High-resolution Fourier transform spectroscopy of the ν2 and ν3 fundamentals of nitrosyl fluoride,FNO

The ν₂ and ν₃ fundamentals of FNO have been recorded with a Fourier transform spectrophotometer at an apodized resolution of approximately 0.004 cm^?1. The Fourier infrared data have been analyzed together with previous microwave data to yield improved molecular parameters for the (000) and (010) vibrational states and the first set of constants for the (001) state. The main results (in cm^?1) are

     

2.

Fourier transform spectroscopy of the A2Δ-X2II electronic transition of the jet-cooled CCI free radical     

《Journal of Molecular Spectroscopy》1987,124(2):489-493

     

3.

Microwave Fourier transform spectroscopy of rotational and rovibrational transitions in the ν2ν4 dyad of silane-28Si     

《Journal of Molecular Spectroscopy》1986,117(2):435-443

     

4.

A study on the best irradiation dose of X-ray for Hep-2 cells by Fourier transform infrared spectroscopy     

《中国光学快报(英文版)》2008,(5)

Fourier transform infrared spectroscopy (FTIR) was employed to study the human epidermis larynx car- cinoma cell lines (Hep-2) which were irradiated by different doses of X-ray.The results show that (1) the irradiation of X-ray damages the structure of the CH_3 groups of the thymine in DNA,which restrains the reproduction of Hep-2 cells effectively,(2) the 8 Gy dose of X-ray irradiation changes the framework and the relative contents of some proteins,lipids and the nucleic acid molecules intercellular in the greatest degree,and (3) the 8 Gy dose of X-ray irradiation is the best irradiation dose for lowering the degree of the cancerization of Hep-2 cells according to the criteria for the degree of the cancerization reported recently.Meanwhile,the apoptosis of these cells were detected by using flow cytometry (FCM) primarily. It shows that the apoptotic ratio of the Hep-2 cells depends on the irradiation dose to some extent,but is not linearly.And the apoptotic ratio of the 12 Gy dose group is the maximum (20.36%),but the apoptotic ratios of the 2 to 8 Gy dose groups change little.     

5.

High-resolution Fourier transform spectroscopy of D2CO in the 8- to 12-μm region     

《Journal of Molecular Spectroscopy》1987,122(2):462-476

The Coriolis-coupled ν₃ (1100 cm⁻¹), ν₆ (989 cm⁻¹), and ν₄ (938 cm⁻¹) fundamental bands of D₂CO have been recorded with a BOMEM Model DA 3.002 Fourier transform spectrometer at an apodized resolution of 0.004 cm⁻¹. A total of 3704 transitions have been assigned in the 780- to 1200-cm⁻¹ spectral region. Constants have been determined for terms up to P⁶ in centrifugal distortion and up to P³ in Coriolis interaction. These constants reproduce the observed spectra with residuals for well-resolved lines that are less than 0.0004 cm⁻¹, one-tenth of the resolution. Relative signs of the transition moments have been determined by comparison of observed and calculated relative intensities of perturbed transitions. Five new assignments for far-infrared laser lines pumped by CO₂ lasers have been obtained as a result of calculations based on the determined constants.     

6.

High-resolution infrared Fourier transform spectroscopy of SO in the X3Σ− and a1Δ electronic states     

《Journal of Molecular Spectroscopy》1987,124(2):379-392

The v = 1 ← 0 vibration-rotation absorption bands of ³²S¹⁶O, ³⁴S¹⁶O, and ³²S¹⁸O in the ground electronic state, X³Σ⁻, and the v = 1 ← 0 vibration-rotation band of ³²S¹⁶O in the first excited electronic state, a¹Δ, were measured at 0.004 cm⁻¹ unapodized resolution with a high-resolution Fourier transform spectrometer coupled to a long path absorption cell. The v = 2 ← 0 vibration-rotation band of ³²S¹⁶O in the X³Σ⁻ state was also observed. Line positions for P- and R-branch transitions up to N = 44 for ³²S¹⁶O have been measured and analyzed yielding improved molecular parameters. The present measurements are compared with previous infrared and microwave measurements.     

7.

Mass analyzed threshold ionization of hydrogen bonded clusters of biological molecules: the 3-methylindole·C6H6 complex     

《Journal of Electron Spectroscopy and Related Phenomena》2005,142(3):207-213

The mass analyzed threshold ionization (MATI) technique has been used for measuring the adiabatic ionization energy of the 3-methylindole·C₆H₆ cluster (58 018 cm⁻¹) and the binding energies in its ground ionic (4448 cm⁻¹) and ground neutral state (1775 cm⁻¹). We compare our results with those recently obtained for the 3-methylindole·H₂O and the indole·C₆H₆ cluster. The small influence of methylation on the binding energies confirms the πhydrogen bonding character in the 3-methylindole·C₆H₆ complex.     

