EPR of N2− centers in strontium chloride

We report the EPR observation of two different color centers due to N₂^? molecular ions. The signals observed between 4 and 120K are attributed to an N₂^? ion substituting for two chlorines. The model is very similar to the O₂^? ions in the same matrix. Above 120K, thermally activated processes induce a spin-lattice relaxation and smear out the spectra. A simple technique is proposed to measure the activation energy of the reorientation.     

Modeling of N2+ first negative spectra excited by electron impact on N2

Previously published intensity formulas for the calculation of N₂⁺ first negative spectra excited by electron impact on N₂ given by Herzberg and Muntz are generalized and adapted to arbitrary N₂X vibrational temperatures. The formulation includes all the quantities necessary for detailed computer modeling. Despite the refinements, the rotational structure and band profiles generated by the different methods agree to within a few percent at both normal (300°K) and elevated (5000°K) rotational and vibrational temperatures. Discrepancies in published A-values are noted and a recalculated array is given.     

Transition densities between the 01+, 21+, 41+, 02+, 22+, 11− and 31− states in 12C derived from the three-alpha resonating-group wave functions

All the multipole transition densities between the seven T = 0 states in ¹²C are calculated with the use of the microscopic 3α resonating-group wave functions which are obtained by dynamically solving the 3α relative motion with the total antisymmetrization taken into account exactly. The observed elastic and inelastic electron scattering form factors for the transition to the 2₁⁺, 4₁⁺, 0₂⁺, 1₁^?and 3₁^? states are well reproduced with no additional effective charge. The existence of a deformed intrinsic state for the 0₁⁺, 2₁⁺and 4₁⁺states is deduced by the analysis of the transition densities between them which are derived by the weak-coupling-type 3α wave functions; the intrinsic density distribution is illustrated. The monopole density distribution of the 0₂⁺, 2₂⁺ and 1₁^?, states is found to be much longer ranged than that of the 0₁⁺, 2₁⁺ and 4₁⁺ states; the 3₁^? state case is intermediate. On the basis of the transition densities between the 0₁⁺, 2₁⁺, 0₂⁺ and 2₂⁺ states, analysis is made of the transition between the shell-like states and the molecule-like states with a large spatial-structure change. Specific, effective nucleon-nucleon interactions are folded into the transition densities here obtained. The evident dependence of the radial shape of the folded nucleon-¹²C form factors on the choice of the interactions and the multi-step form factors for the excitation of the 0₂⁺, 1₁^? and 3₁^? states are discussed.     

The dissociation pathways of N2+ in intense femtosecond laser fields

Using a neutral N2 beam as target,this paper studies the dissociation of N2+ in intense femtosecond laser fields(45 fs,～1×10 16 W/cm 2) at the laser wavelength of 800 nm based on the time-of-flight mass spectra of N + fragment ions.The angular distributions of N+ and the laser power dependence of N + yielded from different dissociation pathways show that the dissociation mechanisms mainly proceed through the couplings between the metastable states(A,B and C) and the upper excited states of N2+.A coupling model of light-dressed potential energy curves of N+2 is used to interpret the kinetic energy release of N+.     

Deperturbation of the N2+ first negative group B2Σu+-X2Σg+

Twelve bands of the N₂⁺B²Σ_u⁺-X²Σ_g⁺ system, including v_B = 0–6 and v_X = 0–8, are reanalyzed. All effects of B²Σ_u⁺ ～ A²Π_u perturbations are explicitly considered. Despite the use of high precision (0.01 cm^?1) line measurements, no evidence for a perturber other than A²Π_u is obtained. Deperturbed constants for the B²Σ_u⁺ and X²Σ_g⁺ states are derived. The deperturbation is shown to be self-consistent and complete (excluding effects of the C²Σ_u⁺ state) by examining semiempirical relationships of the perturbation matrix elements with the spin-rotation constants of the B and X states and atomic spin-orbit parameters. A number of previous analyses of transitions involving the v_B = 3 and 5 levels are found to be incorrect.     

