Emission Oscillator Strengths Research Articles

End Cap Effect on Solution-Processable Deep Blue Lasing Materials with Low-Amplified Spontaneous Emission Thresholds.

Organic lasers have attracted increasing attention owing to their superior characteristics such as lightweight, low-cost manufacturing, high mechanical flexibility, and high emission-wavelength tunability. Recent breakthroughs include electrically pumped organic laser diodes and an electrically driven organic laser, integrated with an organic light-emitting diode pumping. However, the availability of efficient deep blue organic laser chromophores remains limited. In this study, we develop two novel rigid oligophenylenes, end-capped with carbazole and phenylcarbazole groups, to demonstrate exceptional optical and amplified spontaneous emission (ASE) properties. These oligophenylenes are not only solution processable but also exhibit remarkably high solution photoluminescence quantum yields (PLQYs) of 90% and high radiative rates of 1.35 × 109 s-1 in the deep blue range. Our theoretical calculations confirm that the carbazole and phenylcarbazole end groups play a pivotal role in enhancing the optical transitions of the oligophenylene laser chromophores, thereby elevating their emission oscillator strengths. Remarkably, these materials demonstrate low solid-state ASE threshold values of 1.0 and 1.5 μJ/cm2 (at 431 and 418 nm, respectively). To the best of our knowledge, these ASE thresholds represent the lowest reported at these specific ASE wavelengths in the literature, regardless of whether they are solution-processed or thermally evaporated films. Furthermore, they exhibit excellent thermal and photostability, low triplet quantum yields, as well as negligible overlap of excited-state absorption within the ASE emission region, making them excellent candidates for a new class of deep blue materials for organic lasers. By integrating insights from theoretical calculations and experimental validation, our study provides a comprehensive understanding of the design principles behind these high-performing organic laser chromophores, paving the way for the development of advanced organic lasers with enhanced performance characteristics.

The controllable of BODIPY dimers without installing blocking groups as both fluorescence and singlet oxygen generators

AbstractWe compared a range of BODIPY dimer derivatives without installing blocking groups by optimizing geometry structures and analyzing energies, frontier molecular orbitals, Chole&Cele map, electron density difference, spin‐orbit coupling (SOC) matrix and decay rate constants from excited states. The dihedral angles of the β‐β‐linked BODIPY dimer and the α‐α‐linked BODIPY dimer tend to flatten in the T1 state, which is detrimental to the occurrence of the intersystem crossing (ISC). Conversely, the dihedral angle of the meso‐β‐linked BODIPY dimer, the meso‐meso‐linked BODIPY dimer and α‐γ‐linked BODIPY dimer is within the range of 125°–143° in the T1 state, facilitating ISC and the generation of singlet oxygen. Notably, the transition from S1 to S0 involving lowest unoccupied molecular orbital to highest occupied molecular orbital with long‐wavelength emission and moderate oscillator strength underpins the remarkable long emission peaks observed experimentally for α‐γ‐linked BODIPY dimer. Moreover, the apparent SOC matrix enhances the ISC process, resulting in a respectable efficiency in generating singlet oxygen for this dimer. In meso‐β‐linked BODIPY, meso‐meso‐linked BODIPY, and α‐γ‐linked BODIPY, the S1→T1 process is characterized by a significant charge transfer, specifically transitioning from the 1CT state to the 3LE state, indicative of a spin‐orbit charge transfer ISC (SOCT‐ISC) mechanism. The ability to regulate the photosensitivity of BODIPY dimers by adjusting the dihedral angle between the two units in the T1 state unveils new avenues for designing high‐performance photosensitizers for both therapeutic and imaging applications.

