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.     

Effects on spectroscopic parameters of several low-lying electronic states of GeS by core-valence correlation and relativistic corrections

The potential energy curves (PECs) of six low-lying electronic states (X¹Σ⁺, a³Σ⁺, b³Π, A¹Π, 1³Σ⁻ and 1⁵Σ⁺) of GeS molecule have been investigated employing the full valence complete active space self-consistent field (CASSCF) method followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach with large correlation-consistent basis sets for internuclear separations from 0.08 to 2.00 nm. The effects on the spectroscopic parameters by the core-valence correlation, relativistic and nonadiabatic corrections have been discussed in detail. The core-valence correlation correction is carried out at the aug-cc-pCVTZ basis set. The nonadiabatic correction is performed at the aug-cc-pVTZ basis set. And the relativistic correction is made at the level of cc-pV5Z basis set. The way to consider the relativistic correction is to employ the second-order Douglas-Kroll Hamiltonian (DKH2) approximation. To obtain more reliable PECs, the Davidson modification is also included in the present study. To reduce the incomplete basis set error, the PECs of these electronic states are extrapolated to the complete basis set (CBS) limit. With these PECs, the spectroscopic parameters of these low-lying electronic states are determined. On the one hand, analyses demonstrate that the effects on the spectroscopic parameters by the core-valence correlation correction, relativistic correction and Davidson modification are very obvious, whereas the effect on the spectroscopic parameters by the nonadiabatic correction is very small. On the other hand, comparison with the RKR data shows that the two-point total-energy extrapolation could improve the quality of spectroscopic parameters. On the whole, as expected, the most accurate spectroscopic parameters of GeS molecule are determined by the MRCI+Q/CV+DK+Q5 calculations.     

Effects on spectroscopic properties for several low-lying electronic states of CS molecule by core-valence correlation and relativistic corrections

The potential energy curves (PECs) of six low-lying electronic states (X¹Σ⁺, a³Π, a′³Σ⁺, d³Δ, e³Σ⁻ and A¹Π) of CS molecule have been investigated 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 with large correlation-consistent basis sets. Effects on the PECs by the core-valence correlation and relativistic corrections have been taken into account. And the two corrections are performed at the level of cc-pV5Z basis set. The way to consider the relativistic corrections is to use the second-order Douglas-Kroll Hamiltonian approximation. Using the CCSD(T), MRCI and MRCI with the Davidson modification (MRCI + Q), the PECs of electronic states involved are extrapolated to the complete basis set (CBS) limit. With the PECs, the spectroscopic parameters (T_e, R_e, ω_e, ω_ex_e, ω_ey_e, α_e, β_e, γ_e and B_e) of the six low-lying electronic states are determined. These parameters are in excellent agreement with the experimental data. The complete vibrational states are computed for the six low-lying electronic states when the rotational quantum number J equals zero, and the inertial rotation constants of the first 23 vibrational states are reported, which agree favorably with the RKR data. Comparison with the measurements shows that the two-point total-energy extrapolation scheme can obviously improve the quality of spectroscopic parameters and molecular constants.     

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.     

Multireference configuration interaction study on spectroscopic properties of low-lying electronic states of As2 molecule

The potential energy curves (PECs) of four electronic states (X1Σ+g , e3△u , a 3 Σ-u , and d 3Πg ) of an As 2 molecule are investigated employing the complete active space self-consistent field (CASSCF) method followed by the valence internally contracted multireference configuration interaction (MRCI) approach in conjunction with the correlation-consistent aug-cc-pV5Z basis set. The effect on PECs by the relativistic correction is taken into account. The way to consider the relativistic correction is to employ the second-order Douglas-Kroll Hamiltonian approximation. The correction is made at the level of a cc-pV5Z basis set. The PECs of the electronic states involved are extrapolated to the complete basis set limit. With the PECs, the spectroscopic parameters (Te , Re , ωe , ωexe , ωeye , αe , βe , γe , and Be ) of these electronic states are determined and compared in detail with those reported in the literature. Excellent agreement is found between the present results and the experimental data. The first 40 vibrational states are studied for each electronic state when the rotational quantum number J equals zero. In addition, the vibrational levels, inertial rotation and centrifugal distortion constants of d 3Πg electronic state are reported which are in excellent agreement with the available measurements. Comparison with the experimental data shows that the present results are both reliable and accurate.     

