LiC分子基态及其低电子激发态的多参考组态相互作用方法研究

采用包含Davidson修正的多参考组态相互作用(MRCI+Q)方法结合6-311++G(3df,3pd)基组计算了LiC分子基态(X4Σ-)以及五个低电子激发态(a2Π,b2Δ,c2Σ-,d2Σ+,A4Π)的势能曲线.将得到的势能曲线拟合到Murrell-Sorbie解析势能函数形式,确定了对应态的平衡结构Re、谐振频率ωe和离解能De等光谱数据,计算值与仅有的几个其他结果进行了比较.通过求解核运动的薛定谔方程首次报道了LiC分子几个低电子态在J=0下的振动能级、转动惯量和六个离心畸变常数(Dν,Hν,Lν,Mν,Nν和Oν).     

Rotational Analysis of the 1–4 Band of the B 2Σ+–X 2Σ+ System of 14C16O+

ABSTRACT

High-resolution emission spectrum of the 1–4 band of the B ²Σ⁺–X ²Σ⁺ transition of ¹⁴C¹⁶O⁺ was observed for the first time by conventional emission spectroscopy. The band spectrum was excited in a water-cooled Geissler lamp filled with commercial gaseous carbon monoxide enriched in about 80% of the radiocarbon ¹⁴C. A rotational analysis has been carried out and obtained molecular constants have been merged with previously published data for the B ²Σ⁺–A ²Π_i and A ²Π_i–X ²Σ⁺ transitions. The principal equilibrium constants for the ground X ²Σ⁺ state obtained from this work are ω_e = 2121.7726(98), ω_e x _e = 13.9055(27), B _e = 1.815290(30), α_e = 1.6594(33) × 10^?2, and γ_e = ? 0.377(73) × 10^?4 cm^?1. Also, presently known experimental equilibrium molecular constants of the X ²Σ⁺ states of the CO⁺ isotopic molecules are summarized and isotopic dependence of the B _e and ω _e constants is discussed.     

用MRCI方法研究CS+同位素离子X2Σ+和A2Π态的光谱常数与分子常数

利用内收缩多参考组态相互作用方法和价态范围内的最大相关一致基aug-cc-pV6Z, 在0.05—0.60 nm的核间距范围内计算了CS⁺离子X²Σ+和A²Π态的势能曲线. 利用CS⁺离子的势能曲线并在同位素质量修正的基础上, 拟合出了X²Σ+和A²Π态的同位素离子^{1 关键词： 同位素识别 势能曲线 光谱常数 分子常数}     

Ab initio calculations on the ground and excited states of InI

Potential energy curves (PECs) of the ground and the low-lying excited states of the InI molecule are computed using the internally contracted multireference singles and doubles configuration interaction with the Davidson correction (ic-MR-CISD + Q) method based on the relativistic effective core potentials (RECPs). The spectroscopic constants are obtained, including the excitation energy (T _e), the equilibrium bond distance (R _e), the dipole moment (μ_e) and the vibrational constants (ω_e and ω_e). Finally, we predict the transition dipole moments, the radiative lifetimes, and the Franc-Condon factors for the transitions of A³Π₀+ ? X¹Σ₀ ⁺ and B³Π^l ? X¹Σ₀ ⁺,. The results reveal that A³Π₀+ and B³Π_l are long-lived states with the lifetimes being of the order of microseconds.     

Ab initio study of PN electronic states – a qualitative interpretation of the perturbation and predissociation effects on observed transitions

Valence and high electronic states of PN have been calculated with accurate quantum chemistry methods. The variety of theoretical methods used includes complete active space self-consistent field, multireference configuration interaction and the newly developed explicitly correlated coupled cluster methods. The large correlation-consistent atomic orbitals basis sets AVQZ, AV5Z and AV(5+d)Z are used for the potential energy curves calculations in the bonding and long-range regions. The spectroscopic constants (R_e, B_e, ω_e, ω_ex_e, α_e, D_e, T_e) and the vibrational levels of the bound valence states (X¹Σ⁺, A¹Π, a³Σ⁺, d ³Δ, e³Σ^?, C¹Σ^?, b³Π, D ¹Δ and E¹Σ⁺ and some higher bound states) are determined and compared with experimental findings when available. Significant spin–orbit interactions between triplet states and A¹Π and E¹Σ⁺ excited states are found near the crossing points of the potential energy curves and could explain predissociation phenomena and the perturbations of the vibrational levels experimentally observed for PN in their A¹Π and E¹Σ⁺ states.     

