The exchange energy, i.e. the splitting $ΔE$ between gerade and ungerade states in the hydrogen molecule has proven very difficult in numerical calculation at large internuclear distances $R$, while known results are sparse and highly inaccurate. On the other hand, there are conflicting analytical results in the literature concerning its asymptotics. In this work we develop a flexible and efficient numerical approach using explicitly correlated exponential functions and demonstrate highly accurate exchange energies for internuclear distances as large as 57.5 au. This approach may find further applications in calculations of inter-atomic interactions. In particular, our results support the asymptotics form $ΔE \sim R^{5/2}e^{-2R}$, but with the leading coefficient being $2\,σ$ away from the analytically derived value.
We extend the semiclassical two-step model for strong-field ionization that describes quantum interference and accounts for the Coulomb potential beyond the semiclassical perturbation theory to the hydrogen molecule. In the simplest case of the molecule oriented along the polarization direction of a linearly polarized laser field, we predict significant deviations of the two-dimensional photoelectron momentum distributions and the energy spectra from the case of atomic hydrogen. Specifically, for the hydrogen molecule the electron energy spectrum falls off slower with increasing energy, and th…
A model for description of nonresonant formation of the muonic molecules in collisions of the muonic hydrogen atoms with the hydrogenic molecules has been developed with taking into account the internal motion of all nuclei. It has been shown that such a motion leads to a significant smearing of the calculated energy-dependent formation rates at low collision energies. In particular, this effect is strong in the $ddμ$ and $dtμ$ formation. An appreciable isotopic effect in the case of nonresonant $ddμ$ formation in $dμ$ collisions with the molecules D$_2$ and HD has been found. All these effect…
The quantum electrodynamic correction to the energy of the hydrogen molecule has been evaluated without expansion in the electron-proton mass ratio. The obtained results significantly improve the accuracy of theoretical predictions reaching the level of 1 MHz for the dissociation energy, in a very good agreement with the parallel measurement [Hölsch et al., Phys. Rev. Lett. 122, 103002 (2019)]. Molecular hydrogen has thus become a cornerstone of ultraprecise quantum chemistry, which opens perspectives for determination of fundamental physical constants from its spectra.
The differential cross sections for low-energy muonic hydrogen atom scattering from hydrogenic molecules are directly expressed by the corresponding amplitudes for muonic atom scattering from hydrogen-isotope nuclei. The energy and angular dependence of these three-body amplitudes is thus taken naturally into account in scattering from molecules, without involving any pseudopotentials. Effects of the internal motion of nuclei inside the target molecules are included for every initial rotational-vibrational state. These effects are very significant as the considered three-body amplitudes often …
We show theoretically that ultracold hydrogen atoms have very favorable properties for sympathetic cooling of molecules to microkelvin temperatures. We calculate the potential energy surfaces for spin-polarized interactions of H atoms with the prototype molecules NH(triplet-Sigma-) and OH(doublet-Pi) and show that they are shallow (50 to 80 cm-1) and only weakly anisotropic. We carry out quantum collision calculations on H+NH and H+OH and show that the ratio of elastic to inelastic cross sections is high enough to allow sympathetic cooling from temperatures well over 1 K for NH and around 250 …
We report on highly accurate calculations of Born-Oppenheimer potentials for excited $n\,Σ^{+}$ states of the hydrogen molecule for all possible combinations of singlet/triplet and gerade/ungerade symmetries up to $n=7$. A relative accuracy of $10^{-10}$ (0.00002 cm$^{-1}$) or better is achieved for all the internuclear distances and all the excited states under consideration -- an improvement with respect to the best results available in the literature by at least 6 orders of magnitude. Presented variational calculations rely on efficient evaluation of molecular integrals with the explicitly …
We calculate the rate of the spontaneous magnetic dipole radiation transitions from ortho- to para-states of the hydrogen molecule at the room temperature with the radiation wavelengths about 0.01 - 0.1 cm. Exponentially small differences between the rotational energies and heat capacities of parahydrogen and orthohydrogen molecules and also diatomic molecules consisting of different hydrogen atoms for high temperatures are derived.
