states to the X(1)0(+)(g) ground state. The X(2)1(g) --> X(1)0(+)(g) transition between the fine-structure components of the X(3)Sigma(-)(g) ground state must be magnetic dipole in nature and thus is the first purely magnetic dipole fine-structure transition observed in the optical region. The 1(u) state is mostly a component of the low-lying inverted A(3)Pi(u) state and so is denoted A(2)1(u). Vibrational analyses have yielded the following electronic energies and vibrational constants for (208)Pb(2) (in cm(-1)): X(1)0(+)(g): omega(e) = 110.20(2), omega(e)x(e) = 0.341(2); X(2)1(g): T(e) = 5304.9(1), omega(e) = 120.57(7), omega(e)x(e) = 0.254(14); A(2)1(u): T(e) = 7817.5(2), omega(e) = 126.45(6), omega(e)x(e) = 0.399(11), where the numbers in parentheses are the standard deviations of the parameters. Copyright 2000 Academic Press.     

Fourier Transform Spectroscopy of Chemiluminescence from the SrO A(1)Sigma(+)-X(1)Sigma(+) Transition

The A(1)Sigma(+)-X(1)Sigma(+) chemiluminescence spectrum of SrO was observed using a Fourier transform spectrometer. SrO was produced in a Broida-type oven from the Sr + N(2)O reaction. A total of 75 bands from (88)SrO, (87)SrO, and (86)SrO were measured in the range of 7600-13 600 cm(-1) at a resolution of 0.04 cm(-1). The vibrational levels of the ground state were observed up to v" = 12 and over 10 000 rovibrational lines with J as high as 153 were analyzed at a precision of about 0.005 cm(-1). Significantly improved spectral constants for the ground state were obtained by representing the perturbed excited state by term values and by adding the known microwave data and infrared data to our fit. Strong perturbations were observed in the upper A state. The vibrational levels of the A(1)Sigma(+) state were measured up to v' = 8 and some new perturbations are reported. Copyright 2000 Academic Press.     

Improvement of the Spectroscopic Constants of the PF(A(3)Pi) State and Assignment of the PF(A-X) Transition Dipole Function

High-resolution laser-excitation spectra were acquired for the v'=3-7 levels of the PF(A(3)Pi(0,1,2)<--X(3)Sigma(-)) transition from PF(X(3)Sigma(-)) molecules generated in a discharge flow reactor. These results were combined with lower resolution excitation spectra for the v'=8-11 levels and with existing high-resolution data in the literature for v'=0 and 1 to assign improved spectroscopic constants for PF(A(3)Pi(0,1,2)). The abnormal vibrational energy level spacings for all spin components of the PF(A(3)Pi) state are evidence for a homogeneous interaction with another (3)Pi state. The Lambda-doublet separation in the PF((3)Pi(0)) substate increases with vibrational level, which is taken as evidence for interaction with the PF(b(1)Sigma(+)) state. Laser-induced fluorescence spectra from individual v'=0-5 levels were used to obtain vibrational band intensities of the A-X transition. The strong dependence of the transition dipole on the r-centroid is consistent with the reduction in the radiative lifetimes with increasing v' level. The similarity between the isovalent PF(A(3)Pi) and SO(A(3)Pi) states is noted and the bond dissociation energy of PF(X(3)Sigma(-)) is discussed. Copyright 2001 Academic Press.     

Fourier Transform Spectroscopy of the O(2) Herzberg Bands. III. Absorption Cross Sections of the Collision-Induced Bands and of the Herzberg Continuum

Absorption spectra of molecular oxygen were measured in the laboratory under temperature and pressure conditions prevailing in the Earth's atmosphere. Spectra of pure O(2), O(2) + N(2), and O(2) + Ar were recorded in the 41 700 to 33 000 cm(-1) region (240-300 nm) at a maximal optical path difference of 0.45 cm using a Fourier transform spectrometer and a multiple reflection gas cell. The different components of the spectra, namely the discrete bands of the three Herzberg systems, the Herzberg continuum, and the collision-induced diffuse Wulf bands, were separated. The contribution of the Herzberg bands was first subtracted using the line parameters determined previously [A. Jenouvrier, M.-F. Mérienne, B. Coquart, M. Carleer, S. Fally, A. C. Vandaele, C. Hermans, and R. Colin, J. Mol. Spectrosc. 198, 136-162 (1999)] from high-resolution data. Spectra recorded at various pressures then made it possible to determine by linear regression the intensity of the Wulf bands and the Herzberg continuum. The characteristics of the Wulf bands have been investigated in details: vibrational analysis, pressure effect, foreign gas effect, and a simulated spectrum are reported. The Herzberg continuum cross section is determined below the dissociation limit. A comparison with literature data is given. The new O(2) absorption cross sections and O(2)-O(2) collision-induced absorption cross sections are useful in connection with atmospheric measurements of ozone and other trace gases in the UV spectral region. Copyright 2000 Academic Press.     

Electronic Spectrum of the Antimony Monoxide Radical

The 0-1 band (4271.3 ?) of the B(2)Sigma(+)-X(2)(2)Pi(3/2) transition, the 0-6 band (4275 ?) of the H(2)Pi(3/2)-X(2)(2)Pi(3/2) transition, the 0-0 band (3776.2 ?) of the B(2)Sigma(+)-X(1)(2)Pi(1/2) transition, and the 2-0 (3251.3 ?) as well as the 3-0 (3194.2 ?) bands of the C(2)Sigma(-)-X(1)(2)Pi(1/2) transition of SbO have been photographed at high resolution using the single isotope of antimony (121)Sb. An unambiguous analysis of the rotational structure of all these bands has been carried out for the first time. The magnitude and sign of the Lambda doubling constant p(0) of the X(1)(2)Pi(1/2) state have been determined and as a result of that, the symmetry of the C state has been uniquely identified as C(2)Sigma(-). Accurate rotational constants of all the states involved have been determined by a global linear least-squares fit. Copyright 2000 Academic Press.     

Observation of completely destructive quantum interference between interacting resonances in molecular predissociation

A unique observation is presented of interacting predissociating resonances which exhibit completely destructive interference in a region between the resonances. The use of a double-resonance technique, in which single rotational levels of the b (1)Sigma(+)(g) state of O2, prepared by pumping the magnetic-dipole b <--X transition, are probed by (2+1) resonance-enhanced multiphoton-ionization spectroscopy, eliminates overlapping rotational structure and enables observation of the interference process. Using a diabatic coupled-channel model, the interacting resonances are shown to be derived from the d (1)Pi(g)(v = 3,J = 17) Rydberg and II (1)Delta(g)(v = 6,J = 17) valence states.