Experimental and Theoretical Study of the Electronic States and Spectra of TeH and TeLi

Gas-phase emission spectra of the hitherto unknown free radical TeLi have been measured in the NIR range with a Fourier-transform spectrometer. The emissions were observed from a fast flow system in which tellurium vapor in argon carrier gas was passed through a microwave discharge and mixed with lithium vapor in an observation tube. Two systems of blue-degraded bands were measured at high spectral resolution in the ranges 8000-9000 and 5700-6700 cm(-1) and vibrational and rotational analyses were performed. In order to aid in the analysis of the experimental data, a series of relativistic configuration interaction calculations has been carried out to obtain potential curves for the low-lying states of TeLi and the isovalent TeH and also electric dipole transition moments connecting them. As in the TeH system, the ground state of TeLi is found to be X(2)Pi(i), but with a remarkably smaller spin-orbit splitting. The TeLi calculations indicate a strongly bound A(2)Sigma(+) state, while in TeH the analogous state is computed to lie significantly higher at approximately 32 000 cm(-1), and it is strongly predissociated. Based on the theoretical analysis, the observed TeLi band systems are assigned to the transitions A(2)Sigma(+)(A1/2)-->X(1)(2)Pi(3/2)(X(1)3/2) and A(2)Sigma(+)(A1/2)-->X(2)(2)Pi(1/2)(X(2)1/2). Analysis of the spectra has yielded the molecular constants (in cm(-1)) X(1)(2)Pi(3/2):omega(e)=457.49(3), omega(e)x(e)=2.482(9), B(0)=0.408908(8); X(2)(2)Pi(1/2): T(e)=2353.44(3), omega(e)=456.28(4), omega(e)x(e)=2.635(8), B(0)=0.414954(8), p(0)=1.00637(4); A(2)Sigma(+): T(e)=8574.64(2), omega(e)=437.81(3), omega(e)x(e)=2.581(8), B(0)=0.423903(8), p(0)=-0.19915(2), where the numbers in parentheses are the standard deviations of the parameters. Comparison of the isovalent TeLi and TeH systems emphasizes that the difference in bonding character (ionic in TeLi vs covalent in TeH) is responsible for qualitative differences in the electronic spectra of these two molecules. Copyright 2001 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 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.     

The (1)(3)Pi Electronic State of LaF

Rotational studies of bands of the infrared systems (1)(3)Pi-->(1)(3)Delta and (1)(3)Pi(1)-->X(1)Sigma(+) of lanthanum monofluoride were carried out with the aim of characterizing the (1)(3)Pi state, assuming the previous representations of X(1)Sigma(+) and (1)(3)Delta (1-3). The vibrational levels of (1)(3)Pi involved in the analyzed transitions were v=0, 1, 2 of the Omega=0 component, v=0, 1 of the Omega=1 component, and v=0 of the Omega=2 component. Perturbations were observed in both systems which were ascribed to spin-uncoupling interactions between (1)(3)Pi(2)(v=0) and (1)(3)Pi(1)(v=1) levels. A 9x9 matrix representation at equilibrium of the complex of interacting levels (v=0, 1, 2) was constructed, each diagonal v-block corresponding to a triplet model of the rovibrational (3)Pi Hamiltonian. The wavenumbers of some 1910 lines in the two systems were simultaneously fitted (rms error of the fit of about 0.0053 cm(-1)), thus yielding a consistent set of accurate spectroscopic constants for the (1)(3)Pi state; the spin-uncoupling interaction parameter was determined as B(Pi)(0, 1)=0.010917(13) cm(-1). Copyright 2001 Academic Press.     

High-Resolution Laser Spectroscopy of YbCl: The A(2)Pi-X(2)Sigma(+) Transition

The A(2)Pi-X(2)Sigma(+) transition of (174)Yb(35)Cl and (172)Yb(35)Cl has been rotationally analyzed for the first time. Doppler-limited laser excitation spectroscopy with selective detection of fluorescence was used to obtain spectra of the 0-0 and 1-0 bands with a measurement accuracy of approximately 0.0035 cm(-1). Resolved fluorescence was used to record the 0-1, 0-2, and 0-3 bands and to unequivocally assign the rotational numbering, N, to the laser excitation spectra. In total, over 1300 line positions have been measured and assigned for each of the two isotopomers and employed in least-squares fits of molecular parameters. The principal results for the A(2)Pi state are A(e) = 1491.494(2) cm(-1) and R(e) = 2.4433(1) ?, and for the X(2)Sigma(+) state, R(e) = 2.4883(2) ? and gamma(e) = 4.59(2) x 10(-3) cm(-1). The interaction between the X(2)Sigma(+) and A(2)Pi states has been investigated and is shown to be the main contributor to the spin-rotation splitting in the ground state. Copyright 2000 Academic Press.     