8.

Comparison of the thermal stability of the α, β and γ phases in poly(vinylidene fluoride) based on in situ thermal Fourier transform infrared spectroscopy     

Anirban Biswas  Karsten Henkel  Dieter Schmeißer 《Phase Transitions》2017,90(12):1205-1213

The electroactive β phase of poly(vinylidene fluoride) (PVDF) is induced due to the aging time of PVDF solutions. The feasibility of the combination of the three crystalline polymorphs (α, β and γ) is demonstrated where their relative proportion within the PVDF film can be tailored by the simple monitoring of the preparation conditions. To identify all these phases, Fourier transform infrared (FT-IR) spectroscopy is carried out and it is spotlighted that the vibrational bands at 510 and 841 cm^?1 are not sufficient to state the formation of the β phase. The main aim of this work is devoted to develop a better understanding on the thermal stability of these several phases of PVDF, which has a longstanding ambiguity persisting in this area. It has been found that the in situ thermal FT-IR spectroscopy is one of the best alternatives to understand this important issue. It is ascertained that the β phase is the least thermally stable phase among α, β and γ phases, whereas the γ phase is the most thermally stable phase.     

9.

Spectroscopic studies of the hydrogen bonded charge transfer complex of 2-aminopyridine with π-acceptor chloranilic acid in different polar solvents     

Khairia M. Al-AhmaryMoustafa M. Habeeb  Eman A. Al-Solmy 《Journal of Molecular Liquids》2011,162(3):129-134

Hydrogen bonded charge transfer complex (HBCT) between 2-aminopyridine (2AP) as electron donor, hydrogen bond acceptor, with chloranilic acid (CHA) as the π-electron acceptor, hydrogen bond donor, has been studied spectrophotometrically in the polar solvents acetonitrile (AN), methanol (MeOH) and ethanol (EtOH). The stoichiometry of the complex has been identified by Job's and photometric titration methods to be 1:1. The Benesi-Hildebrand equation has been applied to estimate the formation constant (K_CT) and molar extinction coefficient (ε). It was found that the value of K_CT is larger in methanol than those in acetonitrile or ethanol. The results were interpreted in terms of Kamlet-Taft α and β solvent parameters. Furthermore, the data were analyzed in terms of standard free energy change (ΔG°), oscillator strength (f), dissociation energy (W), transition dipole moment (μ) and ionization potential (I_P). Also, the solid HBCT-complex was synthesized and characterized by using elemental analysis and FTIR spectroscopy.     

10.

Experimental and theoretical study of the ν(HF) absorption band structure in the H2O…HF complex     

V. P. Bulychev  E. I. Gromova  K. G. Tokhadze 《Optics and Spectroscopy》2004,96(5):774-788

The νHF absorption band shape of the H₂O…HF complex is studied in the gas phase at a temperature of 293 K. The spectra of H₂O/HF gaseous mixtures in the range 4000–3400 cm^?1 are recorded at a resolution of 0.2–0.02 cm^?1 with Bruker IFS-113v and Bruker IFS-120 HR vacuum Fourier spectrometers in a 20-cm cell. The spectra of the H₂O…HF complex in the region of the ν₁(HF) absorption band are obtained by subtracting the calculated spectra of free H₂O and HF molecules from the experimental spectrum. The ν₁ band of the H₂O…HF complex has an asymmetric shape with a low-frequency head, an extended high-frequency wing, and a characteristic vibrational structure. Two approaches are used to calculate the ν1 band shape as a superposition of rovibrational bands of the fundamental and hot transitions involving the low-frequency modes of the complex. The first approach is based on a simplified semiempirical procedure. The second approach relies on a nonempirical anharmonic calculation of the vibrational energy levels, the frequencies and intensities of the corresponding transitions, and the rotational constants. These parameters are obtained by calculating ab initio the potential energy and dipole moment surfaces in the second-order Möller-Plesset approximation and using the variational method to solve one-, two-, and three-dimensional anharmonic vibrational problems. The absorption spectrum of the complex in the range 3600–3720 cm^?1, reconstructed using the nonempirical electro-optical parameters, reproduces rather well the main features of the experimental spectrum, including the relative intensities of peaks of the vibrational structure. However, the interpretation of most of the structural features of the spectrum differs from that adopted in the semiempirical scheme. First of all, it follows from the results of nonempirical calculation that the central, most intense, maximum of the experimental spectrum should correspond to the v ₁=1←0 transition from the ground vibrational state. This fact gives rise to a new value of the vibrational transition frequency ν ₁ ⁰ in the H₂O…HF complex equal to 3635 cm^?1, which is higher than the commonly accepted value of 3608 cm^?1.     

