Fourier transform emission spectroscopy and ab initio calculations on NbCl

The emission spectrum of NbCl has been recorded in the 3000-20 000 cm⁻¹ region using a Fourier transform spectrometer. The bands were observed by microwave excitation of a mixture of NbCl₅ vapor and He. Two groups of bands observed in the 6500-7000 cm⁻¹ and 9800-11 000 cm⁻¹ regions have been assigned to two electronic transitions. Five bands observed in the 6500-7000 cm⁻¹ region consist of R, P, and Q branches with no combination defect or Λ-doubling. They have been assigned as five sub-bands of a ΔΛ=±1 transition with Λ>1. Nine bands observed in the 9800-11 000 cm⁻¹ regions consist of R and P branches, and they are also free from Λ-doubling. These bands have been classified into four sub-bands of a ΔΛ=0 transition (with Λ>1), which has tentatively been assigned as . The two transitions have no electronic states in common. Ab initio calculations have been performed on NbCl and the spectroscopic properties of the low-lying electronic states have been calculated. The ground state of NbCl has been predicted to be a state arising from the 3σ¹ 1δ² 2π¹ configuration, with a low-lying state at 1300 cm⁻¹ from the 3σ¹ 1δ¹ 2π² configuration. The results of our experimental and theoretical studies will be presented. This work represents the first experimental investigation of the spectra of NbCl and the first ab initio prediction of the spectroscopic properties of the low-lying electronic states.     

Rotational spectra of deuterated acetylenes: DCCH, DCCH and DCCH

Rotational spectra of deuterated acetylenes, DCCH, D¹³CCH and DC¹³CH, have been recorded in the millimeter- and submillimeter-wave frequency ranges. In spite of the small dipole moment (0.01001(15) D), ¹³C-containing species have been observed in natural abundance. The present investigation allowed us to provide improved ground state rotational and quartic centrifugal distortion constants for DCCH, D¹³CCH and DC¹³CH. The experimental investigation has also been supported by ab initio calculations.     

Theoretical investigation of the molecular structure and transition dipole moments of the NaK low lying electronic states

The electronic structure and the spectroscopic constants of the low lying electronic states of the NaK⁺ ionic molecule have been determined through using an ab initio approach involving a non-empirical pseudopotential for the Na and K cores and core valence correlation correction. The potential energy of nearly 26 electronic states of ²Σ⁺, ²Π, and ²Δ symmetries has been calculated up to their dissociation limit Na(4d) + K⁺ and Na⁺ + K(6s). Their spectroscopic constants (R_e, D_e, T_e, ω_e, ω_eχ_e, and B_e) are derived and compared with the few available theoretical studies. A good agreement has been found for the ground state and few excited states with previous works. New potential energy curves were presented, for the first time, for the higher excited states. Numerous avoided crossing between electronic states of ²Σ⁺, ²Π symmetries have been localized and analyzed. Their existences are related to the charge transfer between the two ionic molecules Na⁺K and NaK⁺. Furthermore, we have determined the transition dipole moments for several states and analyzed the avoided crossings related to charge transfer between alkaline atoms.     

High-resolution infrared and ab initio investigation of CHD2 79Br: Ro-vibrational analysis of the ν6 fundamental and the 2ν6−ν6 hot band

The high-resolution infrared spectrum of CHD₂ ⁷⁹Br has been investigated by Fourier transform spectroscopy in the range 540–615?cm^?1 at an unapodised resolution of 0.0035?cm^?1. This spectral region is characterised by the ν₆ fundamental (584.8510?cm^?1), corresponding to C–Br stretching mode, and its hot band 2ν₆?ν₆ (578.4333?cm^?1). The spectral analysis resulted in the identification of 3430 transitions (J’?≤?73 and K'_a ?≤?18) for the ν₆ fundamental and 1212 transitions (J’?≤?49 and K'_a ?≤?11) for the hot band 2ν₆?ν₆. The assigned data have been fitted using the Watson’s S-reduced Hamiltonian in the I^r representation and new constants for the ground state from about 24,600 combination differences and sets of parameters for the v ₆?=?1 and 2 vibrational states have been obtained. From spectral simulations the intensity ratio between 2ν₆?ν₆ and ν₆ has been estimated to be 0.15?±?0.02. High-quality ab initio calculations have also been performed at the CCSD(T) level of theory in order to support the experimental investigation through the calculation of molecular parameters relevant to ro-vibrational spectroscopy.     

