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Fluorescence-encoded infrared (FEIR) spectroscopy is a recently developed technique for solution-phase vibrational spectroscopy with detection sensitivity at the single-molecule level. While its spectroscopic information content and important criteria for its practical experimental optimization have been identified, a general understanding of the electronic and nuclear properties required for highly sensitive detection, i.e., what makes a molecule a "good FEIR chromophore," is lacking. This work explores the molecular factors that determine FEIR vibrational activity and assesses computational approaches for its prediction. We employ density functional theory (DFT) and its time-dependent version (TD-DFT) to compute vibrational and electronic transition dipole moments, their relative orientation, and the Franck–Condon factors involved in FEIR activity. We apply these methods to compute the FEIR activities of normal modes of chromophores from the coumarin family and compare these predictions with experimental FEIR cross sections. We discuss the extent to which we can use computational models to predict the FEIR activity of individual vibrations in a candidate molecule. The results discussed in this work provide the groundwork for computational strategies for choosing FEIR vibrational probes or informing the structure of designer chromophores for single-molecule spectroscopic applications. [ABSTRACT FROM AUTHOR]

Relativistic coupled-cluster calculations of the ionization potential, dissociation energy, and excited electronic states under 35 000 cm−1 are presented for the actinium monofluoride (AcF) molecule. The ionization potential is calculated to be IPe = 48 866 cm−1, and the ground state is confirmed to be a closed-shell singlet and thus strongly sensitive to the T , P -violating nuclear Schiff moment of the Ac nucleus. Radiative properties and transition dipole moments from the ground state are identified for several excited states, achieving a mean uncertainty estimate of ∼450 cm−1 for the excitation energies. For higher-lying states that are not directly accessible from the ground state, possible two-step excitation pathways are proposed. The calculated branching ratios and Franck–Condon factors are used to investigate the suitability of AcF for direct laser cooling. The lifetime of the metastable (1)3Δ1 state, which can be used in experimental searches of the electric dipole moment of the electron, is estimated to be of order 1 ms. [ABSTRACT FROM AUTHOR]

We present a time-dependent theory for non-resonant x-ray emission spectrum (XES) and normal Auger spectrum (NAS) calculation, based on a fully quantum description of nuclear dynamics using the vibrational wave packet concept. We compare two formulations of the time-dependent theory, either employing a two-time propagation scheme or using spectral integration over the electron energy continuum. We find that the latter formulation is more efficient for numerical simulations, providing a reasonable accuracy when the integration step is shorter than the lifetime broadening of the core-ionized state. We demonstrate our approach using the example of non-resonant x-ray emission from a water molecule, considering the lowest core-ionized K−1 and first core-ionized shake-up K−1V−1V1 intermediate states. These channels exemplify the developed theory on bound–bound, bound–continuum, continuum–bound, and continuum–continuum transitions. Our results suggest that the time-dependent approach is efficient for simulating XES involving dissociative states, whereas the time-independent approach, based on Franck–Condon factors, is more efficient for bound–bound transitions expressed as discrete frequency dependence in the energy domain. The methods and discussion have general applicability, including both NAS and more complex systems, such as liquid water. [ABSTRACT FROM AUTHOR]

Ab initio CASSCF/MRCI + Q calculations have been used to investigate the electronic structure and transition properties of the alkaline earth astatine molecules SrAt and BaAt. The adiabatic potential energy curves have been computed and plotted for the low-lying electronic states in the representations 2S+1Λ+/− and Ω(±) (with and without spin–orbit coupling effect). The spectroscopic and vibrational constants have been deduced for the corresponding bound states. An analysis of the Franck–Condon factors, the Einstein Coefficients, and the branching ratios among different vibrational levels has shown that both SrAt and BaAt molecules are suitable candidates for Doppler and Sysphus laser cooling. Experimental laser cooling schemes and conditions for these two molecules have been proposed. These results may pave the way for new spectroscopic and laser cooling experiments of alkaline earth astatine molecules. [ABSTRACT FROM AUTHOR]

We report a combined experimental and theoretical investigation of electron–molecule interactions using pyrrole as a model system. Experimental two-dimensional electron energy loss spectra (EELS) encode information about the vibrational states of the molecule as well as the position and structure of electronic resonances. The calculations using complex-valued extensions of equation-of-motion coupled-cluster theory (based on non-Hermitian quantum mechanics) facilitate the assignment of all major EELS features. We confirm the two previously described π resonances at about 2.5 and 3.5 eV (the calculations place these two states at 2.92 and 3.53 eV vertically and 2.63 and 3.27 eV adiabatically). The calculations also predict a low-lying resonance at 0.46 eV, which has a mixed character—of a dipole-bound state and σ* type. This resonance becomes stabilized at one quanta of the NH excitation, giving rise to the sharp feature at 0.9 eV in the corresponding EELS. Calculations of Franck–Condon factors explain the observed variations in the vibrational excitation patterns. The ability of theory to describe EELS provides a concrete illustration of the utility of non-Hermitian quantum chemistry, which extends such important concepts as potential energy surfaces and molecular orbitals to states embedded in the continuum. [ABSTRACT FROM AUTHOR]

The possible laser cooling of AuAl molecules was investigated using high‐level ab initio calculations and considering the spin‐orbit coupling effect. Multi‐reference configuration interaction and the Davidson correction were also employed. Six Λ‐S electronic states were obtained, which were divided into 14 Ω states via spin‐orbit coupling. The optical transition A1Π1→X1∑0+ showed potential for laser‐cooling applications owing to its highly diagonal Franck‐Condon factors and larger vibrational branching ratios. A possible optical cycling scheme using four lasers at near‐resonance wavelengths to eliminate vibrational branching loss is proposed. This scheme can be experimentally tested in future laser‐cooling experiments. [ABSTRACT FROM AUTHOR]

AlF is a relevant molecule in astrochemistry as a tracer of F-bearing molecules. Additionally, AlF presents diagonal Franck-Condon factors and can be created very efficiently in the lab, which makes it a prototypical molecular for laser cooling. However, very little is known about the reaction dynamics of AlF. In this work, we report on the reaction dynamics of AlF–AlF between 200 and 1000 K using ab initio molecular dynamics and a highly efficient active learning approach for the potential energy surface, including all degrees of freedom. As a result, we identify the main reaction mechanisms and the lifetime of the intermediate complex AlF–AlF relevant to astrochemistry environments and regions in buffer gas cells. [ABSTRACT FROM AUTHOR]