Computational screening of multi-resonance thermally activated delayed fluorescence (MR-TADF) molecules for lasing application

Multi-resonance thermally activated delayed fluorescence (MR-TADF) molecules charactering large emission oscillator strengths, effective reverse intersystem crossing (RISC), and narrow emission spectral width, have great potential as laser materials. We propose a molecular descriptor for quick screening MR-TADF molecules as laser candidate materials, A =ΔESTσeffnet,opt, namely, the product of singlet-triplet energy gap and the optical pumping net stimulated emission cross section. These quantities can be calculated by combining quantum chemistry package Gaussian and our own MOMAP program. Through extensive computations benchmarked with existing experiments, we suggest that A value should be larger than 0.311 ⨉ 10−17 cm2 eV for promising lasing molecules. We virtually designed 119 molecules with MR-TADF property, and based on our theoretical protocol by considering descriptor A, we are able to select 10 molecules as lasing molecules. We then further screen out 2 molecules through analyzing the spectral overlap, indicating that only eight molecules are prospective candidates for laser materials. Particularly, we find that ADBNA-Me-BPy molecule possesses large radiative decay rate and large reverse intersystem crossing rate, 1.90 × 106 s−1 and 1.01 × 108 s−1, respectively, implying a low lasing threshold, promising for electrically pumped lasing.

Reversible thermochromic systems based on a new library of flavylium spirolactone leuco dyes

The aim of this work was the design, synthesis, and characterization of new chromogenic spirolactone dyes based on a 2-phenyl-1-benzopyrylium (flavylium) backbone for further development of thermochromic smart labels. The influence of electron-donating and electron-withdrawing groups on the five synthesized dyes was studied in terms of color modification, acid-base behavior and thermochromic properties. By using UV–Vis absorption and emission spectroscopies, molar absorptivity, oscillator strength, Stokes shift, and fluorescence quantum yield were determined for each dye to evaluate the impact on color and excited state properties of the designed structures. The acid-base behavior and the ability to evolve towards leuco species was assessed by titrations with triethylamine and N,N-diisopropylethylamine in non-polar and polar aprotic solvents such as acetonitrile and octan-1-ol. In addition, the reversibility of the color was also evaluated by titrations with polar protic solvents (water and ethanol) and Lewis acids (gallic acid and iron(III) chloride). The number of equivalents of base/acid required to reach the leuco product and then to reverse the color were determined by representing the absorption maximum as a function of added base/acid in acetonitrile (water content less than 0.01-v/v). Finally, the thermochromic properties were evaluated in the presence of long-chain organic amines and water-insoluble solvents with melting points close to room temperature. The synthesized compounds can switch between two species if the appropriate conditions are used. Moreover, the tests carried out to assess their thermochromic behavior concluded that all dyes display thermochromism to some extent. The dyes that have electron-withdrawing groups attached, such as cyano, display stronger chromogenic effects useful for future applications.

Modeling Nonresonant X-ray Emission of Second- and Third-Period Elements without Core-Hole Reference States and Empirical Parameters.

Nonresonant X-ray emission (XE) energies and oscillator strengths are obtained using the effective potential of the generalized Kohn-Sham semi-canonical projected random phase approximation (GKS-spRPA) method. XE energies are estimated as a difference between the valence and core ionization eigenvalues, while the oscillator strengths are obtained within a frozen orbital approximation. This straightforward approach provides accurate XE energies without any need for core-hole reference states, empirical shifting parameters, or tuning of density functionals. To account for relativistic corrections to the core orbitals, we have formulated a scalar relativistic (sr) GKS-spRPA approach based on the spin-free X2C one-electron Hamiltonian. The sr-GKS-spRPA method provides highly reliable XE energies using uncontracted basis-sets on atoms where the core-hole is created prior to emission. For the largest basis-sets used in our study, using completely uncontracted polarized core-valence Dunning basis-sets, the mean absolute errors (MAEs) are within 0.7 eV compared to experimental reference values for a test-set consisting of 27 valence-to-core XE energies of molecules with second- and third-period elements. Considering a balance of accuracy and computational effort, we recommend the use of s-uncontracted def2-TZVP for second-period and all-uncontracted def2-TZVP for third-period elements. For this recommended basis-set, the MAE is 0.2 eV. The analytically continued sr-GKS-spRPA approach, with an computational cost, enables efficient computation of XE spectra of molecules such as S8 and C60 with several core-hole states.