铯原子里德堡态Stark能量及电偶极矩的测量和理论计算

里德堡原子由于具有体积大、寿命长、易极化及在外电场中能级易于操控等特点, 已经成为了目前物理学领域研究的热点之一. 本文在磁光阱中实验测量了铯原子15P_3/2和16P_3/2态的Stark光谱,根据光谱给出了15P_3/2和16P_3/2|m|=1/2 Stark态在0-1400 V/cm场强范围适用的Stark 能量和偶极矩的经验性解析表达式; 用数值方法求解薛定谔方程获得了这些态的Stark能量、偶极矩和电子几率密度分布. 电子几率密度分布定性说明了计算的偶极矩矢量的方向是正确的. 计算的Stark能量、偶极矩与实验结果相一致.     

Far-Infrared Laser Stark Spectroscopy of CH3OD

The high resolution Stark spectra of the singly deuterated methanol isotope, CH₃OD, have been studied using the HCN laser with Stark fields up to approximately 60 000 V/cm. Numerous families of absorption lines have been observed in both parallel and perpendicular polarizations, resulting in the following assignments: with the 311 m line – J _K = 18₁ 18₀ E ₂, _t = 1; and with the 337 m line – J _k = 6₄ 5₃ E ₂, _t = 0 and J _K = 14₆ 13₅ A, _t = 1. Zero-field frequencies for the assigned transitions are in agreement with Fourier transform measurements and those calculated from the available molecular constants.     

Microwave spectrum, molecular structure, dipole moment, and theoretical calculation of cyclopentanone oxime

The microwave spectra of cyclopentanone oxime (C₅H₈NOH) and its deuterated species (C₅H₈NOD) were observed in the frequency region from 9 to 40 GHz. Only a-type R-branch transitions were assigned in the vibrational ground and excited states. The rotational constants of normal species were determined to be A = 5870.80(33), B = 1917.021(8), and C = 1526.784(8) MHz in the vibrational ground state, and A = 5870.16(43), B = 1842.707(9), and C = 1479.401(9) MHz for deuterated species. The dipole moments were determined as μ_a = 0.80(10), μ_b = 0.20(10), and μ_c = 0.40(10) D. The ring-puckering vibrational states were observed up to v = 6. The vibrational mode was nearly harmonic. The fundamental frequency of the ring-puckering mode was found to be 70(20) cm⁻¹. The molecular structure of cyclopentanone oxime was determined to be a twisted configuration by comparing the observed and calculated rotational constants, planar moment of inertia, P_cc, and r_s coordinates of the hydroxyl hydrogen atom. On the molecular geometry, the bond angle, C₂C₁N₆ (Fig. 1), is larger than C₅C₁N₆ by ca. 6°, because of the steric repulsion between the methylene group of C₂ atom and hydroxyl group.     

Theoretical study of the electronic states and transition dipole moments of the LiK molecule

The adiabatic potential energy, the spectroscopic constants and the transition dipole moments of the lowest electronic states of the LiK⁺ molecule, dissociating into Li(2s, 2p, 3s, 3p, 3d, 4s, and 4p) + K⁺ and Li⁺ + K(4s, 4p, 5s, 3d, 5p, 4d, and 6s), have been investigated. We have used an ab initio approach involving a non-empirical pseudopotential for the Li (1s²) and K (1s²2s²2p⁶3s²3p⁶) cores and core valence correlation correction. A very good agreement has been obtained for the ground state for the spectroscopic constants with the available theoretical works. The transition dipole moment from X²Σ, 2²Σ, 3²Σ, and 4²Σ states to higher excited states have been determined. Numerous avoided crossing between electronic states of ²Σ and ²Π symmetries, have been localised and analysed. Their existences are related to the charge transfer process between the two ionic systems Li⁺K and LiK⁺.     

