MRCI study on spectroscopic and molecular properties of several low-lying electronic states of the CN radical

The potential energy curves (PECs) of eight low-lying electronic states (X²Σ⁺, A²Π, B²Σ⁺, a⁴Σ⁺, D²Π, E²Σ⁺, 1²Σ⁻ and F²Δ) of the CN radical have been studied using the ab initio quantum chemical method. The calculations have been performed using the complete active space self-consistent field (CASSCF) method followed by the valence internally contracted multireference configuration interaction (MRCI) approach in combination with the correlation-consistent basis sets of Dunning and co-workers. The effects on the PECs by the core-valence correlation and relativistic corrections are taken into account. The way to consider the relativistic correction is to use the second-order Douglas-Kroll Hamiltonian approximation. The core-valence correlation correction calculations are performed with the cc-pCVQZ basis set. The relativistic correction is carried out at the level of cc-pV5Z basis set. In order to obtain more reliable results, the PECs determined by the MRCI calculations are also corrected for size-extensivity errors by means of the Davidson modification (MRCI+Q). The PECs are extrapolated to the complete basis set (CBS) limit by the total-energy extrapolation scheme. With these PECs, the spectroscopic parameters (T_e, R_e, ω_e, ω_ex_e, ω_eу_e, B_e, α_e and γ_e) are determined and compared with those reported in the literature. Finally, with the PECs obtained by the MRCI+Q/CV+DK+Q5 calculations, the complete vibrational states are computed for the eight electronic states by solving the ro-vibrational Schrödinger equation for the non-rotating radical, and the vibrational levels and inertial rotation and centrifugal distortion constants of the first 11 vibrational states are reported, which agree favorably with the available experimental data. The spectroscopic parameters of 1²Σ⁻ and F²Δ electronic states obtained by the MRCI+Q/CV+DK+Q5 calculations should be good predictions for future laboratory experiments.     

MRCI study on spectroscopic and molecular properties of four low-lying electronic states of the BO radical

The potential energy curves (PECs) of four low-lying electronic states of the BO radical, including two ²Σ⁺ and two ²Π states, have been studied using the full valence complete active space self-consistent field (CASSCF) method followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach in combination with the cc-pV5Z basis set for internuclear separations from 0.05 to 2.0 nm. The effect on the PECs by the relativistic correction has been taken into account. With these PECs, the spectroscopic parameters (T_e, D₀, D_e, R_e, ω_e, ω_ex_e, α_e and B_e) of two main isotopologues (¹¹B¹⁶O and ¹⁰B¹⁶O) have been determined. These parameters have been compared in detail with those of previous investigations reported in the literature, and excellent agreement has been found between the available data and the present results. By solving the radial Schrödinger equation of nuclear motion, 60 vibrational states for the ¹¹B¹⁶O(X²Σ⁺), 60 for the ¹⁰B¹⁶O(X²Σ⁺), 66 for the ¹¹B¹⁶O(A²Π) and 64 for the ¹⁰B¹⁶O(A²Π) are predicted for the non-rotating molecule. For each vibrational state of the ¹¹B¹⁶O(X²Σ⁺), ¹⁰B¹⁶O(X²Σ⁺), ¹¹B¹⁶O(A²Π) and ¹⁰B¹⁶O(A²Π), the vibrational level G(υ), inertial rotation constant B_υ and centrifugal distortion constant D_υ have been determined. Comparison with the available data shows that the present molecular constants are reliable and accurate. The ro-vibrational levels have been calculated for the X²Σ⁺ and A²Π states of two main species for future laboratory research.     

Three-body dissociation dynamics of the low-lying Rydberg states of H3 and D3

The dynamics of the three-body dissociative charge exchange of fast (12 keV) H+3 and D+3 with Cs have been studied using multiparticle translational spectroscopy. The observed partitioning of product momenta was found to be state-specific and yields insights into the nuclear motion during dissociation for the three lowest-lying 2s 2A'1, 2p 2A'2, and 3p 2E' metastable Rydberg states of H3 and the 2s 2A'1 and 2p 2A'2 states for D3. These results provide direct empirical information on the nonadiabatic couplings that govern the three-body dissociation of the lowest-lying Rydberg states of H3 and D3.     

Ab initio MRCI＋Q study on potential energy curves and spectroscopic parameters of low-lying electronic states of CS＋

Carbon monosulfide molecular ion （CS＋）, which plays an important role in various research fields, has long been attracting much interest. Because of the unstable and transient nature of CS＋, its electronic states have not been well investigated. In this paper, the electronic states of CS＋ are studied by employing the internally contracted multireference configuration interaction method, and taking into account relativistic effects （scalar plus spin–orbit coupling）. The spin–orbit coupling effects are considered via the state-interacting method with the full Breit–Pauli Hamiltonian. The potential energy curves of 18 Λ–S states correlated with the two lowest dissociation limits of CS＋ molecular ion are calculated, and those of 10 lowest Ω states generated from the 6 lowest Λ–S states are also worked out. The spectroscopic constants of the bound states are evaluated, and they are in good agreement with available experimental results and theoretical values. With the aid of analysis of Λ–S composition of Ω states at different bond lengths, the avoided crossing phenomena in the electronic states of CS＋ are illuminated. Finally, the single ionization spectra of CS （X1Σ＋） populating the CS＋（X2Σ1/2＋, A2Π3/2, A2Π1/2, and B2Σ1/2＋） states are simulated. The vertical ionization potentials for X2Σ1/2＋, A2Π3/2, A2Π1/2, and B2Σ1/2＋ states are calculated to be 11.257, 12.787, 12.827, and 15.860 eV, respectively, which are accurate compared with previous experimental results, within an error margin of 0.08 eV~0.2 eV.     