Construction and Application of a New Polarity‐Sensitive Fluorescent Probe Based on the Excited‐State Intramolecular Proton Transfer Mechanism

AbstractA new excited‐state intramolecular proton transfer based near‐infrared emission and polarity‐sensitive fluorescent probe (E)‐3‐((E)‐2‐chloro‐3‐((E)‐2‐(3‐ethyl‐1,1‐dimethyl‐1H‐benzo[e]indol‐2(3H)‐ylidene)ethylidene)cyclohex‐1‐en‐1‐yl)‐1‐(2‐hydroxyphenyl)prop‐2‐en‐1‐one (M‐NA) was developed. This probe consisted of benzomerocyanine unit and o‐hydroxyacetophenone unit. In high‐polar solvent, M‐NA displayed higher fluorescence and longer emission wavelength. Theoretical calculations data showed that M‐NA had larger emission oscillator strength and lower non‐radiative decay in high polarity media, corresponding with the fluorescence character. Further experiments verified that M‐NA possessed excellent selectivity and stability, and could further quantify the accurate polarity as well as the water content of binary mixed solvent.

The conformational control of small D-A-D organic solar cells for large power conversion efficiency: A deep quantum chemistry analysis

Four naphthalene diimide (NDI) based small organic solar cells have been studied with for photoexcited and photovoltaic properties. Density functional theory and Tamm-Dancoff Approximation (TDA) with range-separation gap tunning have been used for ground and excited state calculations. The theoretical calculated results are highly reliable as the difference between the fundamental energy gap (Eg) and ionization gap (Ig) are nearly same. During this research study, the positions of donor units changed with symmetrical and unsymmetrical attachment sites which produced the interesting results of optoelectronic properties at both ground and excited states. The triphenyl amine (TPA) donor units at unsymmetrical units de-stabilized the HOMO and stabilized the LUMO energy levels significantly. The small vertical excitation energies of NDI-TPA molecules increased the transition coefficients from HOMO to LUMO. The emission rate of electron from S1 excited state to S0 is large for DPA-based molecules due to large vertical emission oscillator strength.

Laser Cooling with an Intermediate State and Electronic Structure Studies of the Molecules CaCs and CaNa.

The ground and excited electronic states of the diatomic molecules CaCs and CaNa have been investigated by implementing the ab initio CASSCF/(MRCI + Q) calculation. The potential energy curves of the doublet and quartet electronic low energy states in the representation 2s+1Λ(±) have been determined for the two considered molecules, in addition to the spectroscopic constants Te, ωe, Be, Re, and the values of the dipole moment μe and the dissociation energy De. The determination of vibrational constants Ev, Bv, Dv, and the turning points Rmin and Rmax up to the vibrational level v = 100 was possible with the use of the canonical functions schemes. Additionally, the transition and the static dipole moments curves, Einstein coefficients, the spontaneous radiative lifetime, the emission oscillator strength, and the Franck–Condon factors are computed. These calculations showed that the molecule CaCs is a good candidate for Doppler laser cooling with an intermediate state. A “four laser” cooling scheme is presented, along with the values of Doppler limit temperature TD = 55.9 μK and the recoil temperature Tr = 132 nK. These results should provide a good reference for experimental spectroscopic and ultra-cold molecular physics studies.