Vibrational intensity distributions for the various electronic states of O2+, N2+ and CO+ produced by photoionization

The vibrational intensity distributions produced by the process of photoionization are tabulated as a function of wavelength between 745 and 304 Å for all major electronic states of O₂⁺, N₂⁺ and CO⁺. The technique of photoelectron spectroscopy was used with an electron energy analyzer of known luminosity.     

Stereodynamics of the reactions Ne+H2+/Ne+D2+/Ne+T2

The vector correlations between products and reagents for the reactions Ne+H + 2 , Ne+D + 2 , and Ne+T + 2 are calculated by means of the quasi-classical trajectory method on a new potential energy surface constructed by Lü et al. [J. Chem. Phys. 2010 132, 014303]. The polarization-dependent differential cross-sections (2π/σ)(dσ 00 /dω t ), (2π/σ)(dσ 20 /dω t ), (2π/σ)(dσ 22+ /dω t ), and (2π/σ)(dσ 21 /dω t ), and the distributions of P (θ r ), P (φ r ), and P (θ r ,φ r ) are calculated. The isotopic effect, which is associated with the difference in mass factor among the three reactions, is revealed.     

Absolute cross sections of electron attachment to molecular clusters. Part II: Formation of (H2O) N? , (N2O) N? , and (N2) N?

Absolute cross sections σ⁻(E, N) of electron attachment to clusters (H₂O) _N , (N₂O) _N , and (N₂) _N for varying electron energy E and cluster size N are measured by using crossed electron and cluster beams in a vacuum. Continua of σ⁻(E) are found that correlate well with the functions of electron impact excitation of molecules’ internal degrees of freedom. The electron is attached through its solvation in a cluster. In the formation of (H₂O) _N ⁻ , (N₂O) _N ⁻ , and (N₂) _N ⁻ , the curves σ⁻(N) have a well-defined threshold because of a rise in the electron thermalization and solvation probability with N. For (H₂O)₉₀₀, (N₂O)₃₅₀, and (N₂)₂₆₀ clusters at E = 0.2 eV, the energy losses by the slow electron in the cluster are estimated as 3.0 × 10⁷, 2.7 × 10⁷, and 6.0 × 10⁵ eV/m, respectively. It is found that the growth of σ⁻ with N is the fastest for (H₂O) _N and (N₂) _N clusters at E → 0 as a result of polarization capture of the s-electron. Specifically, at E = 0.1 eV and N = 260, σ⁻ = 3.0 × 10⁻¹³ cm² for H₂O clusters, 8.0 × 10⁻¹⁴ cm² for N₂O clusters, and 1.4 × 10⁻¹⁵ cm² for N₂ clusters; at E = 11 eV, σ⁻ = 9.0 × 10⁻¹⁶ cm² for (H₂O)₂₀₀ clusters, 2.4 × 10⁻¹⁴ cm² for (N₂O)₃₅₀ clusters, and 5.0 × 10⁻¹⁷ cm² for (N₂)₂₆₀ clusters; finally, at E = 30 eV, σ⁻ = 3.6 × 10⁻¹⁷ cm² for (N₂O)₁₀ clusters and 3.0 × 10⁻¹⁷ cm² for (N₂)₁₂₅ clusters. Original Russian Text ? A.A. Vostrikov, D.Yu. Dubov, 2006, published in Zhurnal Tekhnicheskoĭ Fiziki, 2006, Vol. 76, No. 12, pp. 1–15.     

Ionic implantation of N2+ in Ni(110) at 300 K

The present work gives results of a preliminary investigation, carried out by SES, AES, LEED and ELS, on the implantation of nitrogen ions in Ni(110) as a function of ion dose and subsequent surface heat treatment at different temperatures. The fine structure in the SES spectrum is the most sensitive to implantation: peaks at 9, 17.5 and 31.5 eV are shifted towards lower energies by E = 1 eV for the first two peaks and 2.8 eV for the last. At high nitrogen doses a disordered layer is observed by LEED. The p(2 × 3) structure is obtained when the crystal is heated to 750 K. The two electron loss peaks of 4.8 and 10 eV arise from an induced electron N_2p level situated 4.8 eV below the Fermi level.     