Laser-Induced Fluorescence and Fourier Transform Spectroscopy of NiCl: Identification of a Low-Lying (2)Sigma(+) State (1768 cm(-1))

From a comparison with the spectrum of NiF, a low-lying (2)Sigma(+) state is expected to lie in the first 2000 cm(-1) above the ground X(2)Pi(3/2) state of NiCl. The identification of this (2)Sigma(+) (v = 0) state (at 1768 cm(-1)) has been carried out through the analysis of two electronic transitions (2)Pi(3/2)-(2)Sigma(+) (22 720 cm(-1)) and (2)Pi(1/2)-(2)Sigma(+) (23 210 cm(-1)) recorded by high-resolution Fourier transform spectroscopy. Dispersed fluorescence spectroscopy allowed these transitions to be located on an absolute energy-level diagram that includes the previously studied electronic states. 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.     

High-Resolution Study of the BaI A(2)Pi Electronic State

Near-infrared and visible spectra of the A(2)Pi-X(2)Sigma(+), C(2)Pi(1/2)-A(2)Pi(1/2), C(2)Pi(1/2)-B(2)Sigma(+), and C(2)Pi(1/2)-X(2)Sigma(+) band systems of the BaI molecule were recorded by using Fourier transform spectroscopy (FTS). The spectra were produced from the chemiluminescent reaction Ba + I(2) and also by using laser-induced fluorescence (LIF) technique in which the laser sources were a Ti:sapphire single-mode laser, a dye single-mode laser, and a Kr(+) multimode ion laser. Resolved rotational data, originating from 19 vibrational levels (0 相似文献   

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 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.     

Optical Spectroscopy of Diatomic Species: Copper with Group 14 Elements (Si, Ge, Sn, Pb)

Electronic band systems of the gaseous diatomic compounds of copper and various X elements of the 14th column (Si, Ge, Sn, Pb) have been observed by thermal excitation in the red part of the visible spectrum. Vibrational analysis of the two subsystems observed for each of these molecules (except for CuPb with only one system) are reported and assigned as (2)Sigma(+)-(2)Pi(3/2) and (2)Sigma(+)-(2)Pi(1/2) transitions. The variation of the spin-orbit splitting of the (2)Pi lower states from CuSi to CuSn follows closely that of the np shell spin-orbit parameters in the group 14 atoms. This fully corroborates previous ab initio calculations that predict a (2)Pi(r) ground state with the ionic Cu(+) (3d(10))X(-)(pvarsigma(2)ppi) configuration for these molecules. Copyright 2000 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.     

Anomalous Vibrational Dependence of the Rotational and Hyperfine Parameters in the B(4)Pi-X(4)Sigma(-) Transition of NbO

The laser excitation spectrum of jet-cooled NbO in the region 16 000-18 000 cm(-1) has been recorded at high resolution, giving rotational and hyperfine constants for the levels v=0-3 of the B(4)Pi state and v=1 of the X(4)Sigma(-) state; zero gaps have also been measured at low resolution for some weaker bands involving higher vibrational levels. Taken together with the laser data for the B-X (0,0) band from Adam et al. (J. Chem. Phys. 94, 6240-6262 (1994)) and the Fourier transform emission data for the doublet manifold from Launila et al. (J. Mol. Spectrosc. 186, 131-143 (1997)), the new data give a very complete picture of the vibrational energy level pattern in this region. Strong irregularities in the vibrational dependences of the B(4)Pi rotational and hyperfine constants can be interpreted in terms of spin-orbit interaction between the B(4)Pi state and the f(2)Pi, e(2)Phi, and d(2)Delta states. The interaction is strong enough that all three doublet states can be seen in absorption from the X(4)Sigma(-) ground state, adding to the complexity of the spectrum. The hitherto unknown sigmadeltasigma* (4)Delta state is estimated to lie near 17 500 cm(-1), from the change of sign in the spin-rotation parameter gamma of the B(4)Pi state between v=2 and 3. Copyright 2001 Academic Press.     