Centrifugal distortion analysis of the millimeter-wave spectrum of 2-fluorobenzonitrile and ab initio DFT calculations

The ground state (ν = 0) rotational spectrum of 2-fluorobenzonitrile has been reinvestigated in the frequency range 40.0-99.0 GHz. The millimeter-wave spectrometer used is a source-modulated system combined with a free space glass cell. Millimeter-wave radiation has been produced using a Gunn diode and frequency doubler combination. High J and K₋₁ (J ? 49 and K₋₁ ? 18) transitions have been measured and accurate rotational and centrifugal distortion constants have been determined. Finally, the experimental values were compared with the corresponding values calculated at the HF/DFT-B3PW91/6-31g(d,p) level of theory. A very good agreement has been found.     

Ab initio dipole moment and theoretical rovibrational intensities in the electronic ground state of PH3

We report a six-dimensional CCSD(T)/aug-cc-pVTZ dipole moment surface for the electronic ground state of PH₃ computed ab initio on a large grid of 10 080 molecular geometries. Parameterized, analytical functions are fitted through the ab initio data, and the resulting dipole moment functions are used, together with a potential energy function determined by refining an existing ab initio surface in fittings to experimental wavenumber data, for simulating absorption spectra of the first three polyads of PH₃, i.e., (ν₂, ν₄), (ν₁, ν₃, 2ν₂, 2ν₄, ν₂ + ν₄), and (ν₁ + ν₂, ν₃ + ν₂, ν₁ + ν₄, ν₃ + ν₄, 2ν₂ + ν₄, ν₂ + 2ν₄, 3ν₂, 3ν₄). The resulting theoretical transition moments show excellent agreement with experiment. A line-by-line comparison of the simulated intensities of the ν₂/ν₄ band system with 955 experimental intensity values reported by Brown et al. [L.R. Brown, R.L. Sams, I. Kleiner, C. Cottaz, L. Sagui, J. Mol. Spectrosc. 215 (2002) 178-203] gives an average absolute percentage deviation of 8.7% (and a root-mean-square deviation of 0.94 cm⁻¹ for the transition wavenumbers). This is very remarkable since the calculations rely entirely on ab initio dipole moment surfaces and do not involve any adjustment of these surfaces to reproduce the experimental intensities. Finally, we predict the line strengths for transitions between so-called cluster levels (near-degenerate levels formed at high rotational excitation) for J up to 60.     

Organic compounds in the C3H6O3 family: Microwave spectrum of cis-cis dimethyl carbonate

Geometry optimization calculations on 13 members of the C₃H₆O₃ family of organic species have been carried out to determine their relative binding energies. Dimethyl carbonate [(CH₃)₂CO₃] is one of the lower energy species in this family, which includes the C₃-sugars 1,3-dihydroxyacetone and glyceraldehyde. The microwave spectrum of dimethyl carbonate has been measured over the frequency range 8.4-25.3 GHz with several pulsed-beam Fourier-transform microwave spectrometers and from 227 GHz to 350 GHz with direct absorption spectrometers. The spectrum of the lowest-energy cis-cis conformer of dimethyl carbonate has been assigned, and ab initio electronic structure calculations of the three possible conformers have been performed. Stark effect measurements were carried out on the cis-cis conformer to provide accurate determinations of the dipole moment components.     

New measurements and global analysis of rotational spectra of Cl-, Br-, and I-benzene: Spectroscopic constants and electric dipole moments

The data available from rotational spectroscopy for chlorobenzene, bromobenzene, and iodobenzene have been extended by new measurements in the mm-wave region and in supersonic expansion in the cm-wave region. All available ground state measurements have been combined in global fits to derive precise rotational, centrifugal, and nuclear quadrupole coupling constants for the molecules. Rotational transitions in first excited states of the lowest frequency normal modes in bromobenzene and iodobenzene have been assigned and fitted. The values of electric dipole moments for ³⁵Cl-, ⁷⁹Br-, ⁸¹Br-, and I-benzene have been determined from Stark effect measurements on selected hyperfine components in the supersonic expansion spectrum, and are compared with values for several other series of monohalogen molecules.     