Li2分子自旋一致激发态a3Σ+u和b3Πu的分析势能函数的从头算

使用对称性匹配簇-组态相互作用方法首次计算了Li₂分子自旋一致激发态a³Σ⁺_u和b³Π_u的离解能、平衡几何及其谐振频率。使用最小二乘法、利用Murrell-Sorbie函数形式拟合出了Li₂分子三重态的第一激发态a³Σ⁺_u 和第二激发态b³Π_u的完整势能函数，并计算了这两个态的光谱常数 (B_e, α_e, ω_e 和 ω_eχ_e) 和力常数 (f₂, f₃和f₄)。得到了Murrell-Sorbie函数形式既适用于基态、又适用于激发态的结论。将计算得到的激发态（a³Σ⁺_u和b³Π_u）的离解能、平衡几何及其谐振频率与实验结果及其它理论计算结果进行了比较。从比较的结果中可以清楚地看出，本文的计算结果在计算精度方面有很大的改进。     

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.     

Isotope shift studies in the spectrum of boron monosulphide

The spectrum of boron monosulphide has been excited in microwave discharge and photographed at moderate dispersion. TheC ²Π _r ?X ²Σ⁺,B ²Σ⁺?A ²Π _i andA ²Π _i ?X ²Σ⁺ band systems extending from 2100–9000 Å have been obtained for B³²S and B³⁴S species. Isotope shifts for all these band systems have been measured. Comparison of the observed isotope shifts with the theoretically calculated isotope shifts confirms the emitter as well as the vibrational assignments of all these band systems.     

Rotational analysis ofA 1Π-X 1Σ+ bands of As14N and As15N: perturbation studies in theA 1Π state

The ultraviolet bands ofA ¹Π-X ¹Σ⁺ system of As¹⁴N and its isotopic species As¹⁵N were excited in a quartz tube containing specpure nitrogen and traces of AsCl₃ vapour, using a microwave discharge (2450 MHz). Bands of As¹⁵N were obtained using¹⁵N₂ enriched to 95.5%. Rotational structure of several bands of As¹⁴N and As¹⁵N photographed under high dispersion (0.14 Å/mm) was reanalysed. Detailed studies of the observed perturbations in the levels ofν′ = 0 to 4 led to the identification of two³Σ^? and aC ¹Σ^? states. Molecular parametersT _e, ω_e, ω_ex_e, B_eandα _ewere determined for all the electronic states studied. Vibrational assignments of the perturbing levels were made using the isotope shift studies.     

The B 2Σ+–X 2Σ+ Transition of 12C17O+: The 2‐υ″ Progression

Abstract

Three new bands of the B ²Σ⁺–X ²Σ⁺ system of ¹²C¹⁷O⁺ have been investigated using conventional spectroscopic techniques. The spectra were observed in a graphite hollow‐cathode lamp by discharging molecular oxygen (enriched in about 45% of the ¹⁷O₂ isotope) under 1.0 Torr pressure. The rotational analysis of the 2–4, 2–5, and 2–6 bands was performed with the effective Hamiltonian of Brown (Brown et al., J. Mol. Spectrosc. 1979; 74: 294–318). Molecular constants were derived from a merge calculation, including both the current wavenumbers and the spectroscopic data published by the authors previously. The principal equilibrium constants for the ground state of ¹²C¹⁷O⁺ are ω_e=2185.9658(84), ω_e x _e = 14.7674(11), B _e=1.927001(38), α_e=1.8236(22)×10^?2, γ_e=?0.331(28)×10^?4, D _e=6.041(12)×10^?6, β_e=0.100(31)×10^?7 cm^?1, and the equilibrium constants for the excited state are σ_e=45876.499(15), ω_e=1712.201(12), ω_e x _e=27.3528(39), B _e=1.754109(35), α_e=2.8706(57)×10^?2, γ_e = ?1.15(19)×10^?4, D _e=7.491(20)×10^?6, β_e=2.13(12)×10^?7, γ_e = 2.0953(97)×10^?2, and α_γe=?9.46(59)×10^?4 cm^?1, respectively. Rydberg–Klein–Rees potential energy curves were constructed for the B ²Σ⁺ and X ²Σ⁺ states of this molecule, and Franck–Condon factors were calculated for the vibrational bands of the B–X system.     