Near-Infrared Spectrum of the A(2)Pi(i)-X(2)Sigma(+) (2,0) Band of CN Studied by Concentration Modulation Laser Spectroscopy

The rotational structure of (2,0) vibrational band of A(2)Pi(i)-X(2)Sigma(+) transition of CN has been studied by concentration-modulation laser spectroscopy using a Ti:sapphire laser. The CN radical was produced in the ac glow discharge of acetonitrile with helium as the carrier gas. All 12 branches including four new branches have been observed and measured with an absolute accuracy of 0.007 cm(-1) in the region 12 450-12 750 cm(-1). Analysis of the spectra has led to improved molecular parameters of the A(2)Pi(i) (v' = 2) state. Copyright 2001 Academic Press.     

Variational Calculations of Rovibrational Energies for CO(2)

In this work, the BaI D(2)Sigma(+) and G(2)Sigma(+) electronic states were investigated using laser-induced fluorescence (LIF) and Fourier transform spectroscopy (FTS). The LIF visible spectra were obtained by using the second harmonic of the Ti:sapphire single-mode laser and the Ar(+) and Kr(+) multimode lasers as excitation sources. Previously recorded data, taken from C. A. Leach, A. A. Tsekouras, and R. N. Zare (1992, J. Mol. Spectrosc. 153, 59-72) and from R. F. Gutterres, J. Vergès, and C. Amiot (1999, J. Mol. Spectrosc. 196, 29-44; 2000, J. Mol. Spectrosc. 200, 253-260; and 2000, J. Mol. Spectrosc. 201, 326-327) were combined with the present data. Accurate and improved molecular constants for the X(2)Sigma(+), B(2)Sigma(+), A('2)Delta, A(2)Pi, C(2)Pi, and D(2)Sigma(+) states and 16 term values of the G(2)Sigma(+) state were derived from a simultaneous treatment of the whole data set (12 684 transitions) with a standard deviation of 3.26x10(-3) cm(-1). Copyright 2001 Academic Press.     

Laser-Excited Fluorescence Spectra of Strontium Monoiodide

Fluorescence spectra of strontium monoiodide excited by Ar++ and Kr+ laser lines have been analyzed by Fourier transform spectrometry. Rotational levels have been populated either directly or after collisional relaxation: (i) in D2Sigma+ (v = 0, 1) by ultraviolet lines of Ar++, inducing numerous fluorescence transitions ending in the levels v = 0-3 of the strongly interacting A2Pi and B2Sigma+ states, (ii) in A2Pi3/2 (v = 0-4) by Kr+ line at 676.44 nm, de-exciting into transitions to X2Sigma+ (v = 0-6). Deperturbed constants for A2Pi and B2Sigma+ states and A approximately B interaction parameter are calculated from the numerical treatment of D2Sigma+ (v = 0, 1) --> A2Pi (v = 0-3) approximately B2Sigma+ (v = 0-3) transitions. Rotational constants for D2Sigma+ (v = 0, 1) are obtained for the first time. The wavenumbers of some 670 fluorescence lines are cataloged. Copyright 1999 Academic Press.     

The KRb (2)(3)Sigma(+) Electronic State

High-resolution spectra of the (3)(1)Pi --> (2)(3)Sigma(+) system of the KRb molecule, obtained after excitation with fixed frequencies Ar(+) laser lines, were recorded on a Connes-type Fourier transform interferometer. Molecular constants of the first 14 vibrational levels of the (2)(3)Sigma(+) state are determined. The RKR potential energy curve is derived. The main spectroscopic constants for this triplet electronic state of the (39)K (85)Rb isotopic species are T(e) = 13 507.146(2) cm(-1), omega(e) = 48.6385(6) cm(-1), B(e) = 0.0254152(5) cm(-1), gamma = 0.00164(4) cm(-1), epsilon = -0.469(2) cm(-1), R(e) = 4.98345 ?, 𝒟(e) = 3447 cm(-1). Copyright 2000 Academic Press.     

The Electronic Spectrum of Germanium Monosulfide: Rotational Structure in the A(1)Pi-X(1)Sigma(+) Transition in (70)GeS

The emission spectrum of the specific isotopomer (70)GeS was excited in a microwave (2450-MHz) discharge and the A(1)Pi-X(1)Sigma(+) transition (270-430 nm) was photographed under high resolution on a 10.6-m Ebert grating spectrograph. The rotational analysis of 43 bands led to the determination of accurate vibrational and rotational constants. Making use of these constants, the potential energy curves for the A(1)Pi and X(1)Sigma(+) states were generated by the RKR method and Franck-Condon factors and r-centroids were computed for the bands analyzed. The present extensive high-resolution study has revealed only a few localized perturbations in the A(1)Pi (v'=4, 5, 9) vibronic states, which contrasts with the situation in the isovalent molecules such as GeO, SiS, and SiSe. Copyright 2001 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.