Full-dimensional quantum scattering calculations are reported for ro-vibrational transitions in HD+HD collisions using a highly accurate interaction potential for the H$_2$-H$_2$ system. Several near-resonant ro-vibrational transitions are identified that conserve the overall rotational angular momentum and nearly conserve the internal energy of the collision partners. Key anisotropic terms that drive the rotational transitions and angular momentum partial waves that contribute to low energy resonant features in the energy dependence of the cross sections are identified. The computed results are in agreement with total cross sections reported in previous experimental results, including resonant features in the energy dependence of the cross section. In particular, low-energy cross sections show a strong resonant feature associated with an $l=3$ partial wave in the incident channel. Rate coefficients for several inelastic rotational and ro-vibrational transitions are reported for temperatures ranging from $0.1$ K to $200$ K and they display a maximum between $1$ K-$10$ K reflecting the important contributions from the $l=3$ shape resonance that occurs around 2.5 K.
The H$_2$+H$_2$ system has long been considered as a benchmark system for ro-vibrational energy transfer in bimolecular collisions. However, most studies thus far have focused on collisions involving H$_2$ molecules in the ground vibrational level or in the first excited vibrational state. While H$_2$+H$_2$/HD collisions have received wide attention due to the important role they play in astrophysics, D$_2$+D$_2$ collisions have received much less attention. Recently, Zhou et al. [Nat. Chem. 4 658 (2022)] examined stereodynamic aspects of rotational energy transfer in collisions of two aligned…
Photodissociation cross sections for the SH$^+$ radical are computed from all rovibrational (RV) levels of the ground electronic state X$~^3Σ^-$ for wavelengths from threshold to 500~Å. The five electronic transitions, $2~ ^3Σ^- \leftarrow$ X$~^3Σ^-$, $3~ ^3Σ^- \leftarrow$ X$~^3Σ^-$, $A~ ^3Π\leftarrow$ X$~^3Σ^-$, $2~ ^3Π\leftarrow$ X$~^3Σ^-$, and $3~ ^3Π\leftarrow$ X$~^3Σ^-$, are treated with a fully quantum-mechanical two-state model, {i.e. no non-adiabatic coupling between excited states was included in our work.}. The photodissociation calculations incorporate adiabatic potentials and trans…
We present a formalism for cold and ultracold atom-diatom chemical reactions that combines a quantum close-coupling method at short-range with quantum defect theory at long-range. The method yields full state-to-state rovibrationally resolved cross sections as in standard close-coupling (CC) calculations but at a considerably less computational expense. This hybrid approach exploits the simplicity of MQDT while treating the short-range interaction explicitly using quantum CC calculations. The method, demonstrated for D+H$_2\to$ HD+H collisions with rovibrational quantum state resolution of the…
Partial wave resonances are quasi-bound states that are formed by tunneling through the centrifugal barrier. Such states are important to collisions that deviate from the Langevin limit where direct collision path is suppressed due to quantum symmetry or a potential barrier. In such a case, quantum resonances play a major role in the dynamics at low temperatures where scattering process can be described mainly by the resonance contribution. Here we present the first observation of the lowest-lying partial wave resonance in the Penning ionization collisions between metastable neon and rovibrati…
We show that the highly excited rovibrational spectra of a diatomic molecule and the closely related slow atomic collision processes contain more systematics and require less parameters to characterize than the Rydberg spectrum of an atom. In the case of a single channel, for example, we show that a single short-range parameter gives a complete description of slow collisions for practically all angular momenta, and covers an energy range of hundreds of millikelvins. The same parameter also describes the highly excited rovibrational spectra in the threshold region, including states of different…
We study an excited atom-polar molecular ion chemical reaction (Ca$^*$ + BaCl$^+$) at low temperature by utilizing a hybrid atom-ion trapping system. The reaction rate and product branching fractions are measured and compared to model calculations as a function of both atomic quantum state and collision energy. At the lowest collision energy we find that the chemical dynamics dramatically differ from capture theory predictions and are primarily dictated by the radiative lifetime of the atomic quantum state instead of the underlying excited-state interaction potential. We provide a simple rule …