The adiabatic potential energy curves of the low lying electronic states of the Be halide anions BeX− (Cl, Br, F, and I) have been investigated in the representation 2s+1Λ(+/−) by using the complete active space self-consistent field with a multireference configuration interaction method. The spectroscopic parameters Te, Re, ωe, and Be and the static and transition dipole moment μe were studied, and a rovibrational study of the investigated electronic states was performed. New electronic states were investigated here for the first time. The calculated highly diagonal Franck–Condon factor and the short radiative lifetime among the lowest vibrational levels of the X1Σ0+ − (1)3Π1 transitions of the molecular anion BeF− prove its candidacy for Doppler laser cooling. The experimental proof of the stability and the calculated experimental parameters, such as the vibrational branching ratio, the slowing distance, the recoil, and Doppler temperatures with the experimental conditions of the buffer gas cell of this anion, open the route for experimental work on the BeF− molecular ion. [ABSTRACT FROM AUTHOR]

Vibrational levels of the electronic ground states in dye molecules have not been previously explored at a high resolution in solid matrices. We present new spectroscopic measurements on single polycyclic aromatic molecules of dibenzoterrylene embedded in an organic crystal made of para-dichlorobenzene. To do this, we use narrow-band continuous-wave lasers and combine spectroscopy methods based on fluorescence excitation and stimulated emission depletion to assess individual vibrational linewidths in the electronic ground state at a resolution of ∼30 MHz dictated by the linewidth of the electronic excited state. In this fashion, we identify several exceptionally narrow vibronic levels with linewidths down to values around 2 GHz. Additionally, we sample the distribution of vibronic wavenumbers, relaxation rates, and Franck–Condon factors, in both the electronic ground and excited states for a handful of individual molecules. We discuss various noteworthy experimental findings and compare them with the outcome of density functional theory calculations. The highly detailed vibronic spectra obtained in our work pave the way for studying the nanoscopic local environment of single molecules. The approach also provides an improved understanding of the vibrational relaxation mechanisms in the electronic ground state, which may help create long-lived vibrational states for applications in quantum technology. [ABSTRACT FROM AUTHOR]

Spectral lines in the optical spectra of atoms, molecules, and other quantum systems are characterized by a range of frequencies ω or a range of wavelengths λ=2πc/ω, where c is the speed of light. Such a frequency or wavelength range is called the width of the spectral lines (linewidth). It is influenced by many specific factors. Thermal motion of the molecules results in broadening of the lines as a result of the Doppler effect (thermal broadening) and by their collisions (pressure broadening). The electric fields of neighboring molecules lead to Stark broadening. The linewidth to be considered here is the so-called parametric broadening (PB) of spectral lines in the optical spectrum. PB can be considered the fundamental type of broadening of the electronic vibrational–rotational (rovibronic) transitions in a molecule, which is the direct manifestation of the basic concept of the collapse of a wavefunction that is postulated by the Copenhagen interpretation of quantum mechanics. Thus, that concept appears to be not only valid but is also useful for predicting physically observable phenomena.

Laser cooling of polyatomic molecules to the ultracold regime may enable some new science and technology applications; however, the related study is still at its very early stage. Here, by means of accurate ab initio and dynamical calculations, we identify two new candidate tetratomic molecules that are suitable for laser cooling and demonstrate the feasibility and advantage of two laser cooling schemes that are able to produce ultracold CaCCH and SrCCH molecules. The internally contracted multiconfiguration reference configuration interaction method is applied, and excellent agreement is achieved between the computed and experimental spectroscopic data. We find that the X 2 Σ 1 / 2 + → A 2 Π 1 / 2 transitions for both candidates feature diagonal Franck–Condon factors, short radiative lifetimes, and no interference from intermediate electronic states. In addition, the crossings with higher electronic states do not interfere. We further construct feasible laser cooling schemes for CaCCH and SrCCH, each of which allows scattering 104 photons for direct laser cooling. The estimated Doppler temperatures for both CaCCH and SrCCH are on the order of μK. [ABSTRACT FROM AUTHOR]

Accurate radiative properties data are required for the further calculations of radiative transfer in thermodynamic nonequilibrium plasmas produced by Earth entry. However, most of the published radiative properties were determined using the outdated spectroscopic constants, transition probabilities, and partition functions, some of which are less accurate and may deviate from the experimental results. In this paper, the spectral emission and absorption coefficients of diatomic molecules in air plasmas are thoroughly calculated based upon the exact line by line approach. In this scheme, the accurate spectroscopic constants and Franck–Condon factors were selected from the recent publications to reconstruct the rotational structure of spectral lines. Moreover, the level populations were determined by means of our newly reported two-temperature partition functions. The required thermodynamic parameters of each species were obtained by simulating a hypersonic flow field of the RAMC II vehicle. The calculated radiative properties were verified by the experimental and numerical equilibrium radiative source strength and the results show good consistency with measured and theoretical values in the available literature. Based upon the obtained flow field parameters, we finally predicted the distributions of nonequilibrium source strength along the stagnation line. Estimates and analysis were also made for the contributions of each transition system of the diatomic molecule to the total source strength. [ABSTRACT FROM AUTHOR]

By using CCSD(T) and EOM-CCSD methods together with quasirelativistic energy-consistent small-core pseudopotentials and large atom-centered basis sets as well as bond functions, the potential energy curves (PECs) for the ground state and several low-lying singlet excited states of the van der Waals molecular systems between cadmium atom interacting with RG atoms (RG = He, Ne, Ar, Kr, Xe and Rn) are obtained. The dispersion coefficients of ground state for Cd-RG have been computed. And the spectroscopic constants of the bound states of Cd-RG molecules have been calculated, the spectroscopic constants of ground state and C1Π state of Cd-RG complexes are in reasonable agreement with the available theoretical and experimental results; the vertical excitation energies of singlet low-lying excited states are also obtained. And the transition dipole moments (TDMs) of (3)1Σ+-X1Σ+ and (4)1Σ+-X1Σ+ transitions are discussed, which would be helpful to understand the transition properties of Cd-RG complex. Furthermore, frequencies of vibrational transitions, rotational constants, Franck-Condon factors (FCFs) of C1Π-X1Σ+ transition and oscillator strengths of Cd-RG have also been acquired. The present work would be of value to understand on the electronically excited states of Cd-RG molecule, especially the electronic structure and spectroscopic characteristics of the singlet excited states. [ABSTRACT FROM AUTHOR]

Definition: Spectral lines in the optical spectra of atoms, molecules, and other quantum systems are characterized by a range of frequencies ω or a range of wavelengths λ = 2 π c / ω , where c is the speed of light. Such a frequency or wavelength range is called the width of the spectral lines (linewidth). It is influenced by many specific factors. Thermal motion of the molecules results in broadening of the lines as a result of the Doppler effect (thermal broadening) and by their collisions (pressure broadening). The electric fields of neighboring molecules lead to Stark broadening. The linewidth to be considered here is the so-called parametric broadening (PB) of spectral lines in the optical spectrum. PB can be considered the fundamental type of broadening of the electronic vibrational–rotational (rovibronic) transitions in a molecule, which is the direct manifestation of the basic concept of the collapse of a wavefunction that is postulated by the Copenhagen interpretation of quantum mechanics. Thus, that concept appears to be not only valid but is also useful for predicting physically observable phenomena. [ABSTRACT FROM AUTHOR]