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.     

Rotational spectra, conformational structures, and dipole moments of thiodiglycol by jet-cooled FTMW and ab initio calculations

The rotational spectra of three low-energy conformers of thiodiglycol (TDG) (HOCH₂CH₂SCH₂CH₂OH) have been measured in a molecular beam using a pulsed-nozzle Fourier-transform microwave spectrometer. To determine the likely conformational structures with ab initio approach, conformational structures of 2-(ethylthio)ethanol (HOEES) (CH₃CH₂SCH₂CH₂OH) were used as starting points together with the consideration of possible intramolecular hydrogen bonding in TDG. Three lower-energy conformers have been found for TDG at the MP2=Full/6311G** level and ab initio results agree nicely with experimentally determined rotational constants. In addition, Stark measurements were performed for two of the three conformers for dipole moment determinations, adding to our confidence of the conformational structure matches between experimental observations and ab initio calculations. Of the three lower-energy conformers, one displays a compact folded-like structure with strong hydrogen bonding between the two hydroxyl groups and the central sulfide atom. Two other conformers have relatively open chain-like structures with hydrogen bonding between each of the hydroxyl groups to the central sulfur atom, of which one has pure b-type dipole moment according to the ab initio results.     

An ab initio calculation of O and Si NMR parameters for SiO2 polymorphs

Ab initio molecular orbital calculations (Hartree–Fock, HF and density functional theories, DFTs) have been carried out for SiO₂ polymorphs coesite, low cristobalite, and α-quartz, in order to investigate the reliability of this method for predicting ²⁹Si and ¹⁷O nuclear magnetic resonance (NMR) properties of silicates. Oxygen- and silicon-centered clusters consisting of one (1T) to three tetrahedral (3T) shells (one to four atomic shells), taken from real crystal structure, have been investigated. It is found that for reasonable predication of both the ²⁹Si and ¹⁷O chemical shifts (δ_i^Si and δ_i^O), the minimum cluster is one that gives the correct second neighbors to the nucleus of interest. Both the δ_i^Si and δ_i^O have reached convergence with respect to cluster size at the OH-terminated two tetrahedral (2T) shell (three atomic shells around Si and four atomic shells around O) model. At convergence, the calculated δ_i^Si values agree well (within ±1 ppm) with experimental data. The calculated ¹⁷O electric field gradient (EFG)-related parameters also agree with experimental data within experimental uncertainties. The calculation also reproduces small differences in δ_i^O for O sites with similar tetrahedral connectivities, but shows deviations up to about 10 ppm in relative difference for O sites with different tetrahedral connectivities. The poor performance for the latter is mainly due to the approximations of the HF method. Our study thus suggests that the ab initio calculation method is a reliable mean for predicting ²⁹Si and ¹⁷O NMR parameters for silicates. Such an approach should find application not only to well-ordered crystalline phases, but also to disordered materials, by combining with other techniques, such as the molecular dynamics simulation method.     

The ab initio calculations of the doping Zr's influence on the electronic structure of AlCo2Ti

The electronic structures of the ternary (Hume-Rothery) L2₁-phase compound AlCo₂Ti are calculated by first-principles using full potential linearized augmented plane wave (FLAPW) method with the generalized gradient approximation (GGA). The ab initio results are analyzed with a simplified model for Al-based compounds containing transition metal (TM) atoms. The results show that the total DOS depends strongly on the positions of TM atoms, and the TM d DOS plays a crucial role in hybridization with other element valence electrons. However, the Al 3s states are repelled far away from the Fermi energy in studied sample, and the Al 3d states are far more extended-like in the character than the d states. Furthermore, the total DOS_s are modulated by Al 3p states and the Al 3p states are more sensitive than d states to change in the electronic interactions. Then, the Al 3p is also important for the ternary stability of the intermetallic compound. The Co-Ti interaction becomes stronger by the doping element Zr in the Al₄Co₈Ti₃Zr structure. Especially, the doping Al₄Co₈Ti₃Zr alloy has a larger value DOS at the Fermi level and makes the total DOS gap smaller than the AlCo₂Ti.     

