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.     

Infrared and EPR Spectroscopic Studies of 2-C(2)H(2)F and 1-C(2)H(2)F Radicals Isolated in Solid Argon

2-fluorovinyl radicals were generated in solid argon by solid-state chemical reactions of mobile F atoms with acetylene and its deuterated analogues. Highly resolved EPR spectra of the stabilized radicals CHF&dbond;(*)CH, CDF&dbond;(*)CD, CHF&dbond;(*)CD, and CDF&dbond;(*)CH were obtained for the first time. The observed spectra were assigned to cis-2-fluorovinyl radical based on excellent agreement between the measured (a(F) = 6.50, a(betaH) = 3.86, a(alphaH) = 0.25 mT) hyperfine constants and those calculated using density functional (B3LYP) theory. Analogous experiments carried out using infrared spectroscopy yielded a complete assignment of the vibrational frequencies. An unusual reversible photochemical conversion is observed in which cis-2-fluorovinyl radicals can be partially converted to 1-fluorovinyl radicals by pulsed laser photolysis at 532 nm. Photolysis at 355 nm converts 1-fluorovinyl back to cis-2-fluorovinyl. High-resolution EPR and infrared spectra of 1-fluorovinyl were obtained for the first time. The measured hyperfine constants (a(F) = 13.71, a(H1) = 4.21, a(H2) = 1.16 mT) are in good agreement with calculated values. Copyright 2001 Academic Press.     

The angleICI Bending Satellites in the Millimeter-Wave Rotational Spectra of CH(2)I(2) and CD(2)I(2)

Rotational transitions in the first four excited states of the low-frequency angleICI bending mode, nu(4), have been assigned in the mm-wave rotational spectra of CH(2)I(2) and of CD(2)I(2). Measurements of transition frequencies, made over the frequency region 167-326 GHz and for J" up to 190, allowed determination of sextic level spectroscopic constants for all states. The changes in spectroscopic constants with vibrational excitation show very small anharmonicity, in spite of the very low frequency of this mode (121 cm(-1)). Vibrational excitation affects the moments of inertia in such a way that the planar moment P(b), about the plane perpendicular to both angleICI and angleHCH, is practically invariant. Vibrational change in P(c), the moment along the principal axis in the HCH plane and perpendicular to the angleHCH bisector, has been successfully reproduced with an ab initio harmonic force field so that there is no discernible vibrational change in angleHCH on excitation of angleICI. Finally, the change in P(a) leads to estimated vibrational change of +0.12 degrees in the value of angleICI itself. 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.     

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 Spectra, Isotopically Independent Parameters, and Interatomic Potentials for the X(1)(2)Pi(3/2) and X(2)(2)Pi(1/2) States of BrO

Observations of the rotational spectrum of BrO have been extended to include vibrational levels up to v = 8 in the X(1)(2)Pi(3/2) and v = 7 in the X(2)(2)Pi(1/2) states. The rotational spectra of isotopically enriched Br(18)O, X(1), v = 0, 1 and X(2), v = 0 have been observed as well. The spectra of all four isotopic species have been fit to a Hamiltonian in which the parameters have fixed isotopic ratios. An extensive set of isotopically independent parameters has been determined. Interatomic potentials have been derived for both the X(1) and X(2) states. The hyperfine constants and their vibrational dependencies have been determined more precisely and several of them have been determined for the first time. These are interpreted in terms of the electronic structure of the molecule. The isotope relations among the constants have provided a means of decorrelating the electron spin-rotation constant gamma from the fine-structure centrifugal distortion constant, A(D), and have allowed the first determination of an effective value for gamma. Copyright 2001 Academic Press.     

Asymptotically free SU(2) × SU(2) × SU(4) model of unified interaction

An asymptotically free SU(2) × SU(2) × SU(4) model of unified interaction is constructed. The gauge coupling constants are taken equal (in the order of magnitude) to the electromagnetic one. The strong interaction and the quark confinement is provided for by a gluonic mechanism. Some physical consequence of the model are briefly discussed.     

High-Resolution Fourier Transform Emission Spectroscopy of the B(2)Sigma(+) (v = 0)-X(2)Sigma(+) (v = 0) Transition of the PN(+) Ion

Ultraviolet emission spectrum of the B(2)Sigma(+) (v = 0)-X(2)Sigma(+) (v = 0) transition of the PN(+) ion has been observed at a resolution of 0.05 cm(-1) by a Fourier transform spectrometer. The rotational analysis led to a great improvement of rotational constants in the B(2)Sigma(+) (v = 0) and X(2)Sigma(+) (v = 0) states as well as to the first determination of centrifugal distortion constants for both levels and spin-rotation interaction constant in the X(2)Sigma(+) (v = 0) state. Rotational perturbation in the B(2)Sigma(+) (v = 0) state was observed. Copyright 2000 Academic Press.     