We study the excitation redistribution from cesium $7\mathrm{P}_{1/2}$ or $7\mathrm{P}_{3/2}$ to neighboring energy levels by Black Body Radiation (BBR) and inter atomic collisions using pump-probe spectroscopy inside a vapor cell. At low vapor densities we measure redistribution of the initial, velocity-selected, atomic excitation by BBR. This preserves the selected atomic velocities allowing us to perform high resolution spectroscopy of the $\mathrm{6D\rightarrow 7F}$ transitions. This transfer mechanism could also be used to perform sub-Doppler spectroscopy of the cesium highly-excited $\ma…
In a proof-of-principle experiment, we demonstrate that metastable nitric oxide molecules, NO(a$^4Π_i$), generated inside a pulsed, supersonic beam, can be detected by reactive gas-phase collisions with electronically excited Li atoms in the $2^2$P$_{3/2}$ state. Since the internal energy of NO(a$^4Π_i$, $v \leq 4$) is lower than the ionization potential of Li in the $2^2$S$_{1/2}$ electronic ground state, we observe that the product ion yield arising from autoionizing NO(a$^4Π_i$)+Li($2^2$S$_{1/2}$) collisions is a factor of 21 lower than the ion yield from NO(a$^4Π_i$)+Li($2^2$P$_{3/2}$) col…
Using a recently developed method for precisely controlling collision energy, we observe a dramatic suppression of inelastic collisions between an atom and ion (Ca + Yb$^+$) at low collision energy. This suppression, which is expected to be a universal phenomenon, arises when the spontaneous emission lifetime of the excited state is comparable to or shorter than the collision complex lifetime. We develop a technique to remove this suppression and engineer excited-state interactions. By dressing the system with a strong catalyst laser, a significant fraction of the collision complexes can be ex…
We measure inelastic collisional cross sections for the ground $^3$F$_2$ state and the excited $^3$P$_0$ state of atomic thorium in cold collisions with $^3$He. We determine for Th ($^3$F$_2$) at 800 mK the ratio $γ\approx 500$ of the momentum-transfer to Zeeman relaxation cross sections for collisions with $^3$He. For Th ($^3$P$_0$), we study electronic inelastic processes and find no quenching even after $10^6$ collisions. We also determine the radiative lifetime of Th ($^3$P$_0$) to be $τ> 130$ ms. This great stability of the metastable state opens up the possibility for further study, incl…
Emission lines from highly-excited states (n >= 5) of H- and He-like ions have been detected in astrophysical sources and fusion plasmas. For such excited states, R-matrix or distorted wave calculations for electron-impact excitation are very limited, due to the large size of the atomic basis set needed to describe them. Calculations for n >= 6 are also not generally available. We study the behaviour of the electron-impact excitation collision strengths and effective collision strengths for the most important transitions used to model electron collision dominated astrophysical plasmas, solar, …
We investigate the ultracold collisions of rotationally excited dipolar molecules in free-space, taking the hetero-nuclear bi-alkali molecule of KRb as an example. We show that we can sharply tune the elastic, inelastic and reactive rate coefficients of lossy molecular collisions when a second rotationally excited colliding channel crosses the threshold of the initial colliding channel, with the help of an applied electric field, as found by Avdeenkov et al. for non-lossy molecules [Phys. Rev. A 73, 022707 (2006)]. We can increase or decrease the loss processes whether the second channel is ab…
The deexcitation of exotic hydrogen atoms in highly excited states in collisions with hydrogen molecules has been studied using the classical-trajectory Monte Carlo method. The Coulomb transitions with large change of principal quantum number n have been found to be the dominant collisional deexcitation mechanism at high n. The molecular structure of the hydrogen target is shown to be essential for the dominance of transitions with large Δn. The external Auger effect has been studied in the eikonal approximation. The resulting partial wave cross-sections are consistent with unitarity and provi…
The atomic cascades in mu-p and pbar-p atoms have been studied in detail using new results for the cross-sections of the scattering of highly excited exotic atoms from molecular hydrogen. The cascade calculations have been done with an updated version of the extended standard cascade model that computes the evolution in the kinetic energy from the beginning of the cascade. The resulting X-ray yields, kinetic energy distributions, and cascade times are compared with the experimental data.
