Search Results (42)

In this work, a comprehensive theoretical investigation is carried out to explore the electronic and spectroscopic properties of selected diatomic molecular ions MgRb⁺ and SrRb⁺. Using high-level ab initio calculations based on a pseudopotential approach, along with large Gaussian basis sets and full valence configuration interaction (FCI), we accurately determine adiabatic potential energy curves, spectroscopic constants, transition dipole moments (TDMs), and permanent electric dipole moments (PDMs). To deepen our understanding of these systems, we calculate radiative lifetimes for vibrational levels in both ground and low-lying excited electronic states. This includes evaluating spontaneous and stimulated emission rates, as well as the effects of blackbody radiation. We also compute Franck–Condon factors and analyze photoassociation processes for both ions. Furthermore, to explore low-energy collisional dynamics, we investigate elastic scattering in the first excited states (2¹Σ⁺) describing the collision between the Ra atom and Mg⁺ or Sr⁺ ions. Our findings provide detailed insights into the theoretical electronic structure of these molecular ions, paving the way for future experimental studies in the field of cold and ultracold molecular ion physics. Full article

Effective laser cooling schemes are fundamental for preparing ultracold triatomic molecules. Here, efficient laser cooling strategies for alkaline-earth hydroxides (XOH, X = Ca, Sr, Ba) are proposed using high-precision quantum calculations. By mapping Λ-S- and Ω-state potential energy surfaces, we identified quasi-closed optical cycles with dominant Franck–Condon factors (FCFs) and strong transition dipoles. The scheme utilizes targeted repumping to suppress vibrational leaks, enabling >10⁴ photon scatters per molecule, exceeding Doppler cooling requirements. These results establish XOH molecules, particularly BaOH, as viable candidates for laser cooling experiments, providing key theoretical insights for ultracold triatomic molecule production. Full article

In our research aimed at replacing precious transition metals like platinum with abundant base metals such as nickel for efficient triplet emitters, we synthesized and studied Ni(II) complexes [Ni(L^NHR)Cl]. These complexes containing the N^C^N cyclometalating dipyridyl-phenide ligand, equipped with pending H-bonding amine groups (NH(C₆H₅) (L^NHPh) and NH(C₆H₅CH₂), ClL^NHBn). Molecular structures determined from experimental X-ray diffractometry and density functional theory (DFT) calculations in the ground state showed marked deviation of the Cl⁻ coligand (ancillary ligand) from the ideal planar coordination, with τ₄ values of 0.35 and 0.33, respectively, along with hydrogen bonding interactions of the ligand NH function with the Cl⁻ coligand. The complexes exhibit long-wavelength absorption bands at approximately 425 nm in solution, with the experimental spectra being accurately reproduced through time-dependent density functional theory (TD-DFT) calculations. Vibrationally structured emission profiles and steady-state photoluminescence quantum yields of 30% for [Ni(L^NHPh)Cl] and 40% for [Ni(L^NHBn)Cl] (along with dual excited state lifetimes in the ns and in the ms range) were found in frozen 2-methyl-tetrahydrofuran (2MeTHF) glassy matrices at 77 K. Furthermore, within a poly(methyl methacrylate) matrix, the complexes showed emission bands centered at around 550 nm within a temperature range from 6 K to 300 K with lifetimes similar to 77 K. Based on TD-DFT potential scans along the metal–ligand (Ni–N) coordinate, we found that in a rigid environment that restricts the geometry to the Franck-Condon region, either the triplet T₅ or the singlet S₄ state could contribute to the photoluminescence. Full article

The change in the geometry of 1,3-dicyanobenzene upon electronic excitation to the lowest excited singlet state has been elucidated by simultaneous Franck–Condon (FC) fits of the fluorescence emission spectra originating from the vibrationless origin and from four vibronic bands. The geometry changes obtained from the FC fits were compared to the results of ab initio calculations at the SCS-CC2/cc-pVTZ level of theory. We found close agreement between the spectral determination and the theoretical prediction of the geometry changes upon excitation. The aromatic ring opens upon excitation, resulting in a symmetrically distorted structure in the excited state. Full article

Ab initio calculations of cross sections for electron capture by protons in collisions with CO₂ are carried out at energies between 100 eV/u and 50 keV/u, employing a semiclassical method within the Franck–Condon framework. The scattering wave function is expanded in a set of ab initio electronic wave functions of the HCO₂⁺ supermolecule. The calculation is performed on several trajectory orientations to obtain orientation-averaged total cross sections. A two-state model with an exponential interaction between the entrance and the lowest charge transfer channel is proposed to describe the main aspects of the charge transfer process and to estimate the precision of the molecular expansion. The symmetry of the HOMO ${\pi }_g$ of CO₂ is relevant to choose the signs of the molecular functions and to set up the orientation average of the cross sections. Very good agreement is found with the experimental charge transfer cross sections. Full article