A counterintuitive scheme to produce ultracold hydrogen via fragmentation of laser cooled diatomic hydrides is presented where the final atomic H temperature is inversely proportional to the mass of the molecular parent. In addition, the critical density for formation of a Bose-Einstein Condensate (BEC) at a fixed temperature is reduced by a factor ratio hydrogen mass: parent mass raised to power 3/2 over directly cooled hydrogen atoms. The narrow Feshbach resonances between a singlet S atom and hydrogen are well suited to a tiny center of mass energy release necessary during fragmentation. Wi…
We calculate the atomic structure of hydrogen and helium, atoms and molecules in an intense magnetic field, analytically and numerically with a judiciously chosen basis.
Precision measurements are performed on highly excited vibrational quantum states of molecular hydrogen. The $v=12, J=0-3$ rovibrational levels of H$_2$ ($X^1Σ_g^+$), lying only $2000$ cm$^{-1}$ below the first dissociation limit, were populated by photodissociation of H$_2$S and their level energies were accurately determined by two-photon Doppler-free spectroscopy. A comparison between the experimental results on $v=12$ level energies with the best \textit{ab initio} calculations shows good agreement, where the present experimental accuracy of $3.5 \times10^{-3}$ cm$^{-1}$ is more precise th…
In this paper we report calculations of potential energy curves in the $1.2 a.u.\le R\le100 a.u.$ range at Multireference Configuration Interaction (MRCI) level for doubly excited states of the H$_2$ molecule. We have focused on the $Q_2$ states which lie between the second and third ionization thresholds of H$_2^+$ molecular ion, i.e., $^2Σ_u^+$ state in which lie the H(2l) + H(2l') dissociation channels. The MRCI approach allowed us to successfully identify for the first time the molecular state which dissociates into hydrogen atoms at 2s state. Further, Generalized Oscillator Strength as a …
It has been recently predicted theoretically that due to nuclear motion light and heavy hydrogen molecules exposed to strong electric field should exhibit substantially different tunneling ionization rates (O.I. Tolstikhin, H.J. Worner and T. Morishita, Phys. Rev. A 87, 041401(R) (2013) [1]). We studied that isotope effect experimentally by measuring relative ionization yields for each species in a mixed H2/D2 gas jet interacting with intense femtosecond laser pulses. In a reaction microscope apparatus we detected ionic fragments from all contributing channels (single ionization, dissociation,…
We have implemented the paraxial approximation followed by the time-dependent Hartree-Fock method with frozen core for the single impact ionization of atoms and two-atomic molecules. It reduces the original scattering problem to the five-dimensional time-dependent Schrödinger equation solution. By using this method we calculated the multi-fold differential cross section of the impact single ionization of the helium atom, the hydrogen molecule and the nitrogen molecule by the intermediate energy electrons. Our results for the helium and the hydrogen are quite close to experimental data, but for…
We have measured K-shell x-ray spectra of highly ionized argon and phosphorus following charge exchange with molecular hydrogen at low collision energy in an electron beam ion trap using an x-ray calorimeter array with $\sim$6 eV resolution. We find that the emission at the high-end of the Lyman series is greater by a factor of 2 for phosphorus than for argon, even though the measurement was performed concurrently and the atomic numbers are similar. This does not agree with current theoretical models and deviates from the trend observed in previous measurements.
In this communication, we present the results of the Five-fold Differential Cross Section (5DCS) and Triple Differential Cross Section (TDCS) for the (e,2e) process on molecular hydrogen ($H_2$) by the plane wave and the twisted electron beam impact. The formalism is developed within the first Born approximation using the plane wave and the twisted wave for the incident electron beam. We describe the plane wave, Heitler-London type wave function and Coulomb wave for the scattered electron, $H_2$ molecular state, and the ejected electron respectively. We compare the angular profiles of the 5DCS…
We show that two-particle interferences can be used to probe the nuclear motion in a doubly-excited hydrogen molecule. The dissociation of molecular hydrogen by electron impact involves several decay channels, associated to different molecular rotational states, which produce quantum interferences in the detection of the atomic fragments. Thanks to the correlations between the angular momentum and vibrational states of the molecule, the fragments arising from each dissociation channel carry out a phase-shift which is a signature of the molecule rotation. These phase-shifts, which cannot be obs…
A trial function is presented for the $H_2$ molecule which provides the most accurate (the lowest) Bohr-Oppenheimer ground state energy among few-parametric trial functions (with $\leq 14$ parameters). It includes the electronic correlation term in the form $\sim \exp{(γr_{12})}$ where $γ$ is a variational parameter.