11.

Line strength and collisional broadening studies of hydrogen sulphide in the 1.58 μm region using diode laser spectroscopy     

L. Ciaffoni  B. L. Cummings  W. Denzer  R. Peverall  S. R. Procter  G. A. D. Ritchie 《Applied physics. B, Lasers and optics》2008,92(4):627-633

High resolution diode laser spectroscopy has been applied to the detection of hydrogen sulphide at ppm levels utilizing different transitions within the region of the ν ₁+ν ₂+ν ₃ and 2ν ₁+ν ₂ combination bands around 1.58 μm. Suitable lines in this spectral region have been identified, and absolute absorption cross sections have been determined through single-pass absorption spectroscopy and confirmed in the Doppler linewidth regime using cavity enhanced absorption spectroscopy (CEAS). The desire for a sensitive system potentially applicable to H₂S sensing at atmospheric pressure has led to an investigation on suitable transitions using wavelength modulation spectroscopy (WMS). The set-up sensitivity has been calculated as 1.73×10⁻⁸ cm⁻¹ s^1/2, and probing the strongest line at 1576.29 nm a minimum detectable concentration of 700 ppb under atmospheric conditions has been achieved. Furthermore, pressure broadening coefficients for a variety of buffer gasses have been measured and correlated to the intermolecular potentials governing the collision process; the H₂S–H₂S dimer well depth is estimated to be 7.06±0.09 kJ mol⁻¹.     

12.

High resolution Fourier transform infrared spectroscopy on CH2DI and CHD2I: evaluation of the ground state constants and analyses of the C-I stretching bands ν3     

K. Kyllönen  S. Alanko  J. Lohilahti  V.-M. Horneman 《Molecular physics》2013,111(14-15):1597-1604

Abstract

The high resolution (0.0010cm^?1) Fourier transform infrared spectra of the partially deuterated methyl iodide molecules CH₂DI and CHD₂1 have been recorded and analysed in the ν₃ band regions around 510cm^?1. The fundamental band ν₃ is associated with the stretching of the C-I bond and the spectra appear therefore as an asymmetric rotor hybrid a/b-type band and hybrid a/c-type band for CH₂DI and CHD₂I, respectively. About 4700 transitions in the case of CH₂DI and about 3900 transitions in the case of CHD₂I have been assigned. The ground state rotational constants of CH₂DI and CHD₂I have been obtained using the ground state combination differences calculated from the assigned ν₃ transitions and 16 microwave transitions from literature. The S reduced Watson's Hamiltonian has been used in the calculations. In addition, the upper state parameters describing the v₃=1 vibrational states of these molecules have been determined. The obtained ground state constants as well as the upper state parameters have been compared to the corresponding constants of the symmetric top species CH₃I and CD₃I     

13.

Fourier transform infrared spectra in the regions near 1900 and 700 cm−1 and rovibrational analyses of the ν1ν4 and ν2ν5 fundamentals of unstable H3SnCl,H3SnBr,and H3Snl studied as monoisotopic species     

《Journal of Molecular Spectroscopy》1987,121(1):218-235

     

14.

Infrared spectrum and fourier transform spectroscopy of the 2ν1 band of OCSe: Synthesized by using a heat pipe reactor     

《Journal of Molecular Spectroscopy》1987,124(1):46-52

In order to observe the infrared spectrum of OCSe, a sufficient amount was readily synthesized by using a heat pipe reactor. Thirteen vibrational bands were observed in the region of 400 ∼ 4000 cm⁻¹, seven of which have never been reported. The high-resolution FTIR spectrum of the 2ν₁ band of OCSe was recorded with a resolution of 0.005 cm⁻¹. Analysis provided molecular constants for the 2ν₁ band of ¹⁶O¹²C⁸⁰Se and ¹⁶O¹²C⁷⁸Se in natural abundance.     

15.

Geometry,strength of binding and Br2 charge redistribution in the complex OC ··· Br2 determined by rotational spectroscopy     

