Excellent Ultracold Molecular Candidates From Group VA Hydrides: Whether Do Nearby Electronic States Interfere?

By means of highly accurate ab initio calculations, we identify two excellent ultracold molecular candidates from group VA hydrides. We find that NH and PH are suitable for the production of ultracold molecules, and the feasibility and advantage of two laser cooling schemes are demonstrated, which involve different spin-orbit states (A3Π2 and X3Σ1− ). The internally contracted multireference configuration interaction method is applied in calculations of the six low-lying Λ-S states of NH and PH with the spin-orbit coupling effects included, and excellent agreement is achieved between the computed and experimental spectroscopic data. We find that the locations of crossing point between the A3Π and Σ−5 states of NH and PH are higher than the corresponding v′ = 2 vibrational levels of the A3Π state indicating that the crossings with higher electronic states would not affect laser cooling. Meanwhile, the extremely small vibrational branching loss ratios of the A3Π2 → a1Δ2 transition for NH and PH (NH: 1.81 × 10–8; PH: 1.08 × 10–6) indicate that the a1Δ2 intermediate electronic state will not interfere with the laser cooling. Consequently, we construct feasible laser-cooling schemes for NH and PH using three lasers based on the A3Π2 → X3Σ1− transition, which feature highly diagonal vibrational branching ratio R00 (NH: 0.9952; PH: 0.9977), the large number of scattered photons (NH: 1.04×105; PH: 8.32×106) and very short radiative lifetimes (NH: 474 ns; PH: 526 ns). Our work suggests that feasible laser-cooling schemes could be established for a molecular system with extra electronic states close to those chosen for laser-cooling.

An electron wave packet in the relativistic strophotron FEL

The theory of free electron lasers (FELs) is well developed both in quantum mechanical and classical approaches. In strophotron FEL, in classical approach, resonance frequency and the gain are strongly dependent on initial parameters of electron beam. In the quantum mechanical approach considered by Zaretsky and Nersesov (1983 JETP 57 518), there is no such dependence. The correspondence between the quantum mechanical and classical approaches in a relativistic strophotron FEL is discussed. We study the initial distribution of electrons over vibrational levels determined by the expansion coefficients in relativistic strophotron FEL. It is shown, (presenting electron wave function in the form of Gaussian wave packet), that the number of the vibrational level most efficiently populated at the initial moment of time can be expressed in terms of the initial parameters of the electron beam.

Computational Characterization of Astrophysical Species: The Case of Noble Gas Hydride Cations

Theoretical–computational studies together with recent astronomical observations have shown that under extreme conditions in the interstellar medium (ISM), complexes of noble gases may be formed. Such observations have generated a wide range of possibilities. In order to identify new species containing such atoms, the present study gathers spectroscopic data for noble gas hydride cations, NgH+ (Ng = He, Ne, Ar) from high-level ab initio quantum chemistry computations, aiming to contribute in understanding the chemical bonding and electron sharing in these systems. The interaction potentials are obtained from CCSD(T)/CBS and MRCI+Q calculations using large basis sets, and then employed to compute vibrational levels and molecular spectroscopic constants for all known stable isotopologues of ground state NgH+ cations. Comparisons with previously reported values available are discussed, indicating that the present data could serve as a benchmark for future studies on these systems and on higher-order cationic noble gas hydrides of astrophysical interest.

Cross sections for the two-step radiative decay process $$X(v)\rightarrow A(v^{\prime \prime })\rightarrow X(v^\prime )$$ in e-LiH collisions

The cross sections for the two-step process, represented by the electron-impact vibro-electronic excitation $$X^1\varSigma ^+(v) \rightarrow A^1\varSigma ^+(v'')$$ X 1 Σ + ( v ) → A 1 Σ + ( v ′ ′ ) of the LiH molecule, followed by radiative decay back on the vibrational manifold of the ground state, $$A^1\varSigma ^+(v'')\rightarrow X^1\varSigma ^+(v')$$ A 1 Σ + ( v ′ ′ ) → X 1 Σ + ( v ′ ) , are calculated as a function of the incident electron energy from the threshold to 1000 eV. The final cross sections for the two-step process, which results in an overall vibrational excitation of the molecule, known also as E-v process, are provided for all the possible $$v,v'$$ v , v ′ transitions among the vibrational levels, including the continuum, of the electronic ground state. Graphic abstract

Природа тонкой структуры вращательных уровней основного X-=SUP=-2-=/SUP=-Sigma-=SUP=-+-=/SUP=--состояния радикала CN

By means of ab initio high-level quantum-chemical calculations of non-diagonal matrix elements of spin-orbital and electron-rotational coupling between the ground X2Σ+ and excited (1--4)2Π states the observed regular effect of γ-doubling of the rotational levels of the X2Σ+ state was shown to be mainly determined by intramolecular interactions of the mentioned state with remote states (2--4)2Π. In terms of the nonadiabatic model of the effective radial Hamiltonian of the isolated electronic state, it was possible to create the analytical potential of the X2Σ+ state and the corresponding function γ (R) reproducing the frequencies of rotational and vibrational-rotational transitions (for the lowest vibrational levels ν≤3) of the CN molecule at the experimental (spectroscopic) level of accuracy.