Quantum-classical mechanics and the Franck-Condon principle related to quantum mechanics are discussed as two alternative theoretical approaches to molecular optical spectroscopy. The statement of the problem is connected with the singularity of quantum mechanics in describing the joint motion of electrons and nuclei in the transient state of "quantum" transitions. This singularity can be eliminated by introducing chaos into the transient state. Quantum mechanics itself, supplemented by chaos (dozy chaos), is called quantum-classical mechanics. Using the simplest example of quantum transitions, it is shown that the results of quantum-classical mechanics in the case of strong dozy chaos correspond to the physical picture based on quantum mechanics and the Franck-Condon principle. The same chaos can be strong for small molecules in standard molecular spectroscopy and simultaneously weak in the photochemistry and nanophotonics of large molecules, where quantum mechanics no longer works. To describe the chaotic dynamics of the transient state, it is necessary to apply quantum-classical mechanics. Thus, the erroneous Franck-Condon physical picture of molecular "quantum" transitions is workable from a practical point of view as long as we are dealing with sufficiently small molecules, just as the erroneous geocentric picture of the world was workable until we went out into outer space. [ABSTRACT FROM AUTHOR]

Vibrationally resolved near-edge x-ray absorption spectra at the K-edge for a number of small molecules have been computed from anharmonic vibrational configuration interaction calculations of the Franck–Condon factors. The potential energy surfaces for ground and core-excited states were obtained at the core-valence separated CC2, CCSD, CCSDR(3), and CC3 levels of theory, employing the adaptive density-guided approach scheme to select the single points at which to perform the energy calculations. We put forward an initial attempt to include pair-mode coupling terms to describe the potential of polyatomic molecules. [ABSTRACT FROM AUTHOR]

Molecules with optical cycling centres (OCCs) are highly desirable in the context of fundamental studies as well as applications (e.g. quantum computing) because they can be effectively cooled to very low temperatures by repeated absorption and emission (hence, cycling). Charged species offer additional advantages for experimental control and manipulation. We present a systematic computational study of a series of diatomic radical-cations made of a d-block metal and a p-block ligand, that are isoelectronic (in their valence shell) to the successfully laser-cooled neutral molecules. Using high-level electronic structure methods, we characterise state and transition properties of low-lying electronic states and compute Franck–Condon factors. The computed branching ratios and radiative lifetimes reveal that the electronic transitions analogous to those successfully used in the laser cooling of neutral molecules are less than optimal in the cations. We propose alternative transitions suitable for optical cycling and highlight trends that could assist future designs of OCCs in charged or neutral molecules. [ABSTRACT FROM AUTHOR]

This work presents a theoretical study of the laser cooling feasibility of the molecule LuF, in the fine structure level of approximation. An ab-initio complete active space self-consistent field (CASSCF)/MRCI with Davidson correction calculation has been done in the Λ(±) and Ω(±) representations. The corresponding adiabatic potential energy curves and spectroscopic parameters have been investigated for the low-lying electronic states. The calculated values of the internuclear distances of the X3Σ0+ and (1)3Π0+ states show the candidacy of the molecule LuF for direct laser cooling. Since the existence of the intermediate (1)3Δ1 state cannot be ignored, the investigation has been done by taking into consideration the two transitions (1)3Π0+−(1)3Δ1 and (1)3Π0+ −X3Σ0+. The calculation of the Franck–Condon factors, the radiative lifetimes, the total branching ratio, the slowing distance, and the laser cooling scheme study prove that the molecule LuF is a good candidate for Doppler laser cooling. [ABSTRACT FROM AUTHOR]

By using the multireference configuration interaction method followed by Davidson correction, the electronic structure of the molecule CaI has been investigated. The potential energy curves, the permanent and transition dipole moment curves, and the spectroscopic parameters of 18 electronic states are investigated for these states, along with 111 vibrational levels of the four lowest electronic states. The Franck–Condon factors and the radiative lifetime are calculated for the X2Σ+–(1)2Π transition. For this transition, the vibrational branching ratio, the slowing distance L, and the number of cycles (N) for photon absorption/emission are calculated along with the Doppler and the recoil temperatures. A pre-cooling temperature in a helium buffer gas is studied and a laser cooling scheme is presented. The calculation of these different experimental parameters is crucial to exploring the optimal conditions under which the laser cooling experiment of CaI molecule will be performed. [ABSTRACT FROM AUTHOR]

Damped harmonic oscillators that take into account local‐mode nuclear vibrations interacting with solvent molecules are developed into Franck‐Condon factors within displaced harmonic oscillator approximation. This is practically done by scaling an unperturbed Hessian matrix that represents local modes of force constants for molecules in a gaseous phase, and then by diagonalizing the perturbed Hessian matrix it results in direct modification of Huang–Rhys factors which represent normal modes of solute molecule perturbed by solvent environment. For highly symmetric polycyclic aromatic hydrocarbon molecules in which hydrogen atom vibrations in a solution can be scaled equally, one‐set scaling parameters constructed into damped Franck‐Condon factors can reproduce solvent‐enhanced absorption and fluorescence spectra in solution. However, for low symmetry molecules with atoms other than hydrogen and carbon atoms, multi‐set scaling parameters constructed into damped Franck‐Condon factors can also reproduce solvent‐enhanced absorption and fluorescence spectra in solution. Examples for high symmetry perylene in benzene solution with one‐set scaling parameters and for low symmetry carbazole in n‐hexane solution with multi‐set scaling parameters are given, in both cases, the present damped Franck‐Condon simulation can reproduce solvent‐enhanced absorption and fluorescence spectra in solution. [ABSTRACT FROM AUTHOR]

We study the emission power spectrum of a molecular emitter with multiple vibrational modes in the framework of macroscopic quantum electrodynamics. The theory we present is general for a molecular spontaneous emission spectrum in the presence of arbitrary inhomogeneous, dispersive, and absorbing media. Moreover, the theory shows that the molecular emission power spectra can be decomposed into the electromagnetic environment factor and lineshape function. In order to demonstrate the validity of the theory, we investigate the lineshape function in two limits. In the incoherent limit (single molecules in a vacuum), the lineshape function exactly corresponds to the Franck–Condon principle. In the coherent limit (single molecules strongly coupled with single polaritons or photons) together with the condition of high vibrational frequency, the lineshape function exhibits a Rabi splitting, the spacing of which is exactly the same as the magnitude of exciton–photon coupling estimated by our previous theory [S. Wang et al., J. Chem. Phys. 151, 014105 (2019)]. Finally, we explore the influence of exciton–photon and electron–phonon interactions on the lineshape function of a single molecule in a cavity. The theory shows that the vibronic structure of the lineshape function does not always disappear as the exciton–photon coupling increases, and it is related to the loss of a dielectric environment. [ABSTRACT FROM AUTHOR]