We investigate Cs+Cs scattering in excited Zeeman and hyperfine states. We calculate the real and imaginary parts of the s-wave scattering length; the imaginary part directly provides the rate coefficient for 2-body inelastic loss, while the real part allows us to identify regions of magnetic field where 3-body recombination will be slow. We identify field regions where Cs in its $(f,m_f)=(3,+2)$ and $(3,+1)$ states may be stable enough to allow Bose-Einstein condensation, and additional regions for these and the $(3,0)$ and $(3,-3)$ states where high-density clouds should be long-lived.
We present a theoretical study of charge transfer in collisions of excited ($n=2,3$) hydrogen atoms with He$^+$ and in collisions of excited ($n=2,3$) helium atoms with H$^+$, extending the results of Phys. Rev. A 82 012708 (2010). A combination of quantum-mechanical and semi-classical approaches is employed to calculate the charge-exchange cross sections at collision energies from 0.1 eV/u up to 1 keV/u. These methods are based on accurate ab initio potential energy curves and non-adiabatic couplings for the molecular ion HeH$^+$. Charge transfer can occur either in singlet or in triplet stat…
We consider a neutralization of excited antiprotonic helium ion accompanied by antiproton transitions to lower states in collisions with helium atoms $(\bar{p}\mathrm{He}^{2+})_{nl} + \mathrm{He} \rightarrow \left[ (\bar{p}\mathrm{He}^{2+})_{n_f l_f} e\right]_{1s} + \mathrm{He}^+$ in low-temperature medium. Interactions in the input and output channels are taken similar to the potentials of $\mathrm{H}^+ - \mathrm{He}$ ($X^1Σ$) and $\mathrm{H} - \mathrm{He}^+$ ($A^1Σ$) systems, respectively. The final term is shifted down by the antiproton transition energy. Therefore initial and final terms c…
Full control of molecular interactions, including reactive losses, would open new frontiers in quantum science. Here, we demonstrate extreme tunability of chemical reaction rates by using an external electric field to shift excited collision channels of ultracold molecules into degeneracy with the initial collision channel. In this situation, resonant dipolar interactions mix the channels at long range, dramatically altering the intermolecular potential. We prepare fermionic potassium-rubidium (KRb) molecules in their first excited rotational state and observe a three orders-of-magnitude modul…
Ultracold collisions between Cs atoms and Cs2 dimers in the electronic ground state are observed in an optically trapped gas of atoms and molecules. The Cs2 molecules are formed in the triplet ground state by cw-photoassociation through the outer well of the 0g-(P3/2) excited electronic state. Inelastic atom-molecule collisions converting internal excitation into kinetic energy lead to a loss of Cs2 molecules from the dipole trap. Rate coefficients are determined for collisions involving Cs atoms in either the F=3 or F=4 hyperfine ground state and Cs2 molecules in either highly vibrationally e…
We determine effective collisional radii of positronium (Ps) by considering Ps states in hard-wall spherical cavities. $B$-spline basis sets of electron and positron states inside the cavity are used to construct the states of Ps. Accurate Ps energy eigenvalues are obtained by extrapolation with respect to the numbers of partial waves and radial states included in the bases. Comparison of the extrapolated energies with those of a pointlike particle provides values of the effective radius $ρ_{nl}$ of Ps($nl$) in collisions with a hard wall. We show that for $1s$, $2s$, and $2p$ states of Ps, th…
Low-energy E < 2 eV electron elastic collisions with Ge, Sn and Pb atoms yield stable excited Ge-, Sn- and Pb- anions. The recent Regge-pole methodology is used with Thomas-Fermi type potential incorporating the crucial core-polarization interaction to calculate elastic total and Mulholland partial cross sections. For excited Ge- and Sn- anions the extracted binding energies from the unique characteristic sharp Regge resonances manifesting stable excited states formed during the collisions agree excellently with experimental values; for Pb- the prediction requires experimental verification. Th…
Polarization measurements of the $2s$--$2p_{3/2}$ VUV transition in N$^{4+}$ excited by electron collisions
Institute for Laser Science, The University of Electro-Communications（电波研究所激光科学研究所）；National Astronomical Observatory of Japan（日本国立天文台）；National Institute for Fusion Science（国立研究开发法人核融合科学研究所）
The possibility of electron attachment to the valence $^{3}Π$ state of CO is examined using an {\it ab initio} bound-state multireference configuration interaction approach. The resulting resonance has $^{4}Σ^{-}$ symmetry; the higher vibrational levels of this resonance state coincide with, or are nearly coincident with, levels of the parent $a^{3}Π$ state. Collisional relaxation to the lowest vibrational levels in hot plasma situations might yield the possibility of a long-lived CO$^-$ state.