E. R. WACLAWIK  J. M. A. THUMWOOD  D. G. LISTER  P. W. FOWLER  A. C. LEGON 《Molecular physics》2013,111(1-2):159-166

The ground-state rotational spectra of the six isotopomers ¹⁶O¹²C ··· ⁷⁹Br⁷⁹Br, ¹⁶O¹²C ··· ⁸¹Br⁷⁹Br, ¹⁶O¹²C ··· ⁸¹Br⁸¹Br, ¹⁶O¹²C ··· ⁷⁹Br⁸¹Br, ¹⁶O¹³C ··· ⁷⁹Br⁷⁹Br, ¹⁶O¹³C ··· ⁸¹Br⁷⁹Br, were observed by pulsed-nozzle, Fourier-transform microwave spectroscopy. The spectroscopic constants B _O, D _J, χ _aa (Br_i), χ _aa (Br_o), M_bb (Br_i) and M _bb (Br_o), where i = inner and o = outer, were determined for each isotopomer. The complex is linear, with the weak bond between the C atom of CO and Br_i. The rotational constants were used to determine the distance r(C ··· Br_i) = 3.1058Å and to show that the Br—Br bond lengthens by ～0.005–0.01Å on complex formation. The intermolecular stretching force constant kσ = 5.0 Nm^?1 was obtained from D_J and the Br nuclear quadrupole coupling constants were interpreted to reveal that a fraction δ = 0.02 of an electronic charge is transferred from Br_i to Br_o when Br₂ is subsumed into the complex. Properties of the two series OC ··· XY and H₃N ··· XY, where XY = C1₂, Br₂ and BrC1, are compared.     

16.

Near infrared diode laser spectroscopy of C2H2, H2O, CO2 and their isotopologues and the application to TDLAS, a tunable diode laser spectrometer for the martian PHOBOS-GRUNT space mission     

G. Durry  J. S. Li  I. Vinogradov  A. Titov  L. Joly  J. Cousin  T. Decarpenterie  N. Amarouche  X. Liu  B. Parvitte  O. Korablev  M. Gerasimov  V. Zéninari 《Applied physics. B, Lasers and optics》2010,99(1-2):339-351

A near-infrared tunable diode laser spectrometer called TDLAS has been developed that combines telecommunication-type as well as new-generation antimonide laser diodes to measure C₂H₂, H₂O, CO₂ and their isotopologues in the near infrared. This sensor is devoted to the in situ analysis of the soil of the Martian satellite PHOBOS, within the framework of the Russian space mission PHOBOS-GRUNT. In the first part of the paper, we report accurate spectroscopic measurements of C₂H₂ and ¹³C¹²CH₂ near 1.533 μm, of H₂O and CO₂ at 2.682 μm and of the isotopologues ¹³C¹⁶O₂ and ¹⁶O¹²C¹⁸O near 2.041 μm and H₂ ¹⁷O, H₂ ¹⁸O and HDO near 2.642 μm. The achieved line strengths are thoroughly compared to data from molecular databases or from former experimental determinations. In the second part of the paper, we describe the TDLAS spectrometer for the PHOBOS-GRUNT mission.     

17.

The high-resolution Fourier transform spectrum of monoisotopic C80Se2 in the ν2, ν3, and ν1 + ν3 regions: Equilibrium,ground, and excited state parameters determined by rovibrational analyses     

《Journal of Molecular Spectroscopy》1988,128(1):221-235

     

18.

Effect of electron-donating and electron-withdrawing atoms on the C–H…Y hydrogen bond in model X3CH…YZ (X = B,F; YZ = BF,CO, N2) complexes     

Sean A. C. McDowell  Kayrel E. K. Edwards 《Molecular physics》2017,115(24):3199-3205

A computational study of model complexes X₃CH…YZ (X = B, F; YZ = BF, CO, N₂) was undertaken to assess the effect of electron-donating and electron-withdrawing X atoms on the properties of the C–H…Y hydrogen bond. Sequential substitution of the B atoms in B₃CH by F atoms to produce F₃CH allowed for the elucidation of interesting trends in the corresponding hydrogen-bonded complexes. The dipole moments and the dipole moment derivative with respect to C–H bond displacement for the proton donors and the chemical hardness of the Y atom of the proton acceptor YZ were found to be useful parameters for understanding these trends. It was found that a positive dipole derivative favours red-shifted hydrogen bonds, whereas a negative dipole derivative favours blue-shifted hydrogen bonds. However, decreasing hardness of Y (which correlates with increasing intermolecular attraction) modifies the interaction such that either greater C–H bond extensions/red shifts or smaller C–H bond compressions/blue shifts are obtained.     

19.