We report a synchrotron radiation vacuum ultraviolet photoionization study of the hydroperoxyl radical (HO2), a key reaction intermediate in combustion and atmospheric chemistry as well as astrochemistry, using double imaging photoelectron photoion coincidence spectroscopy. The HO2 radical is formed in a microwave discharge flow tube reactor through a set of reactions initiated by F atoms in a CH4/O2/He gas mixture. The high-resolution threshold photoelectron spectrum of HO2 in the 11 eV–12 eV energy range is acquired without interferences from other species and assigned with the aid of theoretically calculated adiabatic ionization energies (AIEs) and Franck–Condon factors. The three vibrational modes of the radical cation HO2+, the H–O stretch, the H–O–O bend, and the O–O stretch, have been identified, and their individual frequencies are measured. In addition, the AIEs of the X3A″ ground state and the a1A′ first excited electronic state of HO2+ are experimentally determined at 11.359 ± 0.003 eV and 11.639 ± 0.005 eV, respectively, in agreement with high-level theoretically computed results. Furthermore, the former AIE value provides validation of thermochemical networks used to extract the enthalpy of formation of the HO2 radical. [ABSTRACT FROM AUTHOR]

We present here a synchrotron radiation vacuum ultraviolet photoionization study of the simplest alkoxy radical, CH3O, a key reaction intermediate in atmospheric and combustion chemistry. A microwave discharge fast flow tube connected to a molecular beam sampling system is employed as a chemical reactor to initiate reactions and generate radicals. The CH3O+ cation from direct ionization of the CH3O radical is detected successfully in the photoionization mass spectrum close to its ionization threshold. In addition, after identifying and removing the contribution of the 13C-isotopic formaldehyde H213CO with the same isobaric mass m/z = 31, the high-resolution threshold photoelectron spectrum of CH3O is obtained and assigned with the aid of calculated Franck–Condon factors. The adiabatic ionization energy of CH3O is determined at 10.701 eV with an accuracy of 0.005 eV. [ABSTRACT FROM AUTHOR]

We report a photodetachment spectroscopy and high-resolution resonant photoelectron imaging study of cryogenically cooled 2-naphthoxide anions (C10H7O−). The photodetachment spectrum revealed a dipole-bound state (DBS) 202(4) cm−1 below the detachment threshold and 38 resonances corresponding to the vibrational levels of the DBS. By tuning the detachment laser to these above-threshold resonances, we obtained 38 resonantly enhanced photoelectron spectra, which were highly non–Franck–Condon as a result of mode-selective vibrational autodetachment from the DBS. The resonances were assigned by comparing the resonant and non-resonant photoelectron spectra, assisted by the computed vibrational frequencies. Specifically, vibrational features with low Franck–Condon factors or from Franck–Condon-forbidden vibrational modes were significantly enhanced in the resonant photoelectron spectra, resulting in much richer spectroscopic information. The electron affinity of the 2-naphthoxy radical was measured accurately to be 19 387(4) cm−1 or 2.4037(5) eV. In addition, a total of 17 vibrational frequencies were obtained for the 2-naphthoxy radical. In particular, seven Franck–Condon-forbidden out-of-plane bending modes, including the two lowest frequency modes (ν48 at 102 cm−1 and ν47 at 171 cm−1), were observed, demonstrating the advantages of combining photodetachment spectroscopy and resonant photoelectron spectroscopy in obtaining vibrational information for polar radical species via DBS. [ABSTRACT FROM AUTHOR]

The NL-eEDM collaboration is building an experimental setup to search for the permanent electric dipole moment of the electron in a slow beam of cold barium fluoride molecules [NL-eEDM Collaboration, Eur. Phys. J. D 72, 197 (2018)]. Knowledge of the molecular properties of BaF is thus needed to plan the measurements and, in particular, to determine the optimal laser-cooling scheme. Accurate and reliable theoretical predictions of these properties require the incorporation of both high-order correlation and relativistic effects in the calculations. In this work, theoretical investigations of the ground and lowest excited states of BaF and its lighter homologs, CaF and SrF, are carried out in the framework of the relativistic Fock-space coupled cluster and multireference configuration interaction methods. Using the calculated molecular properties, we determine the Franck-Condon factors (FCFs) for the A 2 Π 1 / 2 → X 2 Σ 1 / 2 + transition, which was successfully used for cooling CaF and SrF and is now considered for BaF. For all three species, the FCFs are found to be highly diagonal. Calculations are also performed for the B 2 Σ 1 / 2 + → X 2 Σ 1 / 2 + transition recently exploited for laser-cooling of CaF; it is shown that this transition is not suitable for laser-cooling of BaF, due to the nondiagonal nature of the FCFs in this system. Special attention is given to the properties of the A′2Δ state, which in the case of BaF causes a leak channel, in contrast to CaF and SrF species where this state is energetically above the excited states used in laser-cooling. We also present the dipole moments of the ground and excited states of the three molecules and the transition dipole moments (TDMs) between the different states. Finally, using the calculated FCFs and TDMs, we determine that the A 2 Π 1 / 2 → X 2 Σ 1 / 2 + transition is suitable for transverse cooling in BaF. [ABSTRACT FROM AUTHOR]

The combined use of the MRCI-SD(T) method with the cc-pV6Z basis set has enabled us to determine the potential energy curves of the molecular cation CH + whose fundamental X 1 Σ + state lies 111.12 nm above the corresponding X 2 Π state of its neutral parent CH at the dissociation limit. With the accurate potential energy curves thus obtained, we have calculated spectroscopic constants which show good agreement with the experimental and other theoretical values available in the literature. To account for perturbations where necessary, spin-orbit coupling effects have been introduced. An understanding of the polarity of CH + studied in the various electronic states is made possible by calculating the dipole moments. In addition, transition dipole moments were computed prior to the obtention of molecular parameters such as oscillator strength, Einstein coefficients, radiative probabilities and Franck–Condon factors. Overall good accuracy is observed. [ABSTRACT FROM AUTHOR]

The paper presents the Morse potential-based calculation of Franck–Condon factors which have not been investigated from the point of view of allowed transitions associated with the first negative and second positive systems. For nonallowed transitions, it is shown that the Morse potential provides an exact calculation of factors, depending on vibrational constants. During the vibrational number increase, the deviation is observed between calculated Franck–Condon factors and those determined by the more accurate Rydberg–Klein–Rees potential. [ABSTRACT FROM AUTHOR]

A promising laser cooling candidate molecule is essential for laser cooling experiments. In this study, the possibility of laser cooling an 88Sr35Cl molecule is investigated using an ab initio method. Seven low-lying Λ-S and six Ω electronic states of the 88Sr35Cl molecule are calculated at a multi-reference configuration interaction level of theory. Spectral constants of bound states of fitted values are in good agreement with experimental values, which are better than the previously obtained theoretical data for higher excitation states. The resulting permanent and transition dipole moments near the equilibrium bond length are close to the theoretical values. Potential energy curves and transition dipole moments are used for obtaining highly diagonally distributed Franck-Condon factors for the A2Π → X2Σ+ transition using the LEVEL program. A short radiative lifetime of the A2Π state is determined; a laser cooling scheme is designed in the vibration level that requires a cooling main laser beam and two repumping laser beams. Transition spectral data of hyperfine energy levels with errors relative to the experimental data do not exceed −0.25∼0.19 MHz when using a quantum effective Hamiltonian approach. This study provides a helpful reference for experimental observation and operation of laser cooling the 88Sr35Cl molecule. [ABSTRACT FROM AUTHOR]