Charge exchange collisions between ultracold fermionic 6Li atoms and 40Ca+ ions are observed in the mK temperature range. The reaction product of the charge exchange collision is identified via mass spectrometry during which the motion of the ions is excited parametrically. The cross-sections of the charge exchange collisions between 6Li atoms in the ground state and 40Ca+ ions in the ground and metastable excited states are determined. Investigation of the inelastic collision characteristics in the atom-ion mixture is an important step toward ultracold chemistry based on ultracold atoms and i…
Differential cross sections for electron collisions with the O$_2$ molecule in its ground ${X}^{3}Σ_g^-$ state, as well as excited ${a}^{1}Δ_g$ and ${b}^{1}Σ_g^+$ states are calculated. As previously, the fixed-bond R-matrix method based on state-averaged complete active space SCF orbitals is employed. In additions to elastic scattering of electron with the O$_2$ ${X}^{3}Σ_g^-$, ${a}^{1}Δ_g$ and ${b}^{1}Σ_g^+$ states, electron impact excitation from the ${X}^{3}Σ_g^-$ state to the ${a}^{1}Δ_g$ and ${b}^{1}Σ_g^+$ states as well as '6 eV states' of ${c}^{1}Σ_u^{-}$, ${A'}^{3}Δ_u$ and ${A}^{3}Σ_u…
Low-energy elastic and inelastic scattering in the Ps(1$s$)-Ps(2$s$) channel is treated in a four-body hyperspherical coordinate calculation. Adiabatic potentials are calculated for triplet-triplet, singlet-singlet, and singlet-triplet spin symmetries in the spin representation of coupled electrons and coupled positrons, with total angular momentum $L=0$ and parity equal to $+1$. The s-wave scattering lengths for the asymptotic Ps(1$s$)-Ps(2$s$) channel are calculated for each spin configuration. Results obtained for the s-wave scattering lengths are $a_{\mathrm{TT}}=$~$7.3(2)a_0-i0.02(1)a_0$,…
At intermediate to high densities, electron (de-)excitation collisions are the dominant process for populating or depopulating high Rydberg states. In particular, the accurate knowledge of the energy changing ($n$-changing) collisional rates is determinant for predicting the radio recombination spectra of gaseous nebula. The different datasets present in the literature come either from impact parameter calculations or semi-empirical fits and the rate coefficients agree within a factor of two. We show in this paper that these uncertainties cause errors lower than 5% in the emission of radio rec…
New experiments were proposed recently to investigate the regime of cold atomic and molecular ion-atom collision processes in a special hybrid neutral-atom--ion trap under high vacuum conditions. The collisional cooling of laser pre-cooled Ca$^+$ ions by ultracold Na atoms is being studied. Modeling this process requires knowledge of the radiative lifetime of the excited singlet A$^1Σ^+$ state of the (NaCa)$^+$ molecular system. We calculate the rate coefficient for radiative charge transfer using a semiclassical approach. The dipole radial matrix elements between the ground and the excited st…
Energy-conserving, angular momentum-changing collisions between protons and highly excited Rydberg hydrogen atoms are important for precise understanding of atomic recombination at the photon decoupling era, and the elemental abundance after primordial nucleosynthesis. Early approaches to $\ell$-changing collisions used perturbation theory for only dipole-allowed ($Δ\ell=\pm 1$) transitions. An exact non-perturbative quantum mechanical treatment is possible, but it comes at computational cost for highly excited Rydberg states. In this note we show how to obtain a semi-classical limit that is a…
We have studied hetero- and homonuclear excited state/ground state collisions by loading both $^{85}$Rb and $^{87}$Rb into a far off resonant trap (FORT). Because of the relatively weak confinement of the FORT, we expect the hyperfine structure of the different isotopes to play a crucial role in the collision rates. This dependence on hyperfine structure allows us to measure collisions associated with long range interatomic potentials of different structure: such as long and short ranged; or such as purely attractive, purely repulsive, or mixed attractive and repulsive. We observe significantl…