Ab initio study of ground and low-lying excited states of MgLi and MgLi+ molecules with valence full configuration interaction and MRCI method

The ground and low-lying excited states of MgLi and MgLi⁺ molecules have been investigated. The potential energy curves and the permanent and transition dipole moments of the MgLi and MgLi⁺ molecules are determined making use of the multi-reference configuration interaction and valence full configuration interaction with large basis sets. The core–valence correlation and scalar relativistic correction are also taken into account with aug-cc-pCVQZ basis set and the third-order Douglas–Kroll Hamiltonian approximation, respectively. The transition dipole moments are used to evaluate the radiative lifetimes of the vibrational levels for the low-lying excited states of the MgLi and MgLi⁺ molecules. The derived spectroscopic constants of the ground and low-lying excited states are in good agreement with available experimental and theoretical works.     

多参考组态相互作用方法研究ZnHg低激发态(1Ⅱ,3Ⅱ)的势能曲线和解析势能函数

采用多参考组态相互作用方法计算了ZnHg二聚体两个低激发Ⅱ态(1Ⅱ,3Ⅱ)的原子间相互作用势能曲线.用Murrel-Sorbie函数拟合得到了相应的解析势能函数,并用其计算力常数,进而确定了光谱常数.所得结果与仅有的理论工作进行了比较.基于所得势能曲线,通过解分子中原子核运动的薛定谔方程预测了各电子态的振动能级.     

Detection and study of Rb I Rydberg states

We describe the details of an experiment using an atomic beam of rubidium which allowed us to detect by field ionization techniques the np Rydberg states from n = 28 up to n = 78, to detect also ns and nd states using a Stark mixing, and for all of these detected states to check the classical law E_c = [16n^*4]^?1 concerning the critical ionizing electric field E_c. It turns out that for n as high as 65 this law is quite well verified.     

Rydberg states of SiBr

New uv absorption spectra have been observed for SiBr. Five Rydberg states are identified to the states $\text{(4sσ)}{}^2\text{Σ}{}^{\mathrm{+}}$, $\text{(5sσ)}{}^2\text{Σ}{}^{\mathrm{+}}$, $\text{(4pπ)}{}^2\text{Π}$, $\text{(3dπ)}{}^2\text{Π}$, and $\text{(3dδ)}{}^2\text{Δ}$ by comparison with SiF and SiCl. The ionization potentials of SiCl and SiBr have been determined for the first time, and were 6.82 and 6.67 eV, respectively.     

Structure of the low-lying states of 47Ti

Deformed configuration-mixing calculations for the nucleus ⁴⁷Ti have been performed in the framework of the projected Hartree-Fock formalism. For each of the angular momentum states, the Hamiltonian has been diagonalized in the basis of about ten of the lowest orthogonalized projected states. The resulting spectrum is in good agreement with the observed spectrum of negative parity states. The eigenstates of the Hamiltonian have been analysed for the possible existence of the “band structure”. Besides the “ground state” $\text{K =}\text{5}\text{2}$ band of states with deformation δ ≈ 0.15, another well defined band of states belonging to the $\text{K =}\text{1}\text{2}$ neutron excited intrinsic state is likely to exist. The calculated and experimental binding energies are in good agreement. The results of the detailed calculation have been extrapolated to obtain an estimate of the level density for ⁴⁷Ti up to 6 MeV excitation energy.     

Theoretical study of the electronic ground states and low-lying singlet excited states of thiophene-based spirofluorenes

The electronic structures and optical properties of oligothiophene substituted spirofluorenes are investigated theoretically with semi-empirical quantum chemical calculations. A theoretical investigation of the interaction between two perpendicular π-systems of various oligothiophene substituted spirofluorenes is conducted. The results demonstrate that the interaction between two perpendicular branches is reduced by oligothiophene substitutions. Photoexcitation induced relaxation is mainly located on one of...     

Rydberg states of the PO molecule

The absorption spectrum of the PO molecule in the region 2100 to 1550 Å has been studied in detail at high resolution. From a rotational analysis of the spectrum, a number of new electronic states have been discovered. Some of these electronic states have been assigned to Rydberg series of the various nl complexes of PO. An upper limit of the ground state dissociation energy has been lowered to 49090 cm^?1 (X²Π, T₀ = 0). Quantum defects are calculated and the first ionization potential of PO is improved to 67 532 cm^?1.     