Quasi-bound resonances of H 2 are produced via two-photon photolysis of H 2 S molecules as reactive intermediates or transition states and detected before decay of the parent molecule into three separate atoms. As was previously reported [K. F. Lai et al., Phys. Rev. Lett. 127, 183001 (2021)] four centrifugally bound quantum resonances with lifetimes of multiple μs, lying energetically above the dissociation limit of the electronic ground state X 1 Σ g + of H 2 , were observed as X (v , J) = (7 , 21) ∗ , (8 , 19) ∗ , (9 , 17) ∗ , and (10 , 15) ∗ , while also the short-lived ( ∼ 1.5 ns) quasi-bound resonance X (11 , 13) ∗ was probed. The present paper gives a detailed account on the identification of the quasi-bound or shape resonances, based on laser detection via F 1 Σ g + - X 1 Σ g + two-photon transitions, and their strongly enhanced Franck-Condon factors due to the shifting of the wave function density to large internuclear separation. In addition, the assignment of the rotational quantum number is verified by subsequent multi-step laser excitation into autoionisation continuum resonances. Existing frameworks of full-fledged ab initio computations for the bound region in H 2 , including Born-Oppenheimer, adiabatic, non-adiabatic, relativistic and quantum-electrodynamic contributions, are extended into the energetic range above the dissociation energy. These comprehensive calculations are compared to the accurate measurements of energies of quasi-bound resonances, finding excellent agreement. They show that the quasi-bound states are in particular sensitive to non-adiabatic contributions to the potential energy. From the potential energy curve and the correction terms, now tested at high accuracy over a wide range of energies and internuclear separations, the s-wave scattering length for singlet H+H scattering is determined at a = 0.2735 31 39 a 0 . It is for the first time that such an accurate value for a scattering length is determined based on fully ab initio methods including effects of adiabatic, non-adiabatic, relativistic and QED with contributions up to m α 6 . [ABSTRACT FROM AUTHOR]

PbF, a valuable candidate for measuring the electron electric dipole moment (eEDM), is of great significance in measuring its spectrum and deriving its molecular constants in experiment. In the present work, the rovibronic spectrum of the B2ÎŁ+â€"X12Î 1/2 transition of PbF in a wavelength range of 260 nmâ€"285 nm is studied by the laser ablation/laser induced fluorescence method. The molecular parameters of the X12Î 1/2 (v ″ = 0) and B2ÎŁ+ (v ′ = 0, 1) states are derived from the recorded spectra of the (0, 0) and (1, 0) bands of the B2ÎŁ+â€"X12Î 1/2 transition. Also, the Franckâ€"Condon factors (FCFs) of the transitions between the B2ÎŁ+ and X12Î 1/2 states are calculated by the RKR/LEVEL method and the Morse potential method, respectively. [ABSTRACT FROM AUTHOR]

Interplay between motion of nuclei and excitations has an important role in molecular photophysics of natural and artificial structures. Here we provide a detailed analysis of coupling between quantized librational modes (librons) and charged excited states (trions) on single phthalocyanine dyes adsorbed on a surface. By means of tip-induced electroluminescence performed with a scanning probe microscope, we identify libronic signatures in spectra of chirally adsorbed phthalocyanines and find that these signatures are absent from spectra of symmetrically adsorbed species. We create a model of the libronic coupling based on the Franck-Condon principle to simulate the spectral features. Experimentally measured librational spectra match very well the theoretically calculated librational eigenenergies and peak intensities (Franck-Condon factors). Moreover, the comparison reveals an unexpected depopulation channel for the zero libron of the excited state that can be effectively controlled by tuning the size of the nanocavity. Our results showcase the possibility of characterizing the dynamics of molecules by their low-energy molecular modes using µeV-resolved tip-enhanced spectroscopy. Vibronic coupling in molecules plays an essential role in photophysics. Here, the authors observe optical fingerprints of the coupling between librational states and charged excited states in a single phthalocyanine molecule chirally absorbed on a surface. [ABSTRACT FROM AUTHOR]

Criegee Intermediates (CIs) and their isomer Vinyl Hydroperoxides (VHPs) are crucial intermediates in the ozonolysis of alkenes. To better understand the underlying chemistry of CIs and VHPs, progress has been made to detect and identify them by photoionization mass spectrometric experiments. Further reliable quantitative information about these elusive intermediates requires their photoionization cross sections. The present work systematically investigated the near-threshold absolute photoionization cross-sections for ten C1–C4 CIs and VHPs, i.e., formaldehyde oxide (CH2OO), acetaldehyde oxide (syn-/anti-CH3CHOO), acetone oxide ((CH3)2COO), syn-CH3-anti-(cis-CH=CH2)COO, syn-CH3-anti-(trans-CH=CH2)COO and vinyl hydroperoxide (CH2CHOOH), 2-hydroperoxypropene (CH2=C(CH3)OOH), syn-CH2 = anti-(cis-CH=CH2)-COOH, syn-CH2 = anti-(trans-CH=CH2)COOH. The adiabatic ionization energies (AIEs) were calculated at the DLPNO-CCSD(T)/CBS level with uncertainties of less than 0.05 eV. The calculated AIEs for C1–C4 CIs and VHPs vary from 8.75 to 10.0 eV with the AIEs decreasing as the substitutions increase. Franck-Condon factors were calculated with the double Duschinsky approximation and the ionization spectra were obtained based on the calculated ionization energies. Pure electronic photoionization cross sections are calculated by the frozen-core Hartree–Fock (FCHF) approximation. The final determined absolute cross sections are around 4.5–6 Mb for the first and second ionization of CIs and 15–25 Mb for VHPs. It is found that the addition of a methyl group or an unsaturated vinyl substitution for the CIs does not substantially change the absolute value of their cross sections. [ABSTRACT FROM AUTHOR]

We show that the Franck-Condon Factor (FCF) associated with a transition between initial and final vibrational states in two different potential energy surfaces, having N and M vibrational quanta, respectively, is equivalent to calculating the number of perfect matchings of a weighted graph with loops that has P = N + M vertices. This last quantity is the loop hafnian of the (symmetric) adjacency matrix of the graph which can be calculated in O(P32P/2) steps. In the limit of small numbers of vibrational quanta per normal mode, our loop hafnian formula significantly improves the speed at which FCFs can be calculated. Our results more generally apply to the calculation of the matrix elements of a bosonic Gaussian unitary between two multimode Fock states having N and M photons in total and provide a useful link between certain calculations of quantum chemistry, quantum optics, and graph theory. [ABSTRACT FROM AUTHOR]