Theoretical Calculations of g Factors and Hyperfine Structure Constants for Co2+ inCd2+(I) and Cd2+(II) Sites of CsCdCl3 Crystal

The g factors g‖,g⊥ and hyperfine structure constants A‖,A⊥ for two trigonal Co2+ centers (i.e.,Co2+ in Cd2+ (I) and Cd2+ (II) sites) in CsCdCl3:Co2+ crystals are calculated from the high-order perturbation formulas based on the cluster approach.In the calculation,the contributionsfrom covalency effect and configuration interaction effect are considered and the parameters related to both effects are obtained from the optical spectrum and the structure data of the studied system.The results are in good agreement with the observed values.     

Study of Enol-Keto Tautomerism of N-(2-Hydroxy-1-Naphthylidene)anils

The enol-keto tautomerism of N-(2-hydroxy-1-naphthylidene)anilines was studied. In response to the action of salts (e.g. CaCl₂), in ethanolic solution the equilibrium is shifted extensively in the direction of the keto form; this allows determination of the concentration of the keto form and of the equilibrium constant of the process. In accordance with the Hammett equation, the equilibrium constant varies as a function of the constants a of the substituents on the aniline ring.     

钠分子B^1∏u与2^1∑g^＋间的碰撞激发转移

The B 1pi(u) electronic state of Na2 was excited by the 441.6 nm He-Cd laser line. The Na atomic transitions and the A 1sigma(u)+ --> X 1sigma(g)+ band of Na2 were recorded. From the intensities and spectra of the Na and Na2 fluorescence several collisional processes in the excited sodium atom-dimer system were identified. The Na atomic lines are the result of collisional energy transfer from Na2 (B 1pi(u)) to Na(3P). Predissociation process may also contribute to atomic fluorescence. The A 1sigma(u)+ --> X 1sigma(g)+ band is interpreted through a populating mechanism involving collisional transfer from B 1pi(u) to 2 1sigma(g)+ followed by a radiative transfer to the A 1sigma(u)+ state. From the decay constants and fluorescence intensities, the rate coefficient at 360 degrees C for collisional energy transfer from Na2 (B 1pi(u)) to Na2 (2 1sigma(g)+) was found to be 5.7 x 10(-10) cm3 x s(-1). The predissociation rate of the B 1pi(u) is 2.7 x 10(6) s(-1).     

High-Resolution Study of the Mid-Infrared Region of FNO(2)

Of the gas-phase IR spectrum of nitrylfluoride, FNO(2), between 1200 and 1900 cm(-1), the bands nu(4), 2nu(6), nu(2) + nu(3), and nu(1) have been studied at a resolution of ca. 0.003 cm(-1). Improved ground state rotational and centrifugal distortion constants have been obtained from a simultaneous analysis of the data from F. Hegelund, H. Bürger, and G. Pawelke [J. Mol. Spectrosc. 184, 350-361 (1997)] and the present data from nu(4) and nu(1). The nu(4) and 2nu(6) bands are free from local perturbations, and upper state spectroscopic constants have been obtained from the conventional Watson Hamiltonian. The bands nu(1) and nu(2) + nu(3) are strongly perturbed by Coriolis interactions with the nearby dark levels nu(5) + nu(6), nu(3) + nu(6), and nu(2) + nu(5). Upper state constants for nu(1) and nu(2) + nu(3) are obtained from triad and tetrad models, respectively, including Coriolis resonances within this system. In addition Coriolis interaction parameters and the vibrational energies for the three dark states together with some of their rotational constants are determined from the observed perturbation effects on nu(1) and nu(2) + nu(3). Copyright 2000 Academic Press.     

N_2(B~3Ⅱ_g)高振动态在Xe原子中的碰撞激发和弛豫

在用双光子激发产生的Xe(5p~56p)原子与N_2分子碰撞过程中,有效地生成了N_2(B~3П_g,v=9～14)振动激发态.观察到相应的Δv=4的N_2(B~3П_g-A~3∑_u~+)辐射跃迁萤光,测量了Xe(6p)原子在N_2中的淬灭速率常数,对碰撞弛豫过程进行了讨论.     

