Rotationally inelastic collisions of excited NaK and NaCs molecules with noble gas and alkali atom perturbers.

We report measurements of rate coefficients at T ≈ 600 K for rotationally inelastic collisions of NaK molecules in the 2(A)1Σ+ electronic state with helium, argon, and potassium atom perturbers. Several initial rotational levels J between 14 and 44 were investigated. Collisions involving molecules in low-lying vibrational levels (v = 0, 1, and 2) of the 2(A)1Σ+ state were studied using Fourier-transform spectroscopy. Collisions involving molecules in a higher vibrational level, v = 16, were studied using pump/probe, optical-optical double resonance spectroscopy. In addition, polarization spectroscopy measurements were carried out to study the transfer of orientation in these collisions. Many, but not all, of the measurements were carried out in the "single-collision regime" where more than one collision is unlikely to occur within the lifetime of the excited molecule. The analysis of the experimental data, which is described in detail, includes an estimate of effects of multiple collisions on the reported rate coefficients. The most significant result of these experiments is the observation of a strong propensity for ΔJ = even transitions in collisions involving either helium or argon atoms; the propensity is much stronger for helium than for argon. For the initial rotational levels studied experimentally, almost all initial orientation is preserved in collisions of NaK 2(A)1Σ+ molecules with helium. Roughly between 1/3 and 2/3 of the orientation is preserved in collisions with argon, and almost all orientation is destroyed in collisions with potassium atoms. Complementary measurements on rotationally inelastic collisions of NaCs 2(A)1Σ+ with argon do not show a ΔJ = even propensity. The experimental results are compared with new theoretical calculations of collisions of NaK 2(A)1Σ+ with helium and argon. The calculations are in good agreement with the absolute magnitudes of the experimentally determined rate coefficients and accurately reproduce the very strong propensity for ΔJ = even transitions in helium collisions and the less strong propensity for ΔJ = even transitions in argon collisions. The calculations also show that collisions with helium are less likely to destroy orientation than collisions with argon, in agreement with the experimental results.

A full analytic potential energy curve for the a 3 Sigma+ state of KLi from a limited vibrational data set.

Fourier transform spectra of near-infrared laser-induced fluorescence in (39)K(6)Li show transitions to high vibrational levels of both the X (1)Sigma(+) and a (3)Sigma(+) electronic states. These include 147 transitions into six vibrational levels of the a (3)Sigma(+) state, which lie between 7 and 88 cm(-1) below the dissociation asymptote. Unfortunately, their energies span less than 30% of the well depth. However, fitting those data to eigenvalues of analytical model potential functions whose outer limbs incorporate the theoretically predicted long-range form, V(R) approximately D-C(6)R(6)-C(8)R(8), yields complete, plausible potential curves for this state. The best fits converge to remarkably similar solutions which indicate that D(e)=287(+/-4) cm(-1) and R(e)=4.99(+/-0.09) A for the a (3)Sigma(+) state of KLi, with omega(e)=47.3(+/-1.4) and 44.2(+/-1.5) cm(-1) for (39)K(6)Li and (39)K(7)Li, respectively. Properties of the resulting potential are similar to those of a published ab initio potential and are consistent with those of the analogous states of Li(2), K(2), Na(2), and NaK.

Fourier Transform Spectra of the E(2)Pi(u)-X(2)Pi(g)((3/2)) System of CuCl(2).

High-resolution Fourier transform spectra of the laser-induced fluorescence of (63)Cu(37)Cl(2) produced in a cell have been recorded following excitation of a single vibronic level of the E(2)Pi(u) electronic state. Fluorescence occurs in combination bands to a broad spread of levels in the ground electronic state. A global vibronic model is proposed for the ground state based on an effective Hamiltonian, which fits the experimental data (2782 fluorescence lines, lower state quantum numbers: v(1) = 0-6, v(2) = 0-2, v(3) = 0-6, and J = 4(1/2)-80(1/2)) to 0.019 cm(-1) rms error. Vibrational, rotational and Renner-Teller parameters are obtained (e.g., omega(2) = 95.195(36) cm(-1), B(e) = 0.055106(3) cm(-1), epsilon = -0.1893(28)). A revised value for the equilibrium internuclear distance Cu-Cl is deduced: r(e)(Cu-Cl) = 0.20341(3) nm. The energy diagram of vibronic levels in the ground state is plotted up to 4000 cm(-1). Copyright 2000 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.

On the 5d 1Pig --> 2 (1)Sigma+u and 5d 1Pig --> C 1Piu Fluorescence in 7Li2.

Following excitation of the 5d 1Pig Rydberg state of 7Li2 by optical-optical double resonance, fluorescence has been observed in the infrared region to the 2 (1)Sigma+u and C 1Piu states. Analysis of high-resolution Fourier transform spectra yields term energies and rotational constants of the lowest seven vibrational levels of the inner well of the 2 (1)Sigma+u "double minimum" state. The equilibrium term value and dissociation energy have been determined to be Te = 30101.45 +/- 0.12 cm-1 and De = 5621.3 +/- 0.2 cm-1. The v = 0 and 1 levels of the C 1Piu state have been analyzed, resulting in new values of Te = 30551.0 +/- 0.1 cm-1 and De = 7773.3 +/- 0.2 cm-1. Copyright 1998 Academic Press.