Exploring the effect of nitrile substituent position on fluorescence quantum yield of ESIPT-based oxazoline derivatives: A TDDFT investigation

We explore the mechanism specifically on quantum yields difference of 2-(4,4-Dimethyl-4,5-dihydrooxazol-2-yl)-3-hydroxybenzonitrile (1-CN) and 4-(4,4-Dimethyl-4,5-dihydrooxazol-2-yl)-3-hydroxybenzonitrile (3-CN) by density functional theory and time-dependent density functional theory within the Tamm-Dancoff approximation. The structures optimization and the potential energy curves scanning of singlet excited state directly prove that the excited state intramolecular proton transfer (ESIPT) can take place in 1-CN and 3-CN molecules. The calculated spectra show that the fluorescence peaks of two molecules come from the emission of keto* configuration. The non-covalent interaction and the atomic dipole moment corrected Hirshfeld charge are also analyzed. Through the comparison of emission oscillator strength between 1-CN and 3-CN molecules suggests that the radiative transition process is not the main reason for the difference on quantum yields. Internal conversion process is also excluded on account of the large energy gap between S0 and S1. Considering the interaction between singlet and triplet states, both molecules can undergo intersystem crossing. The prominent difference is that, compared with 3-CN, the larger spin-orbit coupling constant and smaller energy level difference promote the intersystem crossing process of 1-CN. This provides direct evidence for the fluorescence quantum yield of 1-CN is lower than that of 3-CN. We envision that the present work can provide help for the synthesis and application of ESIPT compounds with high quantum yields.

Comparison between Trion and Exciton Electronic Properties in CdSe and PbS Nanoplatelets

The optoelectronic properties of metal chalcogenide colloidal nanoplatelets are often interpreted in terms of excitonic states. However, recent spectroscopic experiments evidence the presence of trion states, enabled by the slow Auger recombination in these structures. We analyze how the presence of an additional charge in trions modifies the emission energy and oscillator strength as compared to neutral excitons. These properties are very sensitive to dielectric confinement and electronic correlations, which we describe accurately using image-charge and variational Quantum Monte Carlo methods in effective mass Hamiltonians. We observe that the giant oscillator strength of neutral excitons is largely suppressedin trions. Both negative and positive trions are redshifted with respect to the exciton, and their emission energy increases with increasing dielectric mismatch between the platelet and its surroundings, which is a consequence of the self-energy potential. Our results are consistent with experiments in the literature, and assess on the validity of previous theoretical approximations.

Laser cooling and electronic structure studies of CaK and its ions CaK±

Aiming at a laser cooling investigation, we have used ab initio complete active space self consistent field (CASSCF)/(MRCI +Q) calculations to study the electronic structure of the diatomic molecule CaK and its molecular ions CaK+ and CaK−. The potential energy curves and the static dipole moment curves have been investigated for the considered molecules along with the spectroscopic constants T e, ω e, B e, and R e, in addition to the values of dipole moment μ e and dissociation energy D e. Overall, 19 and 14 electronic states have been studied respectively for CaK, CaK+, from which 12 for CaK and six for CaK+ have been investigated here for the first time. Our obtained results agree well with data related to states that have been previously examined. Nineteen electronic states have been explored for CaK−, which up to our knowledge have not been previously calculated. The transition dipole moments have been calculated for the lowest Σ+–Σ+ and Σ+–Π transitions along with the Franck–Condon factor, Einstein coefficient, the spontaneous radiative lifetime, and the emission oscillator strength corresponding to the investigated transitions. A ro-vibrational analysis has been done via the canonical function approach, where the vibrational parameters E v, B v, D v, and the turning points R min and R max have been determined. These calculations showed that the molecule CaK is a suitable candidate for Doppler laser cooling, and we propose a laser cooling scheme to this end. The Doppler limit temperature T D and recoil temperature T r have values as low as T D = 51 μK and T r = 156 nK. The results should provide a useful reference for experimental spectroscopic and ultra-cold molecular physics studies.