Rotational distribution in simultaneously excited electronic states of CH

A²Δ, B²Σ^? and C²Σ⁺ states of CH were excited in discharges through flowing C₂H₂ and C₂H₄ and in flames of C₂H₂. The rotational distributions in these states were determined from the measured integrated intensities of rotational lines for bands of A²Δ → X²Π, B²Σ^? → X²Π and C²Σ⁺ → X²Π. The A²Δ state exhibits a non-Maxwellian distribution while the B²Σ^? and C²Σ⁺ states show Maxwellian distributions. The non-Maxwellian distribution of the A²Δ state and the different rotational distributions in the three states are discussed.     

Spectroscopic parameters and molecular constants of HI(X~1Σ~+),DI(X~1Σ~+) and TI(X~1Σ~+) isotope molecules

The potential energy curve (PEC) of HI(X¹Σ⁺) molecule is studied using the complete active space self-consistent field method followed by the highly accurate valence internally contracted multireference configuration interaction approach at the correlation-consistent basis sets, aug-cc-pV6Z for H and aug-cc-pV5Z-pp for I atom. Using the PEC of HI(X¹Σ⁺), the spectroscopic parameters of three isotopes, HI(X¹Σ⁺), DI(X¹Σ⁺) and TI(X¹Σ⁺), are determined in the present work. For the HI(X¹Σ⁺), the values of D₀, D_e, R_e, ω_e, ω_eχ_e, α_e and B_e are 3.1551 eV, 3.2958 eV, 0.16183 nm, 2290.60 cm^-1, 40.0703 cm^-1, 0.1699 cm^-1 and 6.4373 cm^-1, respectively; for the DI (X¹Σ⁺), the values of D₀, D_e, R_e, ω_e, ω_eχ_e, α_e and B_e are 3.1965 eV, 3.2967 eV, 0.16183 nm, 1626.8 cm^-1, 20.8581 cm^-1, 0.0611 cm^-1 and 3.2468 cm^-1, respectively; for the TI (X¹Σ⁺), the values of D₀, D_e, R_e, ω_e, ω_eχ_e, α_e and B_e are of 3.2144 eV, 3.2967 eV, 0.16183 nm, 1334.43 cm^-1, 14.0765 cm^-1, 0.0338 cm^-1 and 2.1850 cm^-1, respectively. These results accord well with the available experimental results. With the PEC of HI(X¹Σ⁺) molecule obtained at present, a total of 19 vibrational states are predicted for the HI, 26 for the DI, and 32 for the TI, when the rotational quantum number J is equal to zero (J = 0). For each vibrational state, vibrational level G(?), inertial rotation constant B_? and centrifugal distortion constant D_? are determined when J = 0 for the first time, which are in excellent agreement with the experimental results.     

Fourier Transform Infrared Emission Spectroscopy of thebΠ–aΣSystem of BN

The emission spectrum of BN has been investigated in the 1800–9000 cm⁻¹region using a Fourier transform spectrometer. BN was formed in a microwave discharge of He with a trace of BCl₃and N₂. The bands observed in the 3000–7800 cm⁻¹interval have been assigned as theb¹Π–a¹Σ⁺transition, with the 0–0 band at 3513.99040(43) cm⁻¹. This transition is analogous to theA¹Π_u–X¹Σ⁺_g(Phillips) system of the isoelectronic C₂molecule. The rotational analysis of the 0–0, 1–1, 1–0, 2–1, 3–2, 2–0, 3–1, 4–2, and 4–1 bands has been obtained and the molecular constants for theb¹Π anda¹Σ⁺states have been determined. A local perturbation has been observed in thev= 1 vibrational level of theb¹Π state nearJ= 18 caused by the interaction with thev= 3 vibrational level of thea¹Σ⁺state. The principal equilibrium constants for thea¹Σ⁺state are: ω_e= 1705.4032(11) cm⁻¹, ω_ex_e= 10.55338(52) cm⁻¹,B_e= 1.683771(10), α_e= 0.013857(16) cm⁻¹, andr_e= 1.2745081(37) Å. Although theb¹Π–a¹Σ⁺transition has recently been seen in emission from boron nitride trapped in solid neon matrices [J. Chem. Phys.104,3143–3146 (1996)], our work represents the first observation of this transition of BN in the gas phase.     