We report on accurate variational calculations of the Born-Oppenheimer potential for excited states of the hydrogen molecule with $Π$, $Δ$, and $Φ$ symmetries. The obtained potential energy curves reach the relative precision of $10^{-9}$ or better along internuclear distances of 0.01 -- 20 au. Calculations rely on recursive evaluation of two-center two-electron molecular integrals with exponential functions in arbitrary precision arithmetics. Our results for most of the states are the first ever reported, and for the previously calculated states constitute an improvement by several orders of …
In this paper, we describe an experiment which was conducted to explore the macro-coherent amplification mechanism using a two-photon emission process from the first vibrationally-excited state of para-hydrogen molecule. Large coherence in the initial state was prepared by the adiabatic Raman population transfer method, and the lowest Stokes sideband was used as a trigger field. We observed the coherent two-photon emission consistent with the expectation of the paired super-radiance master equation.
Precise solutions of the Hartree-Fock equations for the ground state of the hydrogen molecule are obtained for a wide range of internuclear distances R by means of a two-dimensional fully numerical mesh computational method. The spatial parts of the single-electron wave functions are found to be coinciding for R<2.30a.u. At larger distances they become different and as R->\infty each of them takes the form corresponding to a separate atom. This quantum phase transition occurring at R=2.30a.u. gives a natural boundary between a delocalized behavior of electrons in the molecule and their distrib…
The confined variational method is used to generate a basis of correlated gaussians to describe the interaction region wave function for positron scattering from the H$_2$ molecule. The scattering length was $\approx -2.7$ $a_0$ while the zero energy $Z_{\rm eff}$ of 15.7 is compatible with experimental values. The variation of the scattering length and $Z_{\rm eff}$ with inter-nuclear distance was surprisingly rapid due to virtual state formation at $R \approx 3.4$ $a_0$.
In this paper we investigate some entanglement properties for the Hydrogen molecule considered as a two interacting spin 1/2 (qubit) model. The entanglement related to the $H_{2}$ molecule is evaluated both using the von Neumann entropy and the Concurrence and it is compared with the corresponding quantities for the two interacting spin system. Many aspects of these functions are examinated employing in part analytical and, essentially, numerical techniques. We have compared analogous results obtained by Huang and Kais a few years ago. In this respect, some possible controversial situations ar…
We present an accurate theoretical determination of rovibrational energy levels of the hydrogen molecule and its isotopologues in its electronic ground state. We consider all significant corrections to the Born-Oppenheimer approximation, obtained within nonadiabatic perturbation theory, including the mixed nonadiabatic-relativistic effects. Quantum electrodynamic corrections in the leading $α^5\,m$ and the next-to-leading $α^6\,m$ orders, as well as finite nuclear size effect, are also taken into account but within the Born-Oppenheimer approximation only. Final results for the transition wavel…
We consider the spin-exchange in ultracold collisions of hydrogen ($H$) and antihydrogen ($\bar{H}$) atoms. The cross sections for transitions between various hyperfine states are calculated. We show that the process of spin exchange in $\bar{H}-H$ collisions is basically driven by the strong force between proton and antiproton, that spin-exchange cross-sections are proportional to the difference of singlet and triplet strong force S-wave scattering lengths, while the strong force effects are enhanced about $10^9$ times due to long range atomic forces. We show that any difference in hyperfine …
Highly accurate results from frequency measurements on neutral hydrogen molecules H_2, HD and D_2 as well as the HD^+ ion can be interpreted in terms of constraints on possible fifth-force interactions. Where the hydrogen atom is a probe for yet unknown lepton-hadron interactions, and the helium atom is sensitive for lepton-lepton interactions, molecules open the domain to search for additional long-range hadron-hadron forces. First principles calculations in the framework of quantum electrodynamics have now advanced to the level that hydrogen molecules and hydrogen molecular ions have become …
Studies of muonic hydrogen atoms and molecules have been performed traditionally in bulk targets of gas, liquid or solid. At TRIUMF, Canada's meson facility, we have developed a new type of target system using multilayer thin films of solid hydrogen, which provides a beam of muonic hydrogen atoms in vacuum. Using the time-of-flight of the muonic atoms, the energy-dependent information of muonic reactions are obtained in direct manner. We discuss some unique measurements enabled by the new technique, with emphasis on processes relevant to muon catalyzed fusion.