Isobutanal is an aliphatic aldehyde which has been extensively studied as an important intermediate in isomerization reactions as well as in astrochemically relevant models in the interstellar medium. Herein, we report on the conformer-specific photoionization and conformational stabilities of isobutanal utilizing one-photon mass-analyzed threshold ionization (MATI) spectroscopy with vacuum ultraviolet (VUV) pulses. The conformational population of isobutanal under different supersonic expansion conditions was explored to identify the conformers, from which their intrinsic photoionizations can be directly elucidated by measuring the VUV-MATI spectrum corresponding to each conformer. The observed MATI spectra could be analyzed through Franck–Condon simulations at the B3LYP/cc-pVTZ level for the isobutanal conformers, trans and gauche, for which the adiabatic ionization energies were precisely determined to be 78 133 ± 3 cm−1 (9.6873 ± 0.0004 eV) and 78 557 ± 3 cm−1 (9.7398 ± 0.0004 eV), respectively. Notably, only the gauche conformer undergoes a unique geometrical change upon ionization, resulting in the progression of the CHO torsional mode in the MATI spectra. Consequently, we determined the conformational stabilities of isobutanal by conformer-specific photoionization, given that the gauche is more stable than the trans by 162 ± 50 cm−1 in the neutral ground state, while the cationic gauche is less stable than the cationic trans by 262 ± 50 cm−1. [ABSTRACT FROM AUTHOR]

In this paper, we study the realization of a multi-contact switch using the double-dressing regularity of probe, fluorescence, and six-wave mixing signals in a five-level 85Rb atomic system. For the first time, we compare the dressing regularity of Rydberg states by observing electromagnetically induced transparency and signals. With the scanning probe and dressing fields, both large and small line shifts in signals are observed. The small line shifts are induced by double-dressed line shifts. Also, the big line shifts result from the Rydberg dressing. In addition, with an increase in the principal quantum number n of the Rydberg state, all the signals become weaker, while the line shifts of the signals become enhanced. Using the regularity in line shifts of the signals and an acoustic optical modulator to modulate the frequency detuning, we can realize a multi-contact switch action and fast conversion between different contacts. [ABSTRACT FROM AUTHOR]

We present the slow electron velocity map imaging spectroscopy of cryogenically cooled phenoxide, 1-naphthoxide, and 2-naphthoxide anions. The results allow us to examine the ground state and the lowest energy excited state in the corresponding neutral radicals. Care was taken to minimize autodetachment signals in the photoelectron spectra, allowing for more straightforward comparisons with Franck-Condon analyses. The ground states of these three aromatic oxide radicals all have the unpaired electron residing in a π orbital delocalized throughout the molecule. The electron affinity of 1-naphthoxy is measured to be 2.290(2) eV, while that of 2-naphthoxy is measured to be 2.404(2) eV, both of which are higher than that of the smaller phenoxy molecule at 2.253(1) eV. The first excited states have the unpaired electron residing in a more localized σ orbital, yielding measured term energies for the à state of 1.237(2) eV in 1-naphthoxy and 1.068(1) eV in 2-naphthoxy, while that of phenoxy is lower at 0.952(1) eV. The calculated Franck-Condon spectra generally showed good agreement with the experimental spectra, yielding assignments of the more active vibrations in each electronic state. Significant autodetachment signals arising from dipole bound states near the ground states of all three radicals were observed in our efforts to avoid them, and comparably less autodetachment signals were observed near the excited states. Besides this type of non-Franck-Condon intensities in the photoelectron spectra, we also observed minor features arising due to vibronic coupling in the ground states of all three radicals. [ABSTRACT FROM AUTHOR]

A complex comprising one [Re(CO)3]+ unit and a phthalocyanine (Pc) ligand (Re1Pc) is shown to function as a photo‐induced CO‐releasing molecule (photoCORM) in the presence of O2 and a coordinative solvent under irradiation with red light, which can deeply penetrate living tissues. Transient absorption spectroscopic measurements indicate very short excited‐state lifetimes and ultrafast intersystem crossing for Re1Pc and Re2Pc, which contains two [Re(CO)3]+ units. The excited‐state properties are ascribed to efficient spin–orbit coupling and large Franck–Condon factors originating from the complexes' distorted structures, that is, unsymmetric coordination of [Re(CO)3]+ unit(s), one of which was confirmed by single‐crystal X‐ray analysis of a symmetrically substituted Pc with two [Re(CO)3]+ units. Re1Pc represents a promising red‐light‐driven photoCORM that can be applied in biological environments or therapeutic applications. [ABSTRACT FROM AUTHOR]

• High-level computational study of the experimentally unknown species NaBi+. • Well-determined low-lying Λ-S and Ω electronic states. • Determinations of spectroscopic constants. • Predictions of transition properties. • Analyses of the spin-orbit effect. We present a high-level ab initio investigation of the diatomic sodium bismuth (NaBi+), which is a hitherto experimentally unknown species. The explicitly correlated multireference configuration interaction method is used to calculate energy points of thirteen low-lying Λ-S electron states associated with five dissociation limits. Detailed information on structural features, electronic characters, and spectroscopic constants is acquired. Our calculated relative energies between each of the interested higher dissociation limits and the lowest one for NaBi+, as well as splittings of energy levels for Bi, agree well with experimental data. Besides, we have identified and discussed the transition properties of bands from excited Ω states to the ground one, including transition dipole moments, Einstein coefficients, Franck-Condon factors, vibrational branching ratios, and radiative lifetimes. The extent of perturbations originating from the spin-orbit coupling effect to the present species is quantified through discussions on term values of spin-orbit matrix elements, and the spin-orbit coupling effect is proved to have introduced a significant effect to the low-lying electronic states of NaBi+. [ABSTRACT FROM AUTHOR]

