E. A. Pazyuk

High resolution spectroscopy and channel-coupling treatment of the A 1Σ+–b 3Π complex of NaRb

The paper presents the study of the fully mixed A 1Σ+–b 3Π complex of the NaRb molecule based on high-resolution sub-Doppler spectroscopy and intensity measurements, ab initio relativistic calculations of energies, transition moments and spin–orbit interactions, as well as an inverted channel-coupling approach (ICCA) deperturbation analysis. A two-laser V-type pump–probe excitation scheme was employed to obtain A←X transition frequencies to 16 A-state vibrational levels from v=6 to v=21 with J from 8 to 23. Additionally, relative intensities in laser-induced A→X fluorescence spectra have been recorded, including progressions with all observable transitions to the ground state vibronic levels, the latter yielding unambiguous v assignment of the A-state levels observed. All experimental rovibronic term values and all measured intensity distributions were embedded in a direct simultaneous weighted nonlinear fitting in the framework of an elaborated ICCA allowing us to obtain deperturbed relativistic diabatic...

The c 3Σ+,b 3Π, and a 3Σ+ states of NaK revisited

We present new c 3Σ+→a 3Σ+ laser induced fluorescence spectra of the NaK molecule, which clearly indicate that v0=20 is the first vibrational level of the c 3Σ+ state lying above v=0 of B 1Π state. These spectra are used in a multistep deperturbation (B 1Π∼c 3Σ+∼b 3Π) procedure to obtain improved a 3Σ+, b 3Π and c 3Σ+ potential energy curves. The deperturbation analysis is confirmed by the calculated electronic B 1Π∼c 3Σ+ and c 3Σ+∼b 3Π spin–orbit matrix elements obtained from many-body multipartitioning perturbation theory employing the relativistic effective potential method.

Lifetimes and transition dipole moment functions of NaK low lying singlet states: Empirical and ab initio approach

The paper presents experimental D 1∏ state lifetime τv′J′ data and develops empirical and ab initio approaches concerning D 1∏ and B 1∏ lifetimes, as well as D 1∏–X 1∑+, B 1∏–X 1∑+ and D 1∏–A 1∑+ transition dipole moment functions μ(R) of the NaK molecule. Experimental D 1∏(v′,J′) state τv′J′ values for v′ varying from 1 to 22 have been obtained from experimentally measured electric radio frequency-optical double resonance (rf-ODR) signal contours. The rf-ODR signals have been produced by D 1∏←X 1∑+ laser induced optical transition and rf field (1–900 MHz) induced e–f transition within the D 1∏(v′,J′) level. The possibility to determine empirical absolute μ(R) function in a wide R range from experimental τv′J′ dependence on v′ and J′ has been demonstrated; such an approach has been applied to obtain μ(R) for the B 1∏–X 1∑+ transition on which relative intensity data are absent. The empirical D 1∏–X 1∑+μ(R) function has been considerably improved by simultaneous fitting of relative intensity and lifetime d...

Fourier-transform spectroscopy and coupled-channels deperturbation treatment of the A 1 Σ + – b 3 Π complex of KCs

The laser induced fluorescence (LIF) spectra A1Sigma ~ b3Pi --> X1Sigma+ of KCs dimer were recorded in near infrared region by Fourier Transform Spectrometer with a resolution of 0.03 cm-1. Overall more than 200 LIF spectra were rotationally assigned to 39K133Cs and 41K133Cs isotopomers yielding with the uncertainty of 0.003-0.01 cm-1 more than 3400 rovibronic term values of the strongly mixed singlet A1Sigma+ and triplet b3Pi states. Experimental data massive starts from the lowest vibrational level v_A=0 of the singlet and nonuniformly cover the energy range from 10040 to 13250 cm-1 with rotational quantum numbers J from 7 to 225. Besides of the dominating regular A1Sigma+ ~ b3P Omega=0 interactions the weak and local heterogenous A1S+ ~ b3P Omega=1 perturbations have been discovered and analyzed. Coupled-channel deperturbation analysis of the experimental 39K133Cs e-parity termvalues of the A1S+ ~ b3P complex was accomplished in the framework of the phenomenological 4 x 4 Hamiltonian accounting implicitly for regular interactions with the remote states manifold. The resulting diabatic potential energy curves of the interacting states and relevant spin-orbit coupling matrix elements defined analytically by Expanded Morse Oscillators model reproduce 95% of experimental data field of the 39K133Cs isotopomer with a standard deviation of 0.004 cm-1 which is consistent with the uncertainty of the experiment. Reliability of the derived parameters was additionally confirmed by a good agreement between the predicted and experimental termvalues of 41K133Cs isotopomer. Calculated intensity distributions in the A ~ b --> X LIF progressions are also consistent with their experimental counterparts.