Theoretical line widths in N2O-N2O and N2O-air collisions

Rotational half-widths have been computed at 220°K, 250°K, 280°K, and 300°K for air-broadened absorption lines of N₂O using the Anderson-Tsao-Curnutte theory. The new results are compared with previously available estimates at 300°K. Self-broadened line widths have also been computed at 300°K; good agreement has been obtained with Goody's data.     

N2- and O2-broadening parameters in the ν3 band of 14N216O

Broadening parameters of lines belonging to the ν₃ band of N₂O in collision with N₂ or O₂ molecules have been measured with a vacuum high-resolution grating spectrometer. The measurements were carried out in the R branch, up to J = 73 at 297 K and up to J = 50 at 195 K. The experimental results are compared with values calculated from two semiclassical theories.     

Microwave spectra of D217O and D218O

Forty lines of the microwave spectra of D₂¹⁷O and D₂¹⁸O have been measured in the region from 8 to 400 GHz and analyzed according to Watson's centrifugal distortion theory. Comparison of the results obtained for D₂¹⁶O, D₂¹⁷O, and D₂¹⁸O demonstrates their internal consistency. The transferability of the parameters according to the isotopic substitution rules is evidence for the validity of the model chosen for the study of the ground state of heavy water.The effective rotational constants deduced from the observed spectra are very close to the values calculated using Oka's second order theory. The values obtained in MHz are:

$\text{A = 456766.9,}\text{B = 218041.0,}\text{C = 144701.5}\text{(D}{}_2{}^{17}\text{O;)}$

$\text{A = 451891.9,}\text{B = 218045.2,}\text{C = 144201.7}\text{(D}{}_2{}^{18}\text{O;).}$

The hyperfine structure of the D₂¹⁷O lines has been analyzed using as a reference the corresponding quadrupole coupling tensor of HD¹⁷O with the appropriate rotation. The values of χ_gg in MHz used for the analysis are:

$\text{x}{}_{\mathrm{\chi \chi }}\text{= - 1.2104,}\text{x}{}_{\mathrm{yy}}\text{= 10.1068,}\text{x}{}_{\mathrm{zz}}\text{= - 8.8964.}$

     

Centrifugal distortion analysis of pure rotational spectra of H216O,H217O,and H218O

Centrifugal distortion analyses based entirely on high-quality infrared data are carried out for the ground vibrational states of H₂¹⁶O, H₂¹⁷O, and H₂¹⁸O. As a result of the analyses, the values of 27 rotation and distortion constants for each species are determined. By using these constants it was possible to improve considerably the accuracy of the literature values for rotational energy levels at high J_τ, especially for H₂¹⁷O and H₂¹⁸O. The experimental values for the energy levels are deduced from the observed rotational transitions constituting the fitted data.     

High-Resolution IR Spectroscopy of the N2O-H2O and N2O-D2O van der Waals Complexes

We report high-resolution infrared vibrational-rotational spectra of the weakly bound complexes N₂O-H₂O and N₂O-D₂O in the higher frequency N₂O stretching mode region (ν₃=2223.756693(124) cm⁻¹). The measurements were carried out using a free jet expansion in combination with a lead salt diode laser spectrometer. Rotational constants, quartic centrifugal distortion constants, and band origins have been derived for both isotopomers. The geometrical structure is determined using isotopic substitution. The deduced structure shows evidence for a second hydrogen bond interaction within the complex. The nonrigidity of the complexes gives rise to an internal rotation of the water molecule around its own C_2v symmetry axis. For N₂O-H₂O, a tunneling splitting arising from this internal motion has been observed in the spectra. According to symmetry considerations, the observed splitting in the spectrum of N₂O-H₂O corresponds to the difference between the tunneling frequencies in the ground and vibrationally excited states.     

Analysis of ν2 of H233S and H234S

We have extended our analysis of the (010) vibrational state of H₂S, this time using Watson's A-reduced Hamiltonian (through P⁸ terms) in the I′ rotational representation. We have determined separate sets of (010) upper state constants for each isotopomer (H₂³²S, H₂³³S, and H₂³⁴S) by fitting the ν₂ spectral lines, keeping the ground state constants fixed to the values determined by Flaud, Camy-Peyret, and Johns. Determinable coefficients for H₂³²S and a slightly revised set of ν₂ line assignments for H₂³³S and H₂³⁴S are also reported.     