Spectroscopic behaviour of Dy3+ and Sm3+ impurity-doped strontium magnesium borate glasses: A comparative evaluation

Two new series of strontium magnesium borate glasses with Dy3+ and Sm3+ activation (both in the concentration range of 0.1–1.0 mol%) were prepared using the standard melt-quenching and characterized. The optical and physical properties of these singly impurity-doped glass series were compared. The optical and physical properties of these glasses were determined in terms of the density, molar volume, optical band gap, absorption and emission intensities, oscillator strength, refractive index and molar polarizability. The XRD analyses confirmed the amorphous nature of the as-quenched samples. The EDX spectra revealed the actual elemental compositions and FESEM images showed the samples homogeneity without cracks. The UV–vis-NIR absorption spectra of the Dy3+- and Sm3+-doped glasses showed nine and ten characteristics bands respectively. The PL spectra of the Dy3+- and Sm3+-doped glasses displayed three ((at 481 nm, blue; 570 nm, yellow; and 661 nm, red) four (559, 596, 643 and 709 nm) significant peaks, respectively. The lasing potentials of the Dy3+- and Sm3+-doped glasses were compared via Judd-Ofelt evaluation. The values of branching ratio and stimulated emission cross-section for the 4F9/2 → 6H13/2 transition in Dy3+ and 4G5/2 → 6H7/2 transitions in Sm3+ was maximum, indicating their effectiveness towards photonic devices assembly. The studied glasses have demonstrated high viability for the cutting-edge innovations in the solid―state lighting and high gain optical fibre construction.

Bioluminescent Nanoluciferase–Furimamide Complex: A Theoretical Study on Different Protonation States

Luminescence of furimamide is 150 times brighter than oxidized luciferins in firefly and renilla luciferase. However, we do not have a clear understanding of the structure, function, and dynamic behavior of the nanoluciferase-furimamide complex. Here, for the first time, the absorption and emission properties of eight different possible light emitter forms of furimamide were investigated using the time-dependent density functional theory (TD-DFT) method in the gas phase and aqueous solution. The emission oscillator strengths in the gas phase showed that emission transition may be forbidden for some forms, and fluorescence would not occur. Besides, the charge transfer (CT) as well as the orbitals involved in the transitions were analyzed. Furthermore, molecular docking results showed that furimamide is situated inside the central cavity (β-barrel) of nanoluciferase. Analysis of the trajectory of molecular dynamics (MD) simulations suggested a less compact structure of protein in the presence of furimamide in comparison to its apo form. The quantum mechanical/molecular mechanical (QM/MM) spectroscopic properties of one form in the binding site of nanoluciferase were investigated. The evolution of the excited states (ESs) of furimamide in the binding pocket of the protein confirmed that after photoexcitation and during the relaxation of the system, a crossing point between the first two singlet ESs exists. Thus, the initially populated S2 (a π→π* transition) becomes the first singlet excited state.

Electronic Structure Calculations with the Spin Orbit Effect of the Low-Lying Electronic States of the YbBr Molecule.

This work presents an electronic structure study employing multireference configuration interaction MRCI calculations with Davidson correction (+Q) of the ytterbium monobromide YbBr molecule. Adiabatic potential energy curves (PECs), dipole moment curves, and spectroscopic constants (such as Re, ωe, Be, De, Te, and μe) of the low-lying bound electronic states are determined. The ionic character of the YbBr molecule at the equilibrium position is also discussed. With spin–orbit effects, 30 low-lying states in Ω = 1/2, 3/2, 5/2, 7/2 representation are probed. The electronic transition dipole moment is calculated between the investigated states and then used to determine transition coefficients, for example, the Einstein coefficient of spontaneous emission Aij and emission oscillator strength fij. Vibrational parameters such as Eν, Bν, Dν, Rmin, and Rmax of the low vibrational levels of different bound states in both Λ and Ω representations are also calculated. Upon calculating the Franck–Condon factors, they are found to be perfectly diagonal between three couples of low-lying excited states. Vibrational Einstein coefficients and radiative lifetimes are computed as well for the lowest vibrational transitions. Most of the data reported in this work are presented here for the first time in the literature. Very good accordance is obtained in comparison with the previously reported constants by means of experimental methods.