Fundamental and combination bands of CO2–C2H2 and CO2–C2D2 in the mid-infrared region     

M. Rezaei  J. George  L. Welbanks 《Molecular physics》2014,112(18):2445-2450

Spectra of the weakly bound CO₂–C₂H₂ and CO₂–C₂D₂ complexes are observed in the regions of CO₂ ν₃ (≈ 2349 cm^?1) and C₂D₂ ν₃ (≈ 2440 cm^?1) fundamental vibrations, using an infrared optical parametric oscillator to probe a pulsed supersonic slit-jet expansion. Five bands are measured and analysed: the fundamental asymmetric stretch of the C₂D₂ component, two combination bands involving the out-of-plane torsional vibrations (C₂D₂ ν₃ + torsion and CO₂ ν₃ + torsion) for CO₂–C₂D₂, and two combination bands involving an intermolecular in-plane bending vibration for CO₂–C₂H₂ and CO₂–C₂D₂. The resulting intermolecular frequencies are 61.408(1), 54.5(5), 39.9(5), and 39.961(1) cm^?1 for CO₂–C₂H₂ and CO₂–C₂D₂ in-plane vibrations, and CO₂–C₂D₂ out-of-plane torsional vibrations in CO₂ and C₂D₂ regions, respectively. This is the first experimental determination of these intermolecular vibrational frequencies.     

20.

High-resolution infrared spectroscopy of H12C13CD and H13C12CD in the 470–5200 cm−1 spectral region     

Luciano Fusina  Elisabetta Cané  Gianfranco Di Lonardo 《Molecular physics》2013,111(17-18):2321-2325

The fundamental ro-vibrational bands and the 2ν₄?←?GS, 2ν₅?←?GS, 2ν₃?←?GS, ν₄?+?ν₅?←?GS, ν₃?+?ν₄?←?GS, ν₃?+?ν₄?←?ν?₄, ν₃?+?ν₅?←?ν₅, overtone, combination and hot bands of the two rare isotopologues of acetylene H¹²C¹³CD and H¹³C¹²CD have been detected by Fourier transform infrared spectroscopy (FTIR). The analysis of the data has provided very accurate rotational and vibrational parameters for the ground and for the vibrationally excited states.     

	Ground state	$\text{ν}{}_2$	$\text{ν}{}_3$
A	3.1751882 (17)	3.1861249 (12)	3.1958722 (15)
B	0.39508266 (12)	0.39407878 (14)	0.39211484 (14)
C	0.35051504 (11)	0.34899779 (16)	0.34747411 (14)
$\text{ν}{}_0$	0	765.3551 (4)	519.5980 (4)

A study on the best irradiation dose of X-ray for Hep-2 cells by Fourier transform infrared spectroscopy

Fourier transform infrared spectroscopy (FTIR) was employed to study the human epidermis larynx car- cinoma cell lines (Hep-2) which were irradiated by different doses of X-ray.The results show that (1) the irradiation of X-ray damages the structure of the CH_3 groups of the thymine in DNA,which restrains the reproduction of Hep-2 cells effectively,(2) the 8 Gy dose of X-ray irradiation changes the framework and the relative contents of some proteins,lipids and the nucleic acid molecules intercellular in the greatest degree,and (3) the 8 Gy dose of X-ray irradiation is the best irradiation dose for lowering the degree of the cancerization of Hep-2 cells according to the criteria for the degree of the cancerization reported recently.Meanwhile,the apoptosis of these cells were detected by using flow cytometry (FCM) primarily. It shows that the apoptotic ratio of the Hep-2 cells depends on the irradiation dose to some extent,but is not linearly.And the apoptotic ratio of the 12 Gy dose group is the maximum (20.36%),but the apoptotic ratios of the 2 to 8 Gy dose groups change little.     

High-resolution Fourier transform spectroscopy of D2CO in the 8- to 12-μm region

The Coriolis-coupled ν₃ (1100 cm⁻¹), ν₆ (989 cm⁻¹), and ν₄ (938 cm⁻¹) fundamental bands of D₂CO have been recorded with a BOMEM Model DA 3.002 Fourier transform spectrometer at an apodized resolution of 0.004 cm⁻¹. A total of 3704 transitions have been assigned in the 780- to 1200-cm⁻¹ spectral region. Constants have been determined for terms up to P⁶ in centrifugal distortion and up to P³ in Coriolis interaction. These constants reproduce the observed spectra with residuals for well-resolved lines that are less than 0.0004 cm⁻¹, one-tenth of the resolution. Relative signs of the transition moments have been determined by comparison of observed and calculated relative intensities of perturbed transitions. Five new assignments for far-infrared laser lines pumped by CO₂ lasers have been obtained as a result of calculations based on the determined constants.     

High-resolution infrared Fourier transform spectroscopy of SO in the X3Σ− and a1Δ electronic states

The v = 1 ← 0 vibration-rotation absorption bands of ³²S¹⁶O, ³⁴S¹⁶O, and ³²S¹⁸O in the ground electronic state, X³Σ⁻, and the v = 1 ← 0 vibration-rotation band of ³²S¹⁶O in the first excited electronic state, a¹Δ, were measured at 0.004 cm⁻¹ unapodized resolution with a high-resolution Fourier transform spectrometer coupled to a long path absorption cell. The v = 2 ← 0 vibration-rotation band of ³²S¹⁶O in the X³Σ⁻ state was also observed. Line positions for P- and R-branch transitions up to N = 44 for ³²S¹⁶O have been measured and analyzed yielding improved molecular parameters. The present measurements are compared with previous infrared and microwave measurements.     