Calculation of the eels spectra of the Ni(001) surface with p(2×2) and c(2×2) overlayers of oxygen

We present a force constant slab calculation of the nickel (001) surface phonons with p(2×2) and c(2×2) oxygen overlayers. According to very recent experimental results we assume in both configurations an equal distance of 0.9 Å between the oxygen overlayer and the nickel surface. With two adjustable parameters (the ONi force constants) we are able to reproduce with good accuracy the position and the lineshape of the four peaks present in the experimental EELS spectra. The nature of these peaks is investigated in detail and the noticeable difference between the spectra of the two overlayers is explained.     

Centrifugal Distortion Analysis of a Near-Spherical Top, SO(2)F(2): The First Determination of All Six Quartic Centrifugal Distortion Constants for an Asymmetric Top

The rotational spectrum of the near-spherical top molecule SO(2)F(2) (sulfuryl fluoride) has been investigated by microwave Fourier transform spectroscopy and by millimeter-wave spectroscopy. The ground state spectrum has been measured from 10 to 472 GHz. One of the reasons for studying this molecule is that it is a nearly spherical top and we wanted to verify our theoretical prediction that for such a molecule all six quartic centrifugal distortion constants (and nine sextic distortion constants) should be determinable, while for a standard asymmetric rotor, Watson has shown that only five quartic and seven sextic distortion constants are determinable. The analysis of the spectra confirmed our predictions, because all six quartic constants were well determinable. The results have been confirmed independently by ab initio calculations of the force field and quartic distortion constants. Because the molecule is relatively heavy, contributions of some sextic constants are too small and we have not been able to determine all nine sextic constants predicted by theory. Copyright 2000 Academic Press.     

High-Resolution FTIR Spectrum of the nu(9) Band of Ethylene-D(4) (C(2)D(4))

The spectrum of the nu(9) fundamental band of ethylene-d(4) (C(2)D(4)) has been measured with an unapodized resolution of 0.004 cm(-1) in the frequency range of 2300-2400 cm(-1) using a Fourier transform infrared spectrometer. A total of 549 transitions have been assigned and fitted using a Watson's A-reduced Hamiltonian in the I(r) representation to derive rovibrational constants for the upper state (v(9) = 1) up to five quartic terms with a standard deviation of 0.00087 cm(-1). They represent the most accurate rovibrational constants for the nu(9) band so far. About 30 transitions of K(a)(') = 0, one transition of nu(9) which were identified to be perturbed possibly by the nearby nu(11) and nu(2) + nu(12) transitions, were not included in the final fit. The nu(9) band of C(2)D(4) was found to be basically B-type with an unperturbed band center at 2341.836 94 +/- 0.000 13 cm(-1). Copyright 2000 Academic Press.     

First Observation of the nu(17)-nu(4) Difference Bands of Diborane (10)B(2)H(6) and (11)B(2)H(6)

An analysis of the nu(17)-nu(4) difference bands near 800 cm(-1) of two isotopic species, (10)B(2)H(6) and (11)B(2)H(6), of diborane has been carried out using infrared spectra recorded with a resolution of ca. 0.003 cm(-1). In addition, the nu(17) band of (10)B(2)H(6) has been recorded and assigned. Since this band in (11)B(2)H(6) had already been studied (R. L. Sams, T. A. Blake, S. W. Sharpe, J.-M. Flaud, and W. J. Lafferty, J. Mol. Spectrosc. 191, 331-342 (1998)), it was possible to derive precise energy levels and Hamiltonian constants for the 4(1) vibrational states of both isotopic species. Copyright 2000 Academic Press.     

Analysis of the nu(12) Band of Ethylene-(13)C(2) by High-Resolution FTIR Spectroscopy

The Fourier transform infrared (FTIR) spectrum of the nu(12) fundamental band of ethylene-(13)C(2) ((13)C(2)H(4)) was recorded with an unapodized resolution of 0.004 cm(-1) in the frequency range from 1380 to 1500 cm(-1). Rovibrational constants for the upper state (nu(12)=1) up to five quartic and three sextic centrifugal distortion terms were derived for the first time by assigning and fitting a total of 1177 infrared transitions using a Watson's A-reduced Hamiltonian in the I(r) representation. The rms deviation of the fit was 0.00045 cm(-1). The ground state rovibrational constants were also determined for the first time by a fit of 738 combination differences from the present infrared measurements, with a rms deviation of 0.00060 cm(-1). The A-type nu(12) band with a band center at 1436.65411+/-0.00005 cm(-1) was found to be relatively free from local frequency perturbations. The inertial defect Delta(12) was found to be 0.24300+/-0.00002 u?(2). Copyright 2001 Academic Press.