MRCI studies on ground and excited states of CBr

Potential curves and spectroscopic constants for a large number of doublet and quartet states of CBr were obtained by multireference configuration interaction calculations, using valence triple-zeta basis sets with polarization and diffuse functions. Besides the X²Π ground state, 1⁴Σ^?, 1²Δ and 2²Σ⁺ have been found to be stable. Spectroscopic constants calculated for 1²Δ are in excellent agreement with experimental values obtained by Dixon and Kroto in 1963. Their observed predissociation of one component of 1²Δ can be explained by the crossing of the 1²Δ potential near equilibrium by 1²Σ⁺. The 1²Σ⁺ state is calculated to have a shallow long-range minimum at 2.31?Å. The dissociation energy of X²Π is calculated to be 3.43?eV. An observed T _e of 4.97?eV for 2²Σ⁺ agrees with the theoretical value. Several Rydberg states of the 2π→Ryd and 3σ→Ryd series, starting at T _e ?=?5.25?eV, were identified. Photodissociation of CBr by sunlight, important in the ozone cycle, can occur via direct dissociation of the ground state, or by excitation to 1²Δ followed by predissociation. Most dissocative repulsive states lie at higher energies, and are not expected to participate in the photodisscociation of CBr.     

Quasi-relativistic treatment of the low-lying KCs states

The potential energy curves, permanent and transition dipole moments as well as spin-orbit and angular coupling matrix elements between the KCs electronic states converging to the lowest three dissociation limits were evaluated in the basis of the spin-averaged wavefunctions corresponding to pure Hund’s coupling case (a). The quasi-relativistic matrix elements have been obtained for a wide range of internuclear distance by using of small (9-electrons) effective core pseudopotentials of both atoms. The core-valence correlation has been accounted for a large scale multi-reference configuration interaction method combined with semi-empirical core polarization potentials. The static dipole polarizabilities of the ground X¹Σ⁺ and a³Σ⁺ states were extracted from the closed-shell coupled-cluster energies by the finite-field method. Among the singlet and triplet Σ⁺ states manifold the pronounced avoided crossing effect between repulsive walls of the (2,3)³Σ⁺ states has been discovered and analyzed by finite-difference calculation of radial coupling matrix elements. The resulting transition dipole moments and potentials were used to predict radiative lifetimes and emission branching ratios of excited vibronic states while the calculated angular coupling matrix elements were transformed to Λ-doubling constants of the (1,2)¹Π states and magnetic g-factor of the ground state. The accuracies of the present results are discussed by comparing with experimental data and preceding calculations.     

Lifetimes of low-lying states in 19F

Lifetimes of low-lying states in ¹⁹F were measured using the Doppler-shift attenuation method through the ¹⁵N(α, γ)¹⁹F reaction. Values of τ_m = 3700 ± 700 fs (1.35 MeV), 140 ± 15 (1.46), 19 ± 7 (4.00) and 63 ± 19 (4.03) were obtained for the lowest $\text{5}\text{2}{}^{\mathrm{?}}$, $\text{3}\text{2}{}^{\mathrm{?}}$, $\text{7}\text{2}{}^{\mathrm{?}}$ and $\text{9}\text{2}{}^{\mathrm{?}}$ members, respectively, of the $\text{K}{}^{\mathrm{\pi }}\text{=}\text{1}\text{2}{}^{\mathrm{?}}$ rotational band and 5 ± 3 fs (1.55 MeV) and 370 ± 25 (2.78) for the $\text{3}\text{2}{}^{\mathrm{+}}$ and $\text{9}\text{2}{}^{\mathrm{+}}$ members of the $\text{K}{}^{\mathrm{\pi }}\text{=}\text{1}\text{2}{}^{\mathrm{+}}$ ground-state band. For the Doppler-shift attenuation analysis correction factors of the nuclear and electronic stopping powers were determined by measuring the Doppler-shift attenuation and γ-ray line shape of the 2.78 → 0.20 MeV transition and range values of 100, 200. 300 and 370 keV ¹⁹F nuclei in tantalum. All calculations were done with Monte Carlo methods. The transition strengths are discussed in terms of different theoretical predictions.     

Isospin structure of low-lying Ti states

The 3₁⁻ state of ⁴⁶Ti exhibits unusual γ-decay properties, with E1 decay to the 2₂⁺ state being highly preferred. A theoretical investigation of the isospin structure of the first two 2⁺ states in ^{44, 46, 48}Ti provides a qualitative explanation of this observation.     

A calculation of low-lying collective states in even-even nuclei

We present results of a calculation of the low-lying collective quadrupole states in even-even nuclei within the framework of the proton-neutron interacting boson model.     

钠分子^1Пg里德堡态光谱研究

通过光学－光学以共振（ＯＯＤＲ）光谱方法,研究了钠分子六个高激发＾１Пｇ态,对它们进行了振动和转动归属,获得了分子常数和势能曲线。根据里德堡轨道的ｎｌλ特性,将１－１０＾１Пｇ态划分为实贯穿里德堡态和实非贯穿里堡态。