Mass analyzed threshold ionization of hydrogen bonded clusters of biological molecules: the 3-methylindole·C6H6 complex

The mass analyzed threshold ionization (MATI) technique has been used for measuring the adiabatic ionization energy of the 3-methylindole·C₆H₆ cluster (58 018 cm⁻¹) and the binding energies in its ground ionic (4448 cm⁻¹) and ground neutral state (1775 cm⁻¹). We compare our results with those recently obtained for the 3-methylindole·H₂O and the indole·C₆H₆ cluster. The small influence of methylation on the binding energies confirms the πhydrogen bonding character in the 3-methylindole·C₆H₆ complex.     

Comparison of the thermal stability of the α, β and γ phases in poly(vinylidene fluoride) based on in situ thermal Fourier transform infrared spectroscopy

The electroactive β phase of poly(vinylidene fluoride) (PVDF) is induced due to the aging time of PVDF solutions. The feasibility of the combination of the three crystalline polymorphs (α, β and γ) is demonstrated where their relative proportion within the PVDF film can be tailored by the simple monitoring of the preparation conditions. To identify all these phases, Fourier transform infrared (FT-IR) spectroscopy is carried out and it is spotlighted that the vibrational bands at 510 and 841 cm^?1 are not sufficient to state the formation of the β phase. The main aim of this work is devoted to develop a better understanding on the thermal stability of these several phases of PVDF, which has a longstanding ambiguity persisting in this area. It has been found that the in situ thermal FT-IR spectroscopy is one of the best alternatives to understand this important issue. It is ascertained that the β phase is the least thermally stable phase among α, β and γ phases, whereas the γ phase is the most thermally stable phase.     

Spectroscopic studies of the hydrogen bonded charge transfer complex of 2-aminopyridine with π-acceptor chloranilic acid in different polar solvents

Hydrogen bonded charge transfer complex (HBCT) between 2-aminopyridine (2AP) as electron donor, hydrogen bond acceptor, with chloranilic acid (CHA) as the π-electron acceptor, hydrogen bond donor, has been studied spectrophotometrically in the polar solvents acetonitrile (AN), methanol (MeOH) and ethanol (EtOH). The stoichiometry of the complex has been identified by Job's and photometric titration methods to be 1:1. The Benesi-Hildebrand equation has been applied to estimate the formation constant (K_CT) and molar extinction coefficient (ε). It was found that the value of K_CT is larger in methanol than those in acetonitrile or ethanol. The results were interpreted in terms of Kamlet-Taft α and β solvent parameters. Furthermore, the data were analyzed in terms of standard free energy change (ΔG°), oscillator strength (f), dissociation energy (W), transition dipole moment (μ) and ionization potential (I_P). Also, the solid HBCT-complex was synthesized and characterized by using elemental analysis and FTIR spectroscopy.     

Experimental and theoretical study of the ν(HF) absorption band structure in the H2O…HF complex

The νHF absorption band shape of the H₂O…HF complex is studied in the gas phase at a temperature of 293 K. The spectra of H₂O/HF gaseous mixtures in the range 4000–3400 cm^?1 are recorded at a resolution of 0.2–0.02 cm^?1 with Bruker IFS-113v and Bruker IFS-120 HR vacuum Fourier spectrometers in a 20-cm cell. The spectra of the H₂O…HF complex in the region of the ν₁(HF) absorption band are obtained by subtracting the calculated spectra of free H₂O and HF molecules from the experimental spectrum. The ν₁ band of the H₂O…HF complex has an asymmetric shape with a low-frequency head, an extended high-frequency wing, and a characteristic vibrational structure. Two approaches are used to calculate the ν1 band shape as a superposition of rovibrational bands of the fundamental and hot transitions involving the low-frequency modes of the complex. The first approach is based on a simplified semiempirical procedure. The second approach relies on a nonempirical anharmonic calculation of the vibrational energy levels, the frequencies and intensities of the corresponding transitions, and the rotational constants. These parameters are obtained by calculating ab initio the potential energy and dipole moment surfaces in the second-order Möller-Plesset approximation and using the variational method to solve one-, two-, and three-dimensional anharmonic vibrational problems. The absorption spectrum of the complex in the range 3600–3720 cm^?1, reconstructed using the nonempirical electro-optical parameters, reproduces rather well the main features of the experimental spectrum, including the relative intensities of peaks of the vibrational structure. However, the interpretation of most of the structural features of the spectrum differs from that adopted in the semiempirical scheme. First of all, it follows from the results of nonempirical calculation that the central, most intense, maximum of the experimental spectrum should correspond to the v ₁=1←0 transition from the ground vibrational state. This fact gives rise to a new value of the vibrational transition frequency ν ₁ ⁰ in the H₂O…HF complex equal to 3635 cm^?1, which is higher than the commonly accepted value of 3608 cm^?1.     