Time evolution of the Infrared Laser Induced Breakdown Spectroscopy of DNA bases Guanine and Adenine

Laser-Induced Breakdown Spectroscopy (LIBS) of DNA bases Guanine and Adenine was studied using a high-power CO₂ pulsed laser (λ=10.591 μm, τ _FWHM=64 ns and fluences ranging from 25 to 70 J/cm²). The strong emission of the adenine and guanine plasma, collected using a high-resolution spectrometer, at medium-vacuum conditions (4 Pa) and at 1 mm from the target, exhibits excited molecular bands of CN (B² Σ ⁺–X² Σ ⁺) and excited neutral H and ionized N⁺ and C⁺. The medium-weak emission is due to excited species C²⁺, C³⁺, N, O, O⁺, O²⁺ and molecular band systems of $\mathrm{C}_{2}(\mathrm{d}^{3}\varPi_{\mathrm{g}}\mbox{--}\mathrm{a}^{3}\varPi_{\mathrm{u}};\ \mathrm{D}^{1}\varSigma_{\mathrm{u}}^{+}\mbox{--}\mathrm{X}^{1}\varSigma_{\mathrm{g}}^{+})$ , OH(A² Σ ⁺–X² Π), NH(A³ Π–X³ Σ ^?), CH(A² Π–X² Π), $\mathrm{N}_{2}^{+}(\mathrm{B}^{2}\varSigma_{\mathrm{u}}^{+}\mbox{--} \mathrm{X}^{2}\varSigma_{\mathrm{g}}^{+})$ and N₂(C³ Π _u–B³ Π _g). We focus our attention on the temporal evolution of different atomic/ionic and molecular species. The velocity distributions for various (different) species were obtained from time-of-flight (TOF) measurements. Intensities of some lines from C⁺ were used for determining electron temperature and their Stark-broadened profiles were employed to estimate the temporal evolution of electron density.     

Lifetime measurements of the C1Π1 and B3Pi1 electronic states of InCl by laser induced fluorescence

The laser-induced fluorescence spectra of the InCl molecule over the range 266.5–287.0nm and 332.0–373.0nm are reported and assigned to C¹Π₁-X¹Σ⁺, B₃Π₁-X¹Σ⁺, or A³Π₀-X¹Σ⁺ transitions. It is the first time those radiative lifetimes of the C¹Π₁ and B³Π₁ states have been measured by laser-induced fluorescence. The collision-free fluorescence radiative lifetime τ₀ = 353(7)ns and a quenching rate constant k _Q = 1.985(0.010)x 10^-10 cm³ molecule^-1 s^-1 are proposed for B³Π₁ and τ₀ = 11(1)ns for C¹Π₁ states. From the radiative lifetime τ₀ and the Franck-Condon factors q_v″v′ for the v′ - v″ transitions, the electronic transition moments |R_e|² of the B³Π₁ and C¹Π₁ states have been obtained.     

Transition probabilities of the X1Σ+, A1Π, B1Δ, C1Σ+, and D1Π states of the AlO+ cation

ABSTRACT

This study computes the potential energy curves of the X¹Σ⁺, A¹Π, B¹Δ, C¹Σ⁺, and D¹Π states of AlO⁺ cation and the transition dipole moments between them. The orders of the rotationless radiative lifetimes are 10–100?μs for the A¹Π state, 1–1000?ms for the B¹Δ state, 10?ns for the first well and 100?ns for the second well of the C¹Σ⁺ state, and 1?μs for the D¹Π state. Emissions of the B¹Δ–A¹Π and D¹Π–C¹Σ⁺ systems are so weak that they are hardly measured via spectroscopy, the emissions of the C¹Σ⁺–X¹Σ⁺, C¹Σ⁺–A¹Π, and D¹Π–X¹Σ⁺ systems are so strong that they can be detected readily, and emissions of the A¹Π–X¹Σ⁺ and D¹Π–A¹Π systems can be observed through spectroscopy only by a significant effort. There is a strong great similarity between spontaneous emissions of the A¹Π–X¹Σ⁺ system of the AlO⁺ cation and the A²Π–X²Σ⁺ system of the AlO radical. The emissions of the A²Π–X²Σ⁺ system of the AlO radical have been measured in outer space Therefore, it is highly possible that the emissions of the A¹Π–X¹Σ⁺ system of the AlO⁺ cation can be detected in the astrophysical media.     