It is well known in quantum mechanics that the theory of quantum transitions is based on the convergence of the series of time-dependent perturbation theory. This series converges in atomic and nuclear physics. However, in molecular and chemical physics, this series converges only in the Born–Oppenheimer adiabatic approximation and due to the application of the Franck–Condon principle, and it diverges as a result of going beyond the adiabatic approximation and the Franck–Condon principle. This divergence (singularity) is associated with the incommensurability of the masses of light electrons and heavy nuclei which jointly participate in the full-fledged movement in the transient state of molecular "quantum" transitions. In a new physical theory—quantum–classical mechanics (Egorov, V.V. Heliyon Physics 2019, 5, e02579)—this singularity is damped by introducing chaos into the transient state. This transient chaos is introduced by replacing the infinitely small imaginary additive in the energy denominator of the spectral representation of the total Green's function of the system with a finite value and is called dozy chaos. In this article, resonance at the nanoscale (nano-resonance) between electron and nuclear reorganization motions in the quantum–classical (dozy-chaos) mechanics of elementary electron transfers in condensed media and their applications to polymethine dyes and J-aggregates in solutions are reviewed. Nano-resonance explains the resonant character of the transformation of the shape of the optical absorption band in a series of polymethine dyes in which the length of the polymethine chain changes, as well as the nature of the red-shifted absorption band of the J-aggregates of polymethine dyes (J-band), which is narrow and intense. The process of dye aggregation in an aqueous solution with an increase in its concentration by the formation of J-aggregates is considered a structural tuning of the "polymethine dye + environment" system into resonance with light absorption. For J-aggregates in Langmuir films, the asymmetry of the luminescence and absorption bands, as well as the small value of their Stokes shifts, are explained. The parasitic transformation of the resonant shape of the optical absorption band of a polymethine dye in solution during the transition from one-photon to two-photon absorption is also explained, and the conditions for the restoration of this nano-resonance shape are predicted. [ABSTRACT FROM AUTHOR]

In view of astrophysical application, the ground state molecular parameters such as bond length, dipole moment, rotational constant, harmonic frequency, IR intensity, vibrational temperature of the astrophysically significant diatomic molecule of carbon mono-fluoride (CF) were derived using B3LYP hybrid density functional theory with three basis sets of 3-21G, 6-31G, and 6-311G. The computed data were collectively compared with the values reported in the literature. It was found that the vibrational temperature obtained using the density functional theory approach resembles the favorable temperature for the formation of the CF molecule in an interstellar medium. The transition probability parameters, namely Franck–Condon factors and r-centroids were evaluated for A–X, B–X, and D–X band systems of the CF molecule, using a more reliable numerical integration procedure. The molecular parameters of ground state obtained in the present study was compared with the reported values for better justification. The results of Franck–Condon factors and r-centroids were also discussed in view of astrophysical application. [ABSTRACT FROM AUTHOR]

The correct treatment of vibronic effects is vital for the modeling of absorption spectra of many solvated dyes. Vibronic spectra for small dyes in solution can be easily computed within the Franck-Condon approximation using an implicit solvent model. However, implicit solvent models neglect specific solute-solvent interactions on the electronic excited state. On the other hand, a straightforward way to account for solute-solvent interactions and temperature-dependent broadening is by computing vertical excitation energies obtained from an ensemble of solute-solvent conformations. Ensemble approaches usually do not account for vibronic transitions and thus often produce spectral shapes in poor agreement with experiment. We address these shortcomings by combining zero-temperature vibronic fine structure with vertical excitations computed for a room-temperature ensemble of solutesolvent configurations. In this combined approach, all temperature-dependent broadening is treated classically through the sampling of configurations and quantum mechanical vibronic contributions are included as a zero-temperature correction to each vertical transition. In our calculation of the vertical excitations, significant regions of the solvent environment are treated fully quantum mechanically to account for solute-solvent polarization and charge-transfer. For the Franck-Condon calculations, a small amount of frozen explicit solvent is considered in order to capture solvent effects on the vibronic shape function. We test the proposed method by comparing calculated and experimental absorption spectra of Nile red and the green fluorescent protein chromophore in polar and nonpolar solvents. For systems with strong solute-solvent interactions, the combined approach yields significant improvements over the ensemble approach. For systems with weak to moderate solutesolvent interactions, both the high-energy vibronic tail and the width of the spectra are in excellent agreement with experiments. [ABSTRACT FROM AUTHOR]

Vibrationally resolved electronic absorption spectra including the effect of vibrational pre-excitation are computed in order to interpret and predict vibronic transitions that are probed in the Vibrationally Promoted Electronic Resonance (VIPER) experiment [L. J. G. W. van Wilderen et al., Angew. Chem., Int. Ed. 53, 2667 (2014)]. To this end, we employ time-independent and time-dependent methods based on the evaluation of Franck-Condon overlap integrals and Fourier transformation of timedomain wavepacket autocorrelation functions, respectively. The time-independent approach uses a generalized version of the FC-classes method [F. Santoro et al., J. Chem. Phys. 126, 084509 (2007)]. In the time-dependent approach, autocorrelation functions are obtained by wavepacket propagation and by the evaluation of analytic expressions, within the harmonic approximation including Duschinsky rotation effects. For several medium-sized polyatomic systems, it is shown that selective pre-excitation of particular vibrational modes leads to a redshift of the low-frequency edge of the electronic absorption spectrum, which is a prerequisite for the VIPER experiment. This effect is typically most pronounced upon excitation of modes that are significantly displaced during the electronic transition, such as ring distortion modes within an aromatic π-system. Theoretical predictions as to which modes show the strongest VIPER effect are found to be in excellent agreement with experiment. [ABSTRACT FROM AUTHOR]

Quantum transport of electrons through a molecule is a series of individual electron tunneling events separated by stochastic waiting time intervals. We study the emergence of temporal correlations between successive waiting times for the electron transport in a vibrating molecular junction. Using the master equation approach, we compute the joint probability distribution for waiting times of two successive tunneling events. We show that the probability distribution is completely reset after each tunneling event if molecular vibrations are thermally equilibrated. If we treat vibrational dynamics exactly without imposing the equilibration constraint, the statistics of electron tunneling events become non-renewal. Non-renewal statistics between two waiting times τ1 and τ2 means that the density matrix of the molecule is not fully renewed after time τ1 and the probability of observing waiting time τ2 for the second electron transfer depends on the previous electron waiting time τ1. The strong electron-vibration coupling is required for the emergence of the non-renewal statistics. We show that in the Franck-Condon blockade regime, extremely rare tunneling events become positively correlated. [ABSTRACT FROM AUTHOR]

The Mixed Quantum-Classical Initial Value Representation (MQC-IVR) is a recently introduced approximate semiclassical (SC) method for the calculation of real-time quantum correlation functions. MQC-IVR employs a modified Filinov filtration (MFF) scheme to control the overall phase of the SC integrand, extending the applicability ofSCmethods to complex systems while retaining their ability to accurately describe quantum coherence effects. Here, we address questions regarding the effectiveness of theMFFscheme in combination with SC dynamics. Previouswork showed that this filtering scheme is of limited utility in the context of semiclassical wavepacket propagation, but we find that the MFF is extraordinarily powerful in the context of correlation functions. By examining trajectory phase and amplitude contributions to the real-time SC correlation function in a model system, we clearly demonstrate that the MFF serves to reduce noise by damping amplitude only in regions of highly oscillatory phase leading to a reduction in computational effort while retaining accuracy. Further, we introduce a novel and efficient MQC-IVR formulation that allows for linear scaling in computational cost with the total simulation length, a significant improvement over the more-than quadratic scaling exhibited by the original method. [ABSTRACT FROM AUTHOR]