There is compelling evidence that the absorption of low-energy UV radiation directly by DNA in solution generates guanine radicals with quantum yields that are strongly dependent on the secondary structure. Key players in this unexpected phenomenon are the photo-induced charge transfer (CT) states, in which an electric charge has been transferred from one nucleobase to another. The present work examines the factors affecting the population of these states during electronic relaxation. It focuses on two dinucleotides with opposite orientation: 5′-dApdG-3′ (AG) and 5′-dGpdA-3′ (GA). Quantum chemistry calculations determine their ground state geometry and the associated Franck–Condon states, map their relaxation pathways leading to excited state minima, and compute their absorption spectra. It has been shown that the most stable conformer is anti-syn for AG and anti-anti for GA. The ground state geometry governs both the excited states populated upon UV photon absorption and the type of excited state minima reached during their relaxation. Their fingerprints are detected in the transient absorption spectra recorded with excitation at 266 nm and a time resolution of 30 fs. Our measurements reveal that in the large majority of dinucleotides, chromophore coupling is already operative in the ground state and that the charge transfer process occurs within ~120 fs. The competition among various relaxation pathways affects the quantum yields of the CT state formation in each dinucleotide, which are estimated to be 0.18 and 0.32 for AG and GA, respectively. Full article

In this paper, we present various theoretical models that accurately approximate the spectral density of the optical capture cross-section (${\sigma }_e^0$) obtained through the analysis of photo-capacitance transients using the deep-level optical spectroscopy (DLOS) technique applied to semi-transparent Ni/Au Schottky barrier diodes (SBDs) fabricated on n-GaN films. The theoretical models examined in this study involved a variety of approaches, from the Lucovsky model that assumes no lattice relaxation to more sophisticated models such as the Chantre–Bois and the Pässler models, which consider the electron–phonon coupling phenomenon. By applying theoretical models to the experimentally determined data, we were able to estimate the photoionization (E⁰), trap level position (E_T), and Franck–Condon (d_FC) energy, respectively. In addition, the results of our analysis confirm that the photoionization processes of deep traps in n-GaN grown by the metal–organic vapor-phase epitaxy technique (MOVPE) are strongly coupled to the lattice. Moreover, it was shown that the Pässler model is preferred for the accurate determination of the individual trap parameters of defects present in n-GaN films grown on an Ammono-GaN substrate. Finally, a new trap level, Ec-1.99 eV with d_FC = 0.15, that has not been previously reported in n-GaN films grown by MOVPE was found. Full article

Nanographenes are of increasing importance owing to their potential applications in the photoelectronic field. Meanwhile, recent studies have primarily focused on the pure electronic spectra of nanographenes, which have been found to be inadequate for describing the experimental spectra that contain vibronic progressions. In this study, we focused on the vibronic effect on the electronic transition of a range of chiral nanographenes, especially in the low-energy regions with distinct vibronic progressions, using theoretical calculations. All the calculations were performed at the PBE0-D3(BJ)/def2-TZVP level of theory, adopting both time-dependent and time-independent approaches with Franck–Condon approximation. The resulting calculated curves exhibited good alignment with the experimental data. Notably, for the nanographenes incorporating helicene units, owing to the increasing π-extension, the major vibronic modes in the vibrationally resolved spectra differed significantly from those of the primitive helicenes. This investigation suggests that calculations that account for the vibronic effect could have better reproducibility compared with calculations based solely on pure electronic transitions. We anticipate that this study could pave the way for further investigations into optical and chiroptical properties, with a deeper understanding of the vibronic effect, thereby providing theoretical explanations with higher precision on more sophisticated nanographenes. Full article

Perylenetetracarboxylic diimide (PTCDI) is an n-type organic semiconductor molecule that has been widely utilized in numerous applications such as photocatalysis and field-effect transistors. Polarizability and dipole moment, which are inherent properties of molecules, are important parameters that determine their responses to external electric and optical fields, physical properties, and reactivity. These parameters are fundamentally important for the design of innovative materials. In this study, the effects of external electric fields on absorption and fluorescence spectra were investigated to obtain the PTCDI parameters. The PTCDI substituted by an octyl group (N,N′-Dioctyl-3,4,9,10-perylenedicarboximide) dispersed in a polymethyl methacrylate (PMMA) matrix was studied in this work. The features of vibronic progression in the absorption spectrum were analogous to those observed in solution. The red shift of the absorption band caused by the Stark effect was mainly observed in the presence of an external electric field. Changes in parameters such as the dipole moment and polarizability between the ground and the Franck–Condon excited states of the PTCDI monomer were determined. The fluorescence spectrum shows a contribution from a broad fluorescence band at wavelengths longer than the monomer fluorescence band. This broad fluorescence is ascribed to the excimer-like fluorescence of PTCDI. The effects of the electric field on the fluorescence spectrum, known as the Stark fluorescence or electrofluorescence spectrum, were measured. Fluorescence quenching is observed in the presence of an external electric field. The change in the polarizability of the monomer fluorescence band is in good agreement with that of the electroabsorption spectrum. A larger change in the polarizability was observed for the excimer-like fluorescence band than that for the monomer band. This result is consistent with exciton delocalization between PTCDI molecules in the excimer-like state. Full article