The rotational spectrum of BiO radical in its X1Π1/2 and X2Π3/2 states

Rotational spectra have been observed for BiO produced in a DC discharge through a low pressure mixture of O₂, Ar, and Bi vapor. Because of the highly non-thermal distribution of states, it has been possible to observe spectra arising from the X₁²Π_1/2 level up to v = 9 and for the X₂²Π_3/2 level up to v = 5 near 10 538 cm⁻¹. Precise rotational and hyperfine parameters have been determined for the observed states. By using available near infrared (NIR) data in a merged fit, the 0-0 and 1-1 fine structure intervals have been more precisely determined. Although the quality of the fit is very good, the interpretation of the hyperfine constants is complicated by relativistic effects and the interaction of the X₂ state with A₁⁴Π_3/2 state. The magnetic and quadrupole coupling constants will be compared with those of the Bi atom and related molecules.     

On the high resolution spectroscopy and intramolecular potential function of SO2

Two weak stretching bands, ν₁ + 3ν₃ and 3ν₁ + ν₃, of the sulfur dioxide molecule have been recorded at high resolution and analyzed for the first time with using a Fourier transform Bruker IFS-120 HR interferometer. About 1000 transitions with J^max. = 51, , and 900 transitions with J^max. = 53, have been assigned to the bands ν₁ + 3ν₃ and 3ν₁ + ν₃, respectively. Analysis of the recorded spectra was made using the model of isolated vibrational states. Parameters obtained from the fit reproduce the initial experimental ro-vibrational energies with the rms deviation of 0.0006 and 0.0012 cm⁻¹ for the bands, 3ν₁ + ν₃ and ν₁ + 3ν₃, respectively. The problem of determination of the intramolecular potential function of SO₂ is discussed.     

The optical properties of Dy-doped NaY(MoO4)2 crystal

The Dy³⁺-doped NaY(MoO₄)₂ single crystals were grown successfully by the Czochralski technique. The main spectroscopic properties (absorption, luminescence, decay curve) of Dy³⁺-doped NaY(MoO₄)₂ have been determined for both the σ and π polarizations. By using the Judd-Ofelt theory, the measured room temperature absorption spectra were applied to determine the intensity parameters, spontaneous transition probabilities, branching ratios, and radiative lifetimes of Dy³⁺ transitions. The results show that the Dy³⁺-doped NaY(MoO₄)₂ crystal may realize the yellow laser operation.     

Phase stability and electronic structure of Si2Sb2Te5 phase-change material

On the basis of an ab initio computational study, the present work provide a full understanding on the atomic arrangements, phase stability as well as electronic structure of Si₂Sb₂Te₅, a newly synthesized phase-change material. The results show that Si₂Sb₂Te₅ tends to decompose into Si₁Sb₂Te₄ or Si₁Sb₄Te₇ or Sb₂Te₃, therefore, a nano-composite containing Si₁Sb₂Te₄, Si₁Sb₄Te₇ and Sb₂Te₃ may be self-generated from Si₂Sb₂Te₅. Hence Si₂Sb₂Te₅ based nano-composite is the real structure when Si₂Sb₂Te₅ is used in electronic memory applications. The present results agree well with the recent experimental work.     

Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides

We have investigated the geometric and electronic structures of the cerium oxide (CeO₂)-titanium dioxide (TiO₂) mixed oxides with various Ce/TiO₂ weight ratios prepared by the sol-gel method in detail by means of X-ray diffraction (XRD), high-resolution X-ray photoelectron spectroscopy (XPS), Raman spectroscopy excited by 325 and 514.5 nm lasers, and scanning electron microscope (SEM). Existence of cerium effectively inhibits the phase transition of TiO₂ from the anatase phase to the rutile phase. XRD peaks of TiO₂ anatase attenuate continuously with the increasing amount of CeO₂ in the mixed oxide, but the XRD peaks of cubic CeO₂ appear only after the weight ratio of Ce/TiO₂ reaches 0.50. The average crystalline sizes of TiO₂ anatase and cubic CeO₂ in CeO₂-TiO₂ mixed oxides are smaller than those in the corresponding individual TiO₂ anatase and cubic CeO₂. Raman spectroscopy excited by the 514.5 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.70 whereas Raman spectroscopy excited by the 325 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.90. XPS results demonstrate that Ti exists in the form of Ti⁴⁺ in the CeO₂-TiO₂ mixed oxide. Ce is completely in the form of Ce³⁺ in the mixed oxides with a 0.05 weight ratio of Ce/TiO₂. With the increasing weight ratio of Ce/TiO₂, Ce⁴⁺ dominates. On basis of these results, we proposed that CeO₂ initially nucleates at the defects (oxygen vacancies) within TiO₂ anatase, forming an interface bridged with oxygen between CeO₂ and TiO₂ anatase. At the interface, Ce species cannot substitute Ti⁴⁺ in the lattice of TiO₂ anatase whereas Ti⁴⁺ can substitute Ce⁴⁺ in the lattice of cubic CeO₂. The decreasing concentration of oxygen vacancies, the Ti-O-Ce interface, and the decreasing average crystalline size of TiO₂ anatase act to inhibit the phase transformation of TiO₂ anatase. With the increasing amounts of CeO₂, the CeO₂ clusters continuously grow and form cubic CeO₂ nanocrystals. Spectroscopic results strongly demonstrate that the surface region of CeO₂-TiO₂ mixed oxide is enriched with TiO₂.     

Structure and electronic properties of Hn@C20 molecule

Density functional theory has been employed to optimize the structure of endohedral doped C₂₀ fullerene. We have also investigated electronic properties. We have found that C₂₀ cage can accommodate up to 8 hydrogen atoms. Some hydrogen atoms get chemisorbed on the inner surface of C₂₀ cage and form C-H bond. Structural deformation is found to increase with increase in H-atoms. From the analysis of electronic properties, we observe that due to endohedral doping of hydrogen atoms inside C₂₀, H-atoms acquire net negative charge by accepting electrons and fullerene molecules acquire positive charge by donating electrons to H-atoms. For endohedral complexes where H₃ triangular molecule formation takes place, the nature of net charge transfer changes, i.e. fractional electronic charge is transferred from H-atoms to fullerene. C₂₀ doped with odd number of H-atoms should be more reactive compared to the even number case. Most of the present results are similar to those of endohedral C₆₀.     

Growth, thermal and spectroscopic characterizations of BaNd2(MoO4)4 crystal

A new crystal, BaNd₂(MoO₄)₄, has been grown from the flux melt based on Li₂Mo₃O₁₀ by a spontaneous nucleation method. The phase structure of the obtained crystals was determined by X-ray powder diffraction. The result shows that the as-grown crystals are well crystallized and indexed in a monoclinic crystal system with space group B2/b. The specific heat of BaNd₂(MoO₄)₄ crystal at 20 °C is 0.485 J/g K. Absorption and fluorescence spectra were also measured at room temperature. There are several strong and broad absorption peaks from 200 to 1200 nm and three emission transition bands located at 890, 1060, and 1334 nm are detected.     

High-resolution study of some doubly excited vibrational states of PH2D: the ν1+ν2, ν2+ν5, ν2+ν3, and ν2+ν6 bands

The absorption bands ν₁+ν₂, ν₂+ν₃, and ν₂+ν₆ of PH₂D have been recorded for the first time using a high-resolution Bruker 120 HR interferometer, and rotationally analyzed. Some transitions belonging to the very weak band ν₂+ν₅ and enhanced in intensity by strong interactions with the ν₁+ν₂ band were also assigned. Sets of parameters obtained from the fit reproduce experimental line position of the bands ν₁+ν₂ and ν₂+ν₃ with about the experimental accuracy. The residuals of the ro-vibrational energies of the ν₂+ν₆ band are about 10 times larger. Reasons for the poorer reproduction of the latter data are given.     