NH2偶极矩的量化计算及多元线性回归的解析处理

采用GAUSSIAN98程序计算了NH2的基态的偶极矩面，采用多元线性回归 的拟合方法，由各项的线性相关性和标准偏差确定各项的取舍，得到具有合理标准偏 差的简单解析偶极矩幂级数表达式。     

Structural,elastic and thermodynamic properties of tetragonal and orthorhombic polymorphs of Sr2GeN2: an ab initio investigation

The structural, elastic and thermodynamic properties of the α (tetragonal) and β (orthorhombic) polymorphs of the Sr₂GeN₂ compound have been examined in detail using ab initio density functional theory pseudopotential plane-wave calculations. Apart the structural properties at the ambient conditions, all present reported results are predicted for the first time. The calculated equilibrium lattice parameters and inter-atomic bond-lengths of the considered polymorphs are in good agreement with the available experimental data. It is found that α-Sr₂GeN₂ is energetically more stable than β-Sr₂GeN₂. The two examined polymorphs are very similar in their crystal structures and have almost identical local environments. The single-crystal and polycrystalline elastic parameters and related properties – including elastic constants, bulk, shear and Young’s moduli, Poisson’s ratio, anisotropy indexes, Pugh’s criterion, elastic wave velocities and Debye temperature – have been predicted. Temperature and pressure dependence of some macroscopic properties – including the unit-cell volume, bulk modulus, volume thermal expansion coefficient, heat capacity and Debye temperature – have been evaluated using ab initio calculations combined with the quasi-harmonic Debye model.     

Raman and infrared spectra,conformational stability,ab initio calculations and vibrational assignment of dimethylsilylisocyanate

The Raman (3200‐30 cm⁻¹) and/or infrared spectra (3500 to 400 cm⁻¹) of gaseous, liquid and solid dimethylsilylisocyanate, (CH₃)₂ Si(H)NCO, have been recorded. The MP2(full) calculations, employing a variety of basis sets with and without diffusion functions, have been used to predict the structural parameters, conformational stability, vibrational fundamental wavenumbers, Raman activities, depolarization values and infrared intensities to support the vibrational assignment. The low wavenumber Raman spectrum of the gas with a significant number of Q‐branches for the SiNC(O) bend is consistent with an essentially linear SiNCO moiety. The ab initio calculations supported this conclusion as all possible orientations of the NCO moiety lead to nearly the same energy. This result is at variance with the conclusion from the electron diffraction study that the heavy atom skeleton was bent with an angle of 152(5)° with one stable cis conformer. It is believed that this reported angle difference from 180° is due to the shrinkage effect. The SiH distance of 1.486 Å has been obtained from the isolated SiH stretching wavenumber. From the adjustment of the ab initio MP2(full)/6‐311+G(d,p) predicted structural parameters, a proposed structure is reported, which is expected to give rotational constants within a few megahertz of the actual ones. These experimental and theoretical results are compared with the corresponding quantities of similar molecules. Copyright © 2009 John Wiley & Sons, Ltd.     

Electronic states of neutral and ionized tetrahydrofuran studied by VUV spectroscopy and ab initio calculations

The electronic spectroscopy of isolated tetrahydrofuran (THF) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 5.8–10.6 eV with absolute cross-section measurements derived. In addition, an electron energy loss spectrum was recorded at 100 eV and 10° over the 5–11.4 eV range. The He(I) photoelectron spectrum was also collected to quantify ionisation energies in the 9–16.1 eV spectral region. These experiments are supported by the first high-level ab initio calculations performed on the excited states of the neutral molecule and on the ground state of the positive ion. The excellent agreement between the theoretical results and the measurements allows us to solve several discrepancies concerning the electronic state spectroscopy of THF. The present work reconsiders the question of the lowest energy conformers of the molecule and its population distribution at room temperature. Electronic supplementary material  Supplementary Online Material