The Fluorescent Properties of pH‐Independent Cypridina Oxyluciferin Derivatives

AbstractThe co‐factors independent cypridina bioluminescence was often used to detect molecular oxygen. Whereas the native cypridina oxyluciferin and the majority analogues only emit blue light, it limits the application of the cypridina oxyluciferin derivative in detection active oxygen species. To overcome these limitations, we design two series of oxyluciferin derivatives: 2‐acetamido‐5‐aryl‐3‐(p‐trifluoromethylphenyl)pyrazine and 2‐acetamido‐5‐aryl‐3‐(p‐methoxylphenyl)pyrazine. The results found that the fluorescence emissions of the cypridina oxyluciferin derivatives cover the whole region of visible light. Especially, 2‐acetamido‐5‐(trans‐2,3,6,7‐tetrahydro‐1H,5H‐benzo[i,j]quinolizine‐ethenyl)‐3‐(p‐trifluoromethyl phenyl)pyrazine (1 h) can emit red light. By comparison of the emission spectra and oscillator strengths, it found that electron‐donating group in C3 position contributed to blue shift wavelength and improve luminous efficiency. The increasing conjugated length by introducing a conjugated double bond made the emission spectra shift to red and the luminescence strengths much stronger. Moreover, the analysis of the relative stabilities at the ground and excited states indicates that neutral forms, not amide ions, are dominant at physiological pH.

Investigation of GeSn/Ge quantum dots’ optical transitions for integrated optics on Si substrate

The effects of self-organized GeSn/Ge quantum dot’s size and shape on the direct band gap interband emission energy, oscillator strength and radiative lifetime are evaluated. The electron’s and the hole’s confined energies and their corresponding wave function are driven by solving the 3D Schrodinger equation in Cartesian coordinates using the finite elements method. Dome and pyramidal shaped quantum dots are considered within practically exploitable size and aspect ratio that allows direct band gap transition energies. It is found that bigger quantum dots with higher aspect ratio are likely to have higher oscillator strength and longer radiative lifetime. For smaller aspect ratio, the emission energy, oscillator strength and radiative lifetime are found to be very sensitive to the quantum dot’s size and shape. These results demonstrate that this quantum dot QD system could be very interesting for CMOS compatible light emitters and detectors operating in the mid-IR range.

Electronic structure with dipole moment and rovibrational calculations of the MgLi and MgNa molecules

We investigate an orderly study of the adiabatic potential energy curves for 29 and 30 low-lying 2s+1Λ+/− electronic states of the molecules MgLi and MgNa, respectively. The calculation has been done by using the complete active space self-consistent field followed by multi-reference configuration interaction with Davidson correction. For the investigated electronic states, the static and transition dipole moment curves are calculated along with the Einstein coefficients, the emission oscillator strength, the spontaneous radiative lifetime, the line strength, the classical radiative decay rate of the single-electron oscillator, the spectroscopic constants (Te, ωe, ωexe, Be, Re), and the equilibrium dissociation energy De. By means of the canonical functions approach, the ro-vibrational constants Ev, Bv, Dv, and the abscissas of the turning points, Rmin and Rmax, have been calculated for the considered electronic states up to the vibrational level v = 79. The Franck–Condon factors have been calculated and plotted for the transition between the low-lying electronic states of the two considered molecules. A good agreement is revealed between our calculated values and those available in the literature. Fifty new electronic states are investigated in the present work for the first time.

Theoretical insights into the excited-state properties of room-temperature phosphorescence-emitting N-substituted naphthalimides.