N2- and O2-broadening coefficients and profiles for millimeter lines of N2O

For the purpose of atmospheric applications, we have measured N₂- and O₂-induced broadenings and shapes of rotational lines of N₂O in the 235-350 K temperature range, precisely the J=8←7, J=22←21, and J=23←22 lines, located near 201, 552, and 577 GHz, respectively. The analysis of experimental lineshapes shows up significant deviations from the Voigt profile, which are characteristic of line narrowing processes. In a first step, the Voigt profile was considered for the determination of pressure broadening parameters and of their temperature dependencies. Results are in good agreement with the dependence from rotational quantum number previously observed for other rotational and rovibrational lines. They are well explained by calculations based on a semiclassical formalism that includes the atom-atom Lennard-Jones potential in addition to electrostatic interactions up to hexadecapolar contributions. In a second step, observed lineshapes were analyzed by using the Galatry profile and a speed-dependent Voigt profile. The nonlinear pressure behavior observed for the diffusion rate β involved in the Galatry profile leads to rule out the possible role of velocity/speed changing collisions, and to infer that discrepancies from the Voigt profile result from the dependence of relaxation rates on molecular speeds. This interpretation is supported by the comparison of optical and kinetic radii and confirmed by theoretical calculations of relaxation rates. Finally, it can be claimed that, for the N₂O-N₂ and N₂O-O₂ systems, deviations from the Voigt profile are explained by a speed-dependent Voigt profile.     

A precise study of the rotational spectrum of formaldehyde H212C16O,H213C16O,H212C18O,H213C18O

The rotational spectra of formaldehyde, H₂¹²C¹⁶O and its isotopic species H₂¹³C¹⁶O, H₂¹²C¹⁸O, and H₂¹³C¹⁸O have been investigated in the ground vibrational state in the frequency region between 8 and 460 GHz. For most cases in which measurements of the a-type R- and Q-branch transitions already existed the accuracy of the line position has been improved to about 10 kHz. For H₂¹²C¹⁶O and H₂¹³C¹⁶O a large number of ΔK_a = ±2 transitions were measured with similar accuracy. These new data when combined with all other available data and appropriate weightings lead to a set of ground state parameters which for the first time are compatible with infrared and ultraviolet data. The rotational constants (and 3σ standard deviations) obtained using Watson's A-reduced Hamiltonian are:

     

18.

X-ray spectroscopic studies of the electronic structure of the oxyanions NO ₂⁻, NO ₃⁻ and CO ₃²⁻     

N. Kosuch  E. Tegeler  G. Wiech  A. Faessler 《Journal of Electron Spectroscopy and Related Phenomena》1978,13(3):263-272

Using synchrotron radiation for excitation, the K-emission spectra of nitrogen and oxygen in NO ₂^? and NO ₃^?, and of carbon and oxygen in CO ₃^2? were measured. The X-ray spectra together with available photoelectron spectra permit a precise positioning of the occupied orbitals of the anions. The intensities of the X-ray spectra provide information on the atomic orbital composition. In general the agreement between the experimental results and those of MO-calculations is satisfactory; in some cases, however, there are considerable discrepancies.     

19.

Measurements and theoretical calculations of N₂-broadening and N₂-shift coefficients in the ν₂ band of CH₃D     

Adriana Predoi-Cross  Kyle Hambrook  Jean-Pierre Bouanich 《Journal of Molecular Spectroscopy》2006,235(1):35-53