MRCI study of spectroscopic and molecular properties of X1Σg+ and A1Πu electronic states of the C2 radical

The potential energy curves (PECs) of X1Σ+g and A1Πu electronic states of the C2 radical 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 conjunction with the aug-cc-pV6Z basis set for internuclear separations from 0.08 nm to 1.66 nm. With these PECs of the C2 radical,the spectroscopic parameters of three isotopologues ( 12C2 ,12C13C and 13C2 ) have been determined. Compared in detail with previous studies reported in the literature,excellent agreement has been found. The complete vibrational levels G(υ),inertial rotation constants B υ and centrifugal distortion constants D υ for the 12C2 ,12C13C and 13C2 isotopologues have been calculated for the first time for the X1Σ+g and A1Πu electronic states when the rotational quantum number J equals zero. The results are in excellent agreement with previous experimental data in the literature,which shows that the presented molecular constants in this paper are reliable and accurate.     

High-resolution emission spectroscopy of the AΠ–XΣ system of AlH

The emission spectrum of the A²Π–X²Σ⁺ system of the AlH⁺ ion was investigated in the range of 27 000–29 000 cm⁻¹ by using a conventional spectroscopic technique. The AlH⁺ molecules were formed and excited in an aluminium hollow-cathode lamp with two anodes, filled with a mixture of Ne carried gas and a trace of NH₃. The emission from the discharge was observed with a plane grating spectrograph and recorded by a photomultiplier tube. The full rotational structure of the 0-0 and 1-1 bands has been observed for the first time (12 branches up to J″ = 36.5) and many new constants of the X²Σ⁺ state have been derived from the analysis. For the A²Π, v = 0 and 1 state a considerable irregularities of the Λ-doubling have been observed. The most reasonable explanation for this anomaly is an interaction with unstableness rotational levels of X²Σ⁺ state and perturbing of the A²Π state by the nearly lyingB²Σ⁺ state.     

Perturbations in the A1Π, v = 0 state of 12C18O investigated via complementary spectroscopic techniques

The A¹Π(v = 0) level of ¹²C¹⁸O has been reinvestigated using three different high-resolution spectroscopic methods: (1) 2 + 1′ resonance-enhanced multiphoton ionisation of the A¹Π ? X¹Σ⁺(0, 0) band using narrowband lasers in a Doppler-free geometry; (2) Fourier-transform emission spectroscopy in the visible range probing the B¹Σ⁺ ? A¹Π(0, 0) band in a discharge; (3) Fourier-transform absorption spectroscopy in the vacuum-ultraviolet range measuring the A¹Π ? X¹Σ⁺(0, 0) and B¹Σ⁺ ? X¹Σ⁺(0, 0) bands at multiple temperatures ranging from 90 to 900 K. An effective-Hamiltonian analysis of A¹Π, v = 0 levels was performed up to J = 44 which quantitatively addresses perturbations by the e?³Σ^?(v = 1), d³Δ(v = 4), a′³Σ⁺(v = 9), D?¹Δ(v = 0), and I?¹Σ^?(v = 0, 1) levels.     

Low-lying electronic states of BeH+ with the effect of inner electrons

The potential energy curves of the low-lying electronic states of BeH⁺ molecular ion are performed by using highly accurate multi-reference configuration interaction with AV5Z basis sets for H atom and ACV5Z basis set for Be atom, 1s inner shell of Be is considered as the core orbit and the active orbit, respectively, which are used to characterise the spectroscopic properties of a manifold of singlet and triplet states. Fourteen electronic states correlated with eight dissociation channels are investigated, we have found that the a³Σ⁺ and c³Σ⁺ both are bound states, the 3³Σ⁺ possesses double wells, and the C¹Σ⁺, 3³Σ⁺, 2³Π, 2¹Π, 1¹Δ, 1³Δ, 2³Δ and 2¹Δ states are studied for the first time. Transition dipole moment, Franck–Condon factors q_υ′υ^″ and Einstein coefficients A_υ′υ^″ for A¹Σ⁺–X¹Σ⁺, 2¹Π–B¹Π, c³Σ⁺–a³Σ⁺ and b³Π–a³Σ⁺ systems have been calculated. Radiative lifetime of A¹Σ⁺–X¹Σ⁺ band system has also been determined.