The optical absorption, fluorescence, and phosphorescence properties along with the intersystem crossing (ISC) rate constants of a series of N-substituted naphthalimides (NNIs), which can be used as organic emitters, were calculated using density functional theory (DFT) and time-dependent DFT (TDDFT). The calculated absorption, fluorescence, and phosphorescence energies as well as the fluorescence and ISC rate constants were found to be in good agreement with available experimental data. According to the calculations, the first excited singlet and first excited triplet states are π-π* in nature, and 1π-π*→3n-π* is the dominant ISC channel for 1,8-naphthalimide (NI) and N-methyl-1,8-naphthalimide (Me-NI). Intermolecular charge-transfer (CT) states are observed in the energy region between the 1π-π* and 3π-π* states for NNIs with an electron-donating group. The presence of these CT states leads to a reduction in the S1-state and T1-state energy splitting in NNIs with an electron-donating group compared to the energy splitting observed in NI and Me-NI. The singlet CT state (1CT) has very weak emission oscillator strength, so it is nonemissive. For NNIs with an electron-donating group, the 1CT→3π-π* transition was found to be the dominant ISC channel. Our results indicate that for NNIs with an electron-donating group, the nonemissive S1 state (1CT) transits to the T1 state (3π-π*) via ISC. The 1CT→3π-π* transition increases the population of the T1 state and thus the phosphorescence quantum yield at room temperature, even in the absence of a heavy atom. Graphical Abstract The S1 state (1CT), which is nonemissive, transits to the T1 state (3π-π*) via intersystem crossing and increases the population of the T1 state in N-substituted naphthalimides with an electron-donating group.

Electronic structure of the BaO molecule with dipole moments and ro-vibrational calculations

The twenty-three low-lying electronic states (singlet and triplet) of the BaO molecule have been studied by using an ab initio method. These electronic states have been investigated by using the Complete Active Apace Self-Consistent Field (CASSCF) followed by multi-reference configuration interaction (MRCI+Q) with Davidson correction. The potential energy curves, the internuclear distance Re, the harmonic frequency ωe, the rotational constant Be, the electronic energy with respect to the ground state Te and the static and transition dipole moment have been investigated. The Einstein spontaneous and induced emission coefficients A21 and B21ω as well as the spontaneous radiative lifetime τspon, emission wavelength λ21 and oscillator strength f21 have been calculated by using the transition dipole moment between some doublet electronic states. The calculation of the eigenvalues Ev, the rotational constant Bv, the centrifugal distortion constant Dv, and the abscissas of the turning points Rmin and Rmax have been done by using the canonical functions approach. A very good agreement is shown by comparing the values of our work to those found in the literature for many electronic states. Eighteen new electronic states have been studied here for the first time.

Theoretical electronic structure of the cadmium monohalide molecules CdX (X = F, Cl, Br, I)

The potential energy and dipole moment curves for the lowest electronic states in the representation 2s+1Λ(±) of CdX (X = F, Cl, Br, I) molecules are investigated via complete active space self-consistent field (CASSCF) and multi-reference configuration interaction MRCI (single and double excitation with Davidson correction). For the bound states of CdX diatomic molecules the bond distances Re, the vibrational harmonic frequencies ωe, the rotational constants Be, the electronic energies relative to the ground state Te, and the permanent and transition dipole moments have been computed. The dissociation energy limits of the atomic levels of CdX compounds are also calculated. The transition dipole moment between the ground state X2Σ+ and (2)2Σ+ is investigated. Consequently, the transition dipole moment values of the upper state at its equilibrium position μ21, the emission angular frequency ω21, the Einstein coefficients of spontaneous and induced emissions (A21 and B21ω), the spontaneous radiative lifetime τspon, the emission cross section σ0, the line strength and the emission oscillator strength f21 are calculated along with the ionicity of the X2Σ+ and (2)2Σ+ states. The eigenvalues Ev, the rotational constants Bv, the centrifugal distortion constants Dv and the abscissas of the turning points Rmin and Rmax of X2Σ+ states of the CdX diatomics are computed. The comparison of the results with those available in literature shows a very good agreement.