By Using the variational Monte Carlo (VMC) method, we calculate the 1sσ_g state energies, the dissociation energies and the binding energies of the hydrogen molecule and its molecular ion in the presence of an aligned magnetic field regime between 0 a.u. and 10 a.u. The present calculations are based on using two types of compact and accurate trial wave functions, which are put forward for consideration in calculating energies in the absence of magnetic field. The obtained results are compared with the most recent accurate values. We conclude that the applications of VMC method can be extended…
We observed two-photon emission signals from the first vibrationally excited state of parahydrogen gas excited coherently by counter-propagating laser pulses. A single narrow-linewidth laser source was used to excite the parahydrogen molecules and induce the two-photon emission process. We measured how the signal energy depended on the detuning, target gas pressure, and input pulse energies. These results are qualitatively consistent with those obtained by numerical simulations based on the Maxwell-Bloch equations with one spatial dimension and one temporal dimension. This study of two-photon …
We reevaluate the Zemach, recoil and polarizability corrections to the hyperfine splitting in muonic hydrogen expressing them through the low-energy proton structure constants and obtain the precise values of the Zemach radius and two-photon exchange (TPE) contribution. The uncertainty of TPE correction to S energy levels in muonic hydrogen of 105 ppm exceeds the ppm accuracy level of the forthcoming 1S hyperfine splitting measurements at PSI, J-PARC and RIKEN-RAL.
We demonstrate that the formation of negative hydrogen ions (H-) occurs in a wide class of atomic and molecular collisions. In our experiments, H- emission from hydroxyl cations and acetone molecules was observed in keV-energy collisions. We show that hydride (H-) anions are formed via direct collisional fragmentation of molecules, followed by electron grabbing by fast hydrogen fragments. Such general mechanism in hydrogen-containing molecules may significantly influence reaction networks in planetary atmospheres and astrophysical media and new reaction pathways may have to be added in radioly…
We obtain a model-independent prediction for the two-photon exchange contribution to the hyperfine splitting in muonic hydrogen. We use the relation of the Wilson coefficients of the spin-dependent dimension-six four-fermion operator of NRQED applied to the electron-proton and to the muon-proton sectors. Their difference can be reliably computed using chiral perturbation theory, whereas the Wilson coefficient of the electron-proton sector can be determined from the hyperfine splitting in hydrogen. This allows us to give a precise model-independent determination of the Wilson coefficient for th…
We compute the spin-dependent and spin-independent structure functions of the forward virtual-photon Compton tensor of the proton at one loop using heavy baryon effective theory including the Delta particle. We compare with previous results when existing. Using these results we obtain the leading hadronic contributions, associated to the pion and Delta particles, to the Wilson coefficients of the lepton-proton four fermion operators in NRQED. The spin-independent coefficient yields a pure prediction for the two-photon exchange contribution to the muonic hydrogen Lamb shift, $ΔE_{\rm TPE}(π\&Δ)…
Photoelectron circular dichroism results from one-photon ionization of chiral molecules by circularly polarized light and manifests itself in forward-backward asymmetry of electron emission in the direction orthogonal to the light polarization plane. What is the physical mechanism underlying asymmetric electron ejection? How "which way" information builds up in a chiral molecule and maps into forward-backward asymmetry? We introduce instances of bound chiral wave functions resulting from stationary superpositions of states in a hydrogen atom and use them to show that the chiral response in one…
We propose a two-qubit gate based on dipolar exchange interactions between individually addressable ultracold polar molecules in an array of optical dipole traps. Our proposal treats the full Hamiltonian of the $^1Σ^+$ molecule NaCs, utilizing a pair of nuclear spin states as storage qubits. A third rotationally excited state with rotation-hyperfine coupling enables switchable dipolar exchange interactions between two molecules to generate an iSWAP gate. All three states are insensitive to external magnetic and electric fields. Impacts on gate fidelity due to coupling to other molecular states…