Line strength and collisional broadening studies of hydrogen sulphide in the 1.58 μm region using diode laser spectroscopy

High resolution diode laser spectroscopy has been applied to the detection of hydrogen sulphide at ppm levels utilizing different transitions within the region of the ν ₁+ν ₂+ν ₃ and 2ν ₁+ν ₂ combination bands around 1.58 μm. Suitable lines in this spectral region have been identified, and absolute absorption cross sections have been determined through single-pass absorption spectroscopy and confirmed in the Doppler linewidth regime using cavity enhanced absorption spectroscopy (CEAS). The desire for a sensitive system potentially applicable to H₂S sensing at atmospheric pressure has led to an investigation on suitable transitions using wavelength modulation spectroscopy (WMS). The set-up sensitivity has been calculated as 1.73×10⁻⁸ cm⁻¹ s^1/2, and probing the strongest line at 1576.29 nm a minimum detectable concentration of 700 ppb under atmospheric conditions has been achieved. Furthermore, pressure broadening coefficients for a variety of buffer gasses have been measured and correlated to the intermolecular potentials governing the collision process; the H₂S–H₂S dimer well depth is estimated to be 7.06±0.09 kJ mol⁻¹.     

High resolution Fourier transform infrared spectroscopy on CH2DI and CHD2I: evaluation of the ground state constants and analyses of the C-I stretching bands ν3

Abstract

The high resolution (0.0010cm^?1) Fourier transform infrared spectra of the partially deuterated methyl iodide molecules CH₂DI and CHD₂1 have been recorded and analysed in the ν₃ band regions around 510cm^?1. The fundamental band ν₃ is associated with the stretching of the C-I bond and the spectra appear therefore as an asymmetric rotor hybrid a/b-type band and hybrid a/c-type band for CH₂DI and CHD₂I, respectively. About 4700 transitions in the case of CH₂DI and about 3900 transitions in the case of CHD₂I have been assigned. The ground state rotational constants of CH₂DI and CHD₂I have been obtained using the ground state combination differences calculated from the assigned ν₃ transitions and 16 microwave transitions from literature. The S reduced Watson's Hamiltonian has been used in the calculations. In addition, the upper state parameters describing the v₃=1 vibrational states of these molecules have been determined. The obtained ground state constants as well as the upper state parameters have been compared to the corresponding constants of the symmetric top species CH₃I and CD₃I     

Infrared spectrum and fourier transform spectroscopy of the 2ν1 band of OCSe: Synthesized by using a heat pipe reactor

In order to observe the infrared spectrum of OCSe, a sufficient amount was readily synthesized by using a heat pipe reactor. Thirteen vibrational bands were observed in the region of 400 ∼ 4000 cm⁻¹, seven of which have never been reported. The high-resolution FTIR spectrum of the 2ν₁ band of OCSe was recorded with a resolution of 0.005 cm⁻¹. Analysis provided molecular constants for the 2ν₁ band of ¹⁶O¹²C⁸⁰Se and ¹⁶O¹²C⁷⁸Se in natural abundance.     

Geometry,strength of binding and Br2 charge redistribution in the complex OC ··· Br2 determined by rotational spectroscopy

The ground-state rotational spectra of the six isotopomers ¹⁶O¹²C ··· ⁷⁹Br⁷⁹Br, ¹⁶O¹²C ··· ⁸¹Br⁷⁹Br, ¹⁶O¹²C ··· ⁸¹Br⁸¹Br, ¹⁶O¹²C ··· ⁷⁹Br⁸¹Br, ¹⁶O¹³C ··· ⁷⁹Br⁷⁹Br, ¹⁶O¹³C ··· ⁸¹Br⁷⁹Br, were observed by pulsed-nozzle, Fourier-transform microwave spectroscopy. The spectroscopic constants B _O, D _J, χ _aa (Br_i), χ _aa (Br_o), M_bb (Br_i) and M _bb (Br_o), where i = inner and o = outer, were determined for each isotopomer. The complex is linear, with the weak bond between the C atom of CO and Br_i. The rotational constants were used to determine the distance r(C ··· Br_i) = 3.1058Å and to show that the Br—Br bond lengthens by ～0.005–0.01Å on complex formation. The intermolecular stretching force constant kσ = 5.0 Nm^?1 was obtained from D_J and the Br nuclear quadrupole coupling constants were interpreted to reveal that a fraction δ = 0.02 of an electronic charge is transferred from Br_i to Br_o when Br₂ is subsumed into the complex. Properties of the two series OC ··· XY and H₃N ··· XY, where XY = C1₂, Br₂ and BrC1, are compared.     