We consider the degree of conservation of nuclear spin polarization in the process of optical pumping under typical spin-exchange optical pumping conditions. Previous analyses have assumed that negligible nuclear spin precession occurs in the brief periods of time the alkali-metal atoms are in the excited state after absorbing photons and before undergoing quenching collisions with nitrogen molecules. We include excited-state hyperfine interactions, electronic spin relaxation in collisions with He and N_2, spontaneous emission, quenching collisions, and a simplified treatment of radiation trap…
In excited molecules, the interaction between the covalent Rydberg and ion-pair channels forms a unique class of excited Rydberg states, in which the infinite manifold of vibrational levels are the equivalent of atomic Rydberg states with a heavy electron mass. Production of the ion pair states usually requires excitation through one or several interacting Rydberg states; these interacting channels are pathways for loss of flux, diminishing the rate of ion pair production. Here, we develop an analytical, asymptotic charge transfer model for the interaction between ultracold Rydberg molecular s…
The importance of the excited states of Positronium (Ps) in the formation cross sections(both differential and total) of the negative hydrogen ion (H^-) are investigated theoretically for the charge transfer reaction, Ps (n = 1, 2) + H --> e+ + H^- for a wide range of incident energies (e. g., threshold - 500 eV) . The calculations are performed in the frame work of a qualitative model, the post collisional Coulomb Modified Eikonal Approximation (CMEA) . A comparative study is also made between the capture from ground and excited states of the Ps. The present CMEA model takes account of higher…
In collisions at ultralow temperatures, molecules will possess Feshbach resonances, foreign to ultracold atoms, whose virtual excited states consist of rotations of the molecules. We estimate the mean spacing and mean widths of these resonant states, exploiting the fact the molecular collisions at low energy display chaotic motion. As examples, we consider the experimentally relevant molecules O_2, OH, and PbO. The density of s-wave resonant states for these species is quite high, implying that a large number of narrow resonant states will exist.
Isotopic effect on collisional widths and shifts of Hg clock transition induced by cold Rb atoms
Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University（托伦哥白尼大学物理、天文学和信息学学院物理研究所）；Joint Quantum Institute, University of Maryland and NIST（马里兰大学与美国国家标准与技术研究院联合量子研究所）
Electron-impact cross sections for dissociation processes of vibrationally excited CH radical
University of Tunis El Manar（突尼斯埃尔曼纳大学）；Sukumar Sengupta Mahavidyalaya（苏库马尔森古普塔学院）；Scottish Church College（苏格兰教会学院）；Istituto per la Scienza e Tecnologia dei Plasmi, CNR（意大利国家研究委员会等离子体科学与技术研究所）；Université de Rennes（雷恩大学）
Motional Stark effect (MSE) spectroscopy represents a unique diagnostic tool capable of determining the magnitude of the magnetic field and its direction in the core of fusion plasmas. The primary excitation channel for fast hydrogen atoms in injected neutral beams, with energy in the range of 25-1000 keV, is due to collisions with protons and impurity ions (e.g., He$^{2+}$ and heavier impurities). As a result of such excitation, at the particle density of 10$^{13}$-10$^{14}$ cm$^{-3}$, the line intensities of the Stark multiplets do not follow statistical expectations (i.e., the populations o…
Theoretical study of the excited states of NeH and of their non-adiabiatic couplings: a preliminary for the modeling of the dissociative recombination of NeH+
Excitation and charge transfer in low-energy O+H collisions is studied; it is a problem of importance for modelling stellar spectra and obtaining accurate oxygen abundances in late-type stars including the Sun. The collisions have been studied theoretically using a previously presented method based on an asymptotic two-electron linear combination of atomic orbitals (LCAO) model of ionic-covalent interactions in the neutral atom-hydrogen-atom system, together with the multichannel Landau-Zener model. The method has been extended to include configurations involving excited states of hydrogen usi…