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. Full article

Photophysical properties of a series of bis(arylydene)cycloalkanone dyes with various donor substituents are studied using quantum chemistry. Their capacity for luminescence and nonradiative relaxation through trans–cis isomerization is related to their structure, in particular, to the donor capacity of the substituents and the degree of conjugation due to the central cycloalkanone moiety. It is shown that cyclohexanone central moiety introduces distortions and disrupts the conjugation, thus leading to a nonmonotonic change in their properties. The increasing donor capacity of the substituents causes increase in the HOMO energy (rise in the oxidation potential) and decrease in the HOMO–LUMO gap, which results in the red shift of the absorption spectra. The ability of the excited dye to relax through fluorescence or through trans–cis isomerization is governed by the height of the barrier between the Franck–Condon and S1–S0 conical intersection regions on the potential energy surface of the lowest π-π* excited state. This barrier also correlates with the donor capacity of the substituents and the degree of conjugation between the central and donor moieties. The calculated fluorescence and trans–cis isomerization rates are in good agreement with the observed fluorescence quantum yields. Full article

The purpose of the presented study is to examine the impact of zinc oxide nanoparticles (ZnO NPs) on the spectrum features of poly [2-methoxy-5-(3′,7′-dimethyloctyloxy)-1, 4-phenylenevinylene] (MDMO-PPV). The characteristics of the MDMO-PPV and doped ZnO NPS samples were assessed using several techniques. A set of solutions of MDMO-PPV in toluene that were doped with different ratio percentages of ZnO NPs was prepared to obtain thin films. Pristine and composite solutions were spin-coated on glass substrates. It was observed that MDMO-PPV had two distinct absorbance bands at $310$ and $500 \mathrm{nm}$ in its absorption spectrum. The UV-Vis spectrum was dramatically changed when $5\%$ of ZnO NPs were added. The result showed a significant reduction in absorption of the band $500 \mathrm{nm}$, while $310 \mathrm{nm}$ absorption increased rapidly and became more pronounced. Upon adding (10%) ZnONPs to the sample, no noticeable change was observed in the 500 nm band. However, the 310 nm band shifted towards the blue region. There is a dominant peak in the PL spectrum of MDMO-PPV in its pristine form around $575 \mathrm{nm}$ and a smaller hump around $600 \mathrm{nm}$ of the spectrum. The spectral profile at 600 nm and the intensity of both bands are improved by raising the ZnO NP concentration. These bands feature two vibronic transitions identified as (0-0) and (0-1). When the dopant concentration increased to the maximum dopant percentage ($10\%$), the energy band gap values increased by $0.21 \mathrm{eV}$ compared to the pristine MDMO-PPV. In addition, the refractive index (n) decreased to its lowest value of $2.30$ with the presence of concentrations of ZnO NPs. Full article

Fluorinated organic compounds have superior physicochemical properties than general organic compounds due to the strong C-F single bond; they are widely used in medicine, biology, pesticides, and materials science. In order to gain a deeper understanding of the physicochemical properties of fluorinated organic compounds, fluorinated aromatic compounds have been investigated by various spectroscopic techniques. 2-fluorobenzonitrile and 3-fluorobenzonitrile are important fine chemical intermediates and their excited state S₁ and cationic ground state D₀ vibrational features remain unknown. In this paper, we used two-color resonance two photon ionization (2-color REMPI) and mass analyzed threshold ionization (MATI) spectroscopy to study S₁ and D₀ state vibrational features of 2-fluorobenzonitrile and 3-fluorobenzonitrile. The precise excitation energy (band origin) and adiabatic ionization energy were determined to be 36,028 ± 2 cm⁻¹ and 78,650 ± 5 cm⁻¹ for 2-fluorobenzonitrile and 35,989 ± 2 cm⁻¹ and 78,873 ± 5 cm⁻¹ for 3-fluorobenzonitrile, respectively. The density functional theory (DFT) at the levels of RB3LYP/aug-cc-pvtz, TD-B3LYP/aug-cc-pvtz, and UB3LYP/aug-cc-pvtz were used to calculate the stable structures and vibrational frequencies for the ground state S₀, excited state S₁, and cationic ground state D₀, respectively. Franck–Condon spectral simulations for transitions of S₁ ← S₀ and D₀ ← S₁ were performed based on the above DFT calculations. The theoretical and experimental results were in good agreement. The observed vibrational features in S₁ and D₀ states were assigned according to the simulated spectra and the comparison with structurally similar molecules. Several experimental findings and molecular features were discussed in detail. Full article

In this paper, we theoretically study the laser-induced modification of the vibrational parameters of a carbon dioxide molecule regarding its tunnel ionization. Our study predicts a 5% increase in the ionization rate in anti-Stokes channels that corresponds to pumping the ${\Sigma }_u$ mode up to $v_{ai}=10$. The molecule is imparted with an additional energy from the pre-pumped vibrational states, which is absorbed during ionization. As a result, the tunneling rate increases. This amplification of tunnel ionization of the CO${}_2$ gas target can potentially be used for the laser separation of carbon isotopes. Full article

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. Full article