Spectroscopic characterization of the potential energy functions of Ne2 Rydberg states in the vicinity of the Ne(S0) + Ne(4p′) dissociation limits

The gerade autoionizing Rydberg states of Ne₂ have been studied in the range 162 000-172 000 cm⁻¹ by 1 + 1′ resonant two-photon excitation from the Ne₂ X ground state via different vibrational levels of the Ne₂ C state. A rotationally resolved part of the spectrum allowed the determination of the potential energy functions of two states of 1_g and characters in the vicinity of the Ne(2p⁶¹S₀) + Ne (2p⁵4p′) dissociation limit. The presence of maxima in these potential energy functions is interpreted as originating from a repulsive interaction between the Rydberg electron and the neutral atom.     

High-resolution rotational analysis of HDS: 2ν3, ν2 + 2ν3, 3ν3, and ν2 + 3ν3 bands

High-resolution Fourier transform spectrum of the HD³²S molecule was studied in the region of 5000-9000 cm⁻¹. More than 1600 observed transitions yielded 239, 264, 131, and 116 upper state ro-vibrational energies of the states (002), (012), (003), and (013), respectively. With a Watson-type effective Hamiltonian model, the ro-vibrational parameters of these four upper states were determined by a least-square fitting which can reproduce the ro-vibrational energies close to the experimental accuracy. The relative linestrengths are also discussed.     

Er3+/Yb3+共掺的氟磷酸盐玻璃的光谱性质和热稳定性

研究了Er3+/Yb3+共掺的氟磷酸盐玻璃的光谱性质和热稳定性。应用Judd-Ofelt理论计算了玻璃的三个强度参量Ωｔ (ｔ=2,4,6)，计算了Er3+离子的辐射跃迁几率，荧光支效率和自发辐射几率等光谱参量。 经荧光谱测试发现掺Er3+/Yb3+共掺的氟磷酸盐玻璃的荧光半高宽可达63nm ，应用McCumber理论计算了1.53μｍ处的受激发射截面，可达6.85×10-21 cm2。     

High resolution study of the 6ν1 P-H stretching band of the PHD2 molecule

The high resolution spectrum of a phosphine gas mixture containing PHD₂ was recorded at room temperature in the 12 550-12 770 cm⁻¹ region. A high sensitivity laser photoacoustic spectrometer consisting of a longitudinal resonant cell coupled to a Ti:sapphire ring laser was employed. More than 600 transitions were assigned to the 6ν₁ overtone band of PHD₂ up to J^max=20, K_a^max=6. A Hamiltonian model developed up to the octic centrifugal distortion terms was used. Seven rotational and centrifugal distortion parameters were fitted, the other ones being fixed to their values linearly extrapolated from ν₁ and 2ν₁. The derived parameters reproduce the initial data within the experimental uncertainties. The isolated character of the P-H bond is confirmed.     

Elastic and electronic properties of BeB2 in comparison to superconducting MgB2 and NbB2

A study of the structural, elastic and electronic properties of BeB₂, a promising diboride in view of the lighter mass of Be, has been made using self-consistent Density Functional Theory (DFT). The five independent elastic constants of BeB₂ are predicted for the first time. The elastic behaviour of the compound is compared with those of the superconducting MgB₂ and NbB₂. We also evaluate the electronic structure of BeB₂ in order to obtain further insight into its surprising difference from the superconducting MgB₂.     

Ab initio calculation of electronic transition moments for singlet excited states of the H2 molecule

Ab initio CI electronic dipole transition moments have been calculated for the transitions between singlet states of the hydrogen molecule correlating asymptotically with H(nl)+H(1s) (n=1,2,3). The investigated singlet-singlet transitions include the 30 (n=3) inter-Rydberg transitions and the 32 transitions which may contribute to absorption in the far wings of the Balmer α line of atomic hydrogen perturbed by another hydrogen atom in its ground state. Results are presented for internuclear distances 1.0a₀?R?12a₀. The present results compare well with the previous theoretical calculations available for about half of the transitions treated in the present work. Thirty eight new transitions are presented. Adiabatic potential energies for the and and improved energies for the and states are reported as well.     

Structural and electronic properties of YPd5Al2

We present a study of structural and electronic properties of YPd₅Al₂. Specific-heat measurements reveal a relatively low Sommerfeld coefficient of the electronic contribution γ=4.1 mJ mol⁻¹ K⁻². No superconductivity is found down to 0.4 K. First-principles electronic-structure calculations based on density-functional theory have been performed and have been compared with available experimental structural and electronic data.