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.

Precise Molecular Constants for the 6Li2 A1Sigma+u-X1Sigma+g System by Sub-Doppler Polarization Spectroscopy.

We report here new and more accurate molecular constants from sub-Doppler polarization spectroscopy of the A1Sigma+u-X1Sigma+g system of 6Li2 using single mode cw dye lasers. These new constants cover the range of vibrational levels from v" = 0-8 in the ground state and v' = 0-24 in the excited state. New molecular constants and RKR potential energy curves for the A1Sigma+u and X1Sigma+g states are given. The Te value for the A1Sigma+u state is 14068.043(34) cm-1. The analysis indicates that there is a noticeable breakdown of the Born-Oppenheimer approximation for the 6Li2 and 7Li2 isotopomers. Copyright 1998 Academic Press.

The 4(3)Pi(g) State of Na(2): Vibrational Numbering and Hyperfine Structure.

The Na(2) 4(3)Pi(g) state has been studied by continuous-wave (cw) perturbation-facilitated optical-optical double resonance (PFOODR) fluorescence excitation and resolved fluorescence spectroscopy. The absolute vibrational numbering was determined by resolved fluorescence to the a(3)Sigma(+)(u) state. The OODR excitation lines of the 4(3)Pi(g) (Kv, N) <-- b(3)Pi(u) (Kv(b)('), J') approximately A(1)Sigma(+)(u) (Kv(A)('), J') <-- X(1)Sigma(+)(g) (Kv", J") transitions show hyperfine splittings, and the hyperfine coupling scheme of the upper 4(3)Pi(g) levels is case b(betaS). Although this 4(3)Pi(g) state dissociates to the 3p + 3p atomic limit, it is a Rydberg state at a small internuclear distance, and the hyperfine splitting is caused mainly by the Fermi contact interaction of the varsigma(g)3s valence electron with the nuclei. The Fermi contact constant was determined to be b(F) = 218.3 +/- 3.9 MHz. Copyright 1999 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.

Rotational Pattern Difference in Resolved Fluorescence Spectra with Different Detection Schemes.

The relative intensities of rotational lines in resolved fluorescence spectra are dependent on the detection direction and the choice of the detection scheme when a grating monochromator is used. These differences arise from the spatially anisotropic distribution of the fluorescence, the rotational branch dependence of the fluorescence polarization, and the polarization dependence of the monochromator grating efficiency. Both the anisotropy of the emission and the rotational branch dependence of the fluorescence polarization are enhanced in double-resonance excitation schemes. In the present work, we analyze the relative intensities in the (7)Li(2) 1(3)Sigma(-)(g) --> 1(b)(3)Pi(u) and 1(3)Delta(g) --> 1(b)(3)Pi(u) resolved fluorescence spectra, observed following double-resonance excitation, for three different detection schemes. Copyright 1999 Academic Press.

New Vibrational Numbering and Potential Energy Curve for the 3(3)Pig Electronic State of the Li2 Molecule.

An experimental study of the 3(3)Pig electronic state of 7Li2, using the Perturbation-Facilitated Optical-Optical Double Resonance (PFOODR) technique, was recently reported [A. Yiannopoulou et al., J. Chem. Phys. 103, 5898, (1995)]. However, due to the very small number of known 7Li2 A1Sigma+u approximately b3Piu window levels, only 13 ro-vibrational levels (spanning a range of vibrational levels designated upsilonx - 1 to upsilonx + 3 in that reference) could be observed. Dunham coefficients, based on the assignment upsilonx = 7, were found to fit the observed term values and give a qualitative fit to the intensities of the first six lines of the 3(3)Pig (upsilon = upsilonx, N = 11) --> b3Piu emission spectrum. However, due to the limited number of levels used in the fit, both the absolute vibrational numbering and the 3(3)Pig RKR potential curve obtained from the Dunham coefficients, must be considered to be uncertain. In the present work, we show that the previously reported 3(3)Pig RKR curve is unable to reproduce the experimental intensity distribution in the 7Li2 3(3)Pig (upsilonx = 7, N = 11) --> a3Sigma+u emission continuum. We report new experimental data for the 7Li2 3(3)Pig (upsilonx + 1, N = 11) --> a3Sigma+u bound-free continuum and discrete 3(3)Pig (upsilonx +/- 1, N = 11) --> b3Piu spectra obtained using the PFOODR experimental technique. We demonstrate that the correct vibrational numbering and an improved RKR potential curve can be obtained by analyzing the experimental term values in combination with all observed bound-free and discrete spectra. Finally, term values for four 6Li2 3(3)Pig ro-vibrational levels were obtained using PFOODR spectroscopy. The measured isotope shifts confirm the absolute vibrational numbering obtained from the present analysis. Copyright 1999 Academic Press.

The High-Lying Vibrational Levels and Dissociation Energy of the a3Sigma+u State of 7Li2.

Perturbation-facilitated optical-optical double resonance (PFOODR) has been used to access the 2(3)Pig state of 7Li2 via the excitation scheme using two single-mode tunable lasers. The selected () mixed level provides a gateway through which the triplet manifold can be accessed. Fluorescence from single rovibrational levels of 2(3)Pig to the state was detected at high resolution using a Fourier transform spectrometer. Transitions to v = 0-9 in the state were observed, covering the potential well almost to the dissociation limit. The data were analyzed using a near dissociation expansion (NDE) technique and the resulting vibrational and rotational parameters were used to calculate a new RKR potential curve which reproduced the observed energy levels to within a rms error of 0.02 cm-1. The following parameters were obtained for the state: D0 = 301.829 +/- 0.015 cm-1, De = 333.69 +/- 0.10 cm-1, Te = 8183.12 +/- 0.12 cm-1. Copyright 1999 Academic Press.

The Predissociation of the 1(3)Sigma(-)(g) State of (7)Li(2).

The predissociation of the 1(3)Sigma(-)(g) v >/= 10 levels of (7)Li(2) has been observed by pulsed and continuous-wave perturbation-facilitated optical-optical double-resonance spectroscopy (PFOODR). Our ab initio calculation shows that the inner wall of the 1(3)Sigma(-)(g) potential intersects the 1(3)Pi(g) repulsive potential at internuclear distance R = 2.00 Å. The predissociation is due to a DeltaS = 0, DeltaLambda = +/-1 rotational-electronic interaction with the repulsive 1(3)Pi(g) state. Copyright 2001 Academic Press.