In this paper, we report measured Lorentz N₂-broadening and N₂-induced pressure-shift coefficients of CH₃D in the ν₂ fundamental band using a multispectrum fitting technique. These measurements were made by analyzing 11 laboratory absorption spectra recorded at 0.0056 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectra were obtained using two absorption cells with path lengths of 10.2 and 25 cm. The total sample pressures ranged from 0.98 to 402.25 Torr with CH₃D volume mixing ratios of 0.01 in nitrogen. We have been able to determine the N₂ pressure-broadening coefficients of 368 ν₂ transitions with quantum numbers as high as J″ = 20 and K = 16, where K″ = K′ ≡ K (for a parallel band). The measured N₂-broadening coefficients range from 0.0248 to 0.0742 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported N₂-induced pressure-shift coefficients vary from about −0.0003 to −0.0094 cm⁻¹ atm⁻¹. We have examined the dependence of the measured broadening and shift parameters on the J″, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = −J″, J″, and J″ + 1 in the ^QP-, ^QQ-, and ^QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.7%. The N₂-broadening and pressure-shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are in good overall agreement with the experimental data (8.7%). The N₂-pressure shifts whose vibrational contribution is derived from parameters fitted in the ^QQ-branch of self-induced shifts of CH₃D, are also in reasonable agreement with the scattered experimental data (20% in most cases).     

20.

Band intensities of the second positive system of N₂     

Rosalino Lorenzo  José Campos 《Journal of Molecular Spectroscopy》1982,92(1):85-90

Experimental branching ratios for 41 bands of the second positive system of N₂ are given. The variation of the electronic transition moment with internuclear separation was studied by using the r-centroid approximation. The result is $\text{R}{}_{\mathrm{<mtext>e</mtext>}}\text{(r) ～ 1 ? 1.4866r + 0.580r}{}^2\text{(r}\text{in}\text{A}\text{?}\text{)}$.     

	H212C16O	H213C16O	H212C18O	H213C18O
A/MHz	281 970.572 (24)	281 993.258(135)	281 961.94 (39)	281 985.00 (93)
B/MHz	38 836.0456(13)	37 811.0887(25)	36 904.1693(66)	35 859.256(10)
C/MHz	34 002.2034(12)	33 213.9790(25)	32 511.5311(63)	31 697.868(10)

X-ray spectroscopic studies of the electronic structure of the oxyanions NO 2−, NO 3− and CO 32−

Using synchrotron radiation for excitation, the K-emission spectra of nitrogen and oxygen in NO ₂^? and NO ₃^?, and of carbon and oxygen in CO ₃^2? were measured. The X-ray spectra together with available photoelectron spectra permit a precise positioning of the occupied orbitals of the anions. The intensities of the X-ray spectra provide information on the atomic orbital composition. In general the agreement between the experimental results and those of MO-calculations is satisfactory; in some cases, however, there are considerable discrepancies.     

Measurements and theoretical calculations of N2-broadening and N2-shift coefficients in the ν2 band of CH3D

In this paper, we report measured Lorentz N₂-broadening and N₂-induced pressure-shift coefficients of CH₃D in the ν₂ fundamental band using a multispectrum fitting technique. These measurements were made by analyzing 11 laboratory absorption spectra recorded at 0.0056 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectra were obtained using two absorption cells with path lengths of 10.2 and 25 cm. The total sample pressures ranged from 0.98 to 402.25 Torr with CH₃D volume mixing ratios of 0.01 in nitrogen. We have been able to determine the N₂ pressure-broadening coefficients of 368 ν₂ transitions with quantum numbers as high as J″ = 20 and K = 16, where K″ = K′ ≡ K (for a parallel band). The measured N₂-broadening coefficients range from 0.0248 to 0.0742 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported N₂-induced pressure-shift coefficients vary from about −0.0003 to −0.0094 cm⁻¹ atm⁻¹. We have examined the dependence of the measured broadening and shift parameters on the J″, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = −J″, J″, and J″ + 1 in the ^QP-, ^QQ-, and ^QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.7%. The N₂-broadening and pressure-shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are in good overall agreement with the experimental data (8.7%). The N₂-pressure shifts whose vibrational contribution is derived from parameters fitted in the ^QQ-branch of self-induced shifts of CH₃D, are also in reasonable agreement with the scattered experimental data (20% in most cases).     

Band intensities of the second positive system of N2

Experimental branching ratios for 41 bands of the second positive system of N₂ are given. The variation of the electronic transition moment with internuclear separation was studied by using the r-centroid approximation. The result is $\text{R}{}_{\mathrm{<mtext>e</mtext>}}\text{(r) ～ 1 ? 1.4866r + 0.580r}{}^2\text{(r}\text{in}\text{A}\text{?}\text{)}$.