Near infrared diode laser spectroscopy of C2H2, H2O, CO2 and their isotopologues and the application to TDLAS, a tunable diode laser spectrometer for the martian PHOBOS-GRUNT space mission

A near-infrared tunable diode laser spectrometer called TDLAS has been developed that combines telecommunication-type as well as new-generation antimonide laser diodes to measure C₂H₂, H₂O, CO₂ and their isotopologues in the near infrared. This sensor is devoted to the in situ analysis of the soil of the Martian satellite PHOBOS, within the framework of the Russian space mission PHOBOS-GRUNT. In the first part of the paper, we report accurate spectroscopic measurements of C₂H₂ and ¹³C¹²CH₂ near 1.533 μm, of H₂O and CO₂ at 2.682 μm and of the isotopologues ¹³C¹⁶O₂ and ¹⁶O¹²C¹⁸O near 2.041 μm and H₂ ¹⁷O, H₂ ¹⁸O and HDO near 2.642 μm. The achieved line strengths are thoroughly compared to data from molecular databases or from former experimental determinations. In the second part of the paper, we describe the TDLAS spectrometer for the PHOBOS-GRUNT mission.     

Effect of electron-donating and electron-withdrawing atoms on the C–H…Y hydrogen bond in model X3CH…YZ (X = B,F; YZ = BF,CO, N2) complexes

A computational study of model complexes X₃CH…YZ (X = B, F; YZ = BF, CO, N₂) was undertaken to assess the effect of electron-donating and electron-withdrawing X atoms on the properties of the C–H…Y hydrogen bond. Sequential substitution of the B atoms in B₃CH by F atoms to produce F₃CH allowed for the elucidation of interesting trends in the corresponding hydrogen-bonded complexes. The dipole moments and the dipole moment derivative with respect to C–H bond displacement for the proton donors and the chemical hardness of the Y atom of the proton acceptor YZ were found to be useful parameters for understanding these trends. It was found that a positive dipole derivative favours red-shifted hydrogen bonds, whereas a negative dipole derivative favours blue-shifted hydrogen bonds. However, decreasing hardness of Y (which correlates with increasing intermolecular attraction) modifies the interaction such that either greater C–H bond extensions/red shifts or smaller C–H bond compressions/blue shifts are obtained.     

Fundamental and combination bands of CO2–C2H2 and CO2–C2D2 in the mid-infrared region

Spectra of the weakly bound CO₂–C₂H₂ and CO₂–C₂D₂ complexes are observed in the regions of CO₂ ν₃ (≈ 2349 cm^?1) and C₂D₂ ν₃ (≈ 2440 cm^?1) fundamental vibrations, using an infrared optical parametric oscillator to probe a pulsed supersonic slit-jet expansion. Five bands are measured and analysed: the fundamental asymmetric stretch of the C₂D₂ component, two combination bands involving the out-of-plane torsional vibrations (C₂D₂ ν₃ + torsion and CO₂ ν₃ + torsion) for CO₂–C₂D₂, and two combination bands involving an intermolecular in-plane bending vibration for CO₂–C₂H₂ and CO₂–C₂D₂. The resulting intermolecular frequencies are 61.408(1), 54.5(5), 39.9(5), and 39.961(1) cm^?1 for CO₂–C₂H₂ and CO₂–C₂D₂ in-plane vibrations, and CO₂–C₂D₂ out-of-plane torsional vibrations in CO₂ and C₂D₂ regions, respectively. This is the first experimental determination of these intermolecular vibrational frequencies.     

High-resolution infrared spectroscopy of H12C13CD and H13C12CD in the 470–5200 cm−1 spectral region

The fundamental ro-vibrational bands and the 2ν₄?←?GS, 2ν₅?←?GS, 2ν₃?←?GS, ν₄?+?ν₅?←?GS, ν₃?+?ν₄?←?GS, ν₃?+?ν₄?←?ν?₄, ν₃?+?ν₅?←?ν₅, overtone, combination and hot bands of the two rare isotopologues of acetylene H¹²C¹³CD and H¹³C¹²CD have been detected by Fourier transform infrared spectroscopy (FTIR). The analysis of the data has provided very accurate rotational and vibrational parameters for the ground and for the vibrationally excited states.