Identification of Deeply Bound Heteronuclear Molecules Using Pulsed Laser Depletion Spectroscopy

We demonstrate that a near-dissociation photoassociation resonance can be used to create a deeply bound molecular sample of ultracold NaCs. To probe the resulting vibrational distribution of the sample, we use a new technique that can be applied to any ultracold molecular system. We utilize a tunable pulsed dye laser to produce efficient spectroscopic scans (∼ 700 cm at a time) in which we observe the 1Σ → 2Σ − 2Π vibrational progression, as well as the dissociation limit to the Cs 62P3/2 asymptote. We assign 1 Σ(v = 4, 5, 6, 11, 19) vibrational levels in our sample.

Molecular hydrogen 3s,d 3Λg+ complex revisited

The rovibronic term values, Lande factors, and radiative properties of all bound levels in the 3s,d 3Λg+ complex of H2, D2, and HD are evaluated in the framework of fully ab initio channel-coupling approach. The modified multichannel quantum-defect theory is employed to transform highly accurate ab initio Born–Oppenheimer electronic matrix elements borrowed from a literature to their diabatic counterparts avoiding explicit consideration of radial coupling effects. The radiative lifetimes of the most critical levels in the H2 complex are remeasured by a delayed coincidence method. The accuracy of the predicted term values, Lande factors, transition probabilities and experimental lifetimes is sufficient to indicate the sources of disagreement in existing theory and experimental data.

Permanent electric dipoles in B 1Π and D 1Π states of NaRb: Experiment and theory

The paper presents experimentally obtained permanent electric dipole moment values (μ) in electronically excited B 1Π and D 1Π states of 23Na85Rb and 23Na87Rb isotopomer molecules for a number of vibrational and rotational levels (v′,J′). The method is based on measuring relative intensities of “forbidden” fluorescence lines appearing due to dc Stark effect induced e/f parity mixing for a particular (v′,J′)-level, combined with electric radio frequency–optical double resonance measurement of Λ-splitting energy Δe,f. The measured D 1Π state μ values are close to 6 D, representing minor changes with the vibrational level v′ varying from 0 to 12 and J′ in the region between 7 and 50, while the measured B 1Π state μ values are about 3 D for v′=4, 5 and 6. The X 1Σ+, B 1Π, and D 1Π dipole moment functions μ(R) are calculated ab initio using the many body multipartitioning perturbation theory for explicit treatment of core-valence correlations. The theoretical and experimental dipole moment estimates are in a p...

APPROXIMATE SUM RULE FOR DIATOMIC VIBRONIC STATES AS A TOOL FOR THE EVALUATION OF MOLECULAR PROPERTIES

Abstract The approximate sum rule ≈ Σv2 (Ev1 - Ev2)n, where f, g are operators which couple the vibrational levels v1, v2 of two interacting electronic states and ΔU=U1—U2 is the difference of the corresponding internuclear potentials, is numerically tested for radiative lifetimes, electronic polarizabilities, fine-structure constants and Lande factors for the vibronic states of the NaK molecule. The approximation is demonstrated to have high accuracy and efficiency for non-diagonal systems, especially for those with significant continuum contributions. Simple ways of estimating the sum rule accuracy are given.

The I-2(B) predissociation by solving an inverse atoms-in-molecule problem

The valence electronic states of the iodine molecule are analysed by means of a simple atoms-in-molecule model which accounts for the lowest 2P states of iodine atoms and approximates the spin-orbit interaction by its atomic part. For this model, an inverse problem is solved, i.e. non-relativistic potential energy curves and diabatic couplings are determined by a least-squares fit to known relativistic potential energy curves. The resulting adiabatic wave functions are used to calculate the electronic matrix elements responsible for natural, hyperfine and magnetic predissociation of the iodine molecule in the B0+ u: state. The results are in reasonable agreement with experimental data, being stable enough with respect to the variation of input relativistic potentials. They also indicate the importance of diabatic couplings between the non-relativistic states of the same symmetry.

Molecular constants of the NbN molecule

Abstract Absorption spectrum of NbN has been obtained in the 560–670 nm region by intracavity laser spectroscopy. Vibrational and rotational analyses of 3φ - 3Δ transition has been caried out. Molecular constants for the upper (3φ) and ground (3Δ) states have been determined.