• Potential energy curves. • Molecular spectroscopic constants. • Radiative properties. • Optical cycles. • Transport properties. The KFr diatomic molecule represents a promising candidate for photoassociation and indirect laser cooling. It has not yet been investigated experimentally and remains the only representative of the family of alkali-metal diatomics, which is scarcely researched theoretically. The potential energy curves of the states belonging to the three lowest dissociation limits of the KFr molecule are calculated using the Fock-space relativistic coupled cluster theory for the first time. Properties and parameters, such as electronic term energies, equilibrium internuclear distances, transition and permanent dipole moments, sequences of vibrational energies, harmonic vibrational frequencies, Franck–Condon factors, and radiative lifetimes (including bound and free transitions), are predicted. We analyzed and evaluated the probabilities of the two-step schemes (optical cycles) for the transfer process of the KFr molecules from excited vibronic states to the ground vibronic state. The transport properties (diffusion, viscosity, and thermal conductivity coefficients) of two-component dilute gas media of potassium and francium atoms as functions of the translation temperature up to 3000 K are also calculated. The data obtained would be useful for laser cooling and spectral experiments with KFr molecules. [Display omitted] [ABSTRACT FROM AUTHOR]

[Display omitted] • Spin-Orbit coupling effects lead to large splitting in the electronic structure of the HfH molecule. • HfH molecule is a suitable candidate for laser cooling, according to electronic structure ab-initio quantum mechanical calculations. • Three lasers in the infrared region are enough to cool HfH molecule to temperatures as low as 44 nK. • The experimental setup for HfH laser cooling should be feasible in the lab. The electronic structure, including the spin–orbit coupling effect of the HfH molecule, has been studied to determine if it can be cooled through Doppler and Sysphus laser cooling techniques. The multi-reference configuration interaction plus Davidson correction (MRCI + Q) method has been used to calculate its potential energy curves (P.E.C.s) in the Ω(±) and 2s+1Ʌ(+/-) representation. The spectroscopic constants T e , R e , ω e , B e , α e , the dipole moment µ e , and the dissociation energies D e agree very well with previously published work. In addition, we present in this work twenty new doublet and quartet states in the Ω(±) representation. The electronic transition dipole moment curves (TDMCs) between the lowest-lying electronic states have been investigated for the Δ - Π, Π - ∑+ and Δ - Φ transitions among specific Ω(±) states. The Franck-Condon factors (FCFs), the Einstein coefficient of spontaneous emission A ν ′ ν , and the radiative lifetime τ have been computed for the investigated transitions. In addition, properties of the molecules' electronic and vibrational states, such as the static dipole moment curves (D.M.C.s), the ionic character f ionic, and the rovibrational constants are calculated. We deduce from our results that the HfH molecule is indeed a laser-cooling candidate that can reach a temperature as low as the nK regime. We present a complementary scheme with suitable experimental parameters. These results can be of great interest to experimental spectroscopists interested in ultracold diatomic molecules and their applications. [ABSTRACT FROM AUTHOR]

Magnesium monofluoride (MgF) is proposed as an ideal candidate radical for direct laser cooling. Here, the rotationally resolved laser spectra of MgF for the A2Π−X2Σ+ electronic transition system were recorded by using laser induced fluorescence technique. The MgF radicals were produced by discharging SF6/Ar gas mixtures between the tips of two magnesium needles in a supersonic jet expansion. We recorded a total of 19 vibrational bands belonging to three sequences of Δv=0, ±1 in the region of 348-370 nm. Accurate spectroscopic constants for both X2Σ+ and A2Π states are determined from rotational analysis of the experimental spectra. Spectroscopic parameters, including the Franck-Condon factors (FCFs), are determined from the experimental results and the Rydberg-Klein-Rees (RKR) calculations. Significant discrepancies between the experimentally measured and RKR-calculated FCFs are found, indicating that the FCFs are nearly independent of the spin-orbit coupling in the A2Π state. Potential energy curves (PECs) and FCFs determined here provide necessary data for the theoretical simulation of the laser-cooling scheme of MgF. [ABSTRACT FROM AUTHOR]

A new ultraviolet (UV) and vacuum ultraviolet (VUV) spectrum for iodopentafluorobenzene (C6F5I) using synchrotron radiation is reported. The measurements have been combined with those from a recent high-resolution photoelectron spectroscopic study. A major theoretical study, which includes both Franck-Condon (FC) and Herzberg-Teller (HT) analyses, leads to conclusions, which are compatible with both experimental studies. Our observation that the VUV multiplet at 7.926 eV in the VUV spectrum is a Rydberg state rather than a valence state leads to a fundamental reassignment of the VUV Rydberg spectrum over previous studies and removes an anomaly where some previously assigned Rydberg states were to optically forbidden states. Adiabatic excitation energies (AEEs) were determined from equations-of-motion coupled cluster with singles and doubles excitation; these were combined with time dependent density functional theoretical methods. Frequencies from these two methods are very similar, and this enabled the evaluation of both FC and HT contributions in the lower valence states. Multi-reference multi-root configuration interaction gave a satisfactory account of the principal UV+VUV spectral profile of C6F5I, with vertical band positions and intensities. The UV spectral onset consists of two very weak transitions assigned to 1¹B1 (πσ*) and 1¹B2 (&#963&#963*) symmetries. The lowest unoccupied molecular orbital of a &#963*(a1) symmetry has a significant C-I* antibonding character. This results in considerable lengthening of the C-I bond for both these excited states. The vibrational intensity of the lowest 1¹B1 state is dominated by HT contributions; the 1¹B2 state contains both HT and FC contributions; the third band, which contains three states, two ππ*(1¹A1, 2¹B2) and one πσ*(2¹B1), is dominated by FC contributions in the ¹A1 state. In this ¹A1 state, and the spectrally dominant bands near 6.7 (¹A1) and 7.3 eV (¹A1 + ¹B2), the C-I bond length is in the normal range, and FC components dominate. [ABSTRACT FROM AUTHOR]

High resolution Fourier transform emission spectroscopy of the Ã2Πi-X2Πi band of the OCS+ ion was performed in the UV region to observe the ν1 (CO stretch) progression bands (υ1 = 0 → 2-5) for both the Ω = 3/2 and 1/2 spin components. Accurate molecular constants including the rotational constants, B0 = 0.194 765(13) and 0.187 106(13) cm-1, and the spin-orbit interaction constants, A0 = -381.0(56) and -126.5(56) cm-1, were determined for the X 2Π and Ã2Π states, respectively, by the simultaneous analysis of the observed progression bands. The CO bond length (rCO = 1.2810 Å) for the Ã2Π state, derived from the rotational constant B0 and Franck-Condon factors, is longer by 0.1756 Å than that (1.1054 Å) for the X 2Π state, while the CS bond length for the Ã2Π state is shorter by 0.0905 Å than that for the X2Π state. Pure rotational transition frequencies in the ground X 2Π state are predicted, as well as transition frequencies of the ν1 fundamental band, with the present molecular constants. [ABSTRACT FROM AUTHOR]