Near-Infrared Spectrum (3000-10 000 cm) of 4-Chlorophenol in Solution

The near-infrared spectra (3000-10 000 cm⁻¹) of 4-chlorophenol-OH and 4-chlorophenol-OD are studied at room temperature in carbon tetrachloride. Some data are also reported for 4-bromophenol-OH and 4-bromophenol-OD. The observed absorptions are assigned to overtones or combinations involving the fundamental transitions which have been recently calculated at the B3LYP/6-311++G(df,pd) level (J. Phys. Chem. A104, 11 685 (2000)). The anharmonicities and the harmonic frequencies of the local ν(OH) and ν(CH) modes and the coupling constants for the binary or ternary combinations are obtained. The extinction coefficients of these transitions are discussed. The half-band width of the ν(OH) and ν(CH) vibrations increases with the absorption frequencies. The experimental harmonic frequencies are obtained from the anharmonicity constants. Comparison with the theoretical frequencies indicates that the low scaling factors ranging from 0.950 to 0.960 characterizing the ν(OH) and ν(CH) vibrations can be accounted for by the large anharmonicity of these vibrations. For these vibrations, the ratio of the experimental harmonic frequencies to the computed frequencies is 0.993. This value does not significantly differ from the average scaling factors of 0.987-0.989 obtained for all the other vibrational modes.     

Perpendicular bands of cyclopropane in the 3000 cm−1 region

The ν₈ and ν₂ + ν₉ bands of cyclopropane when studied with high resolution exhibit Q-branches at the band centers. The ζ constants calculated using these measured band spacings are +0.12 for ν₈ and +0.07 for ν₂ + ν₉.     

High-Resolution Study of Strongly Interacting Vibrational Bands of HDO in the Region 7600-8100 cm(-1)

The high-resolution Fourier transform spectrum of the HDO molecule was recorded and analyzed in the region 7600-8100 cm(-1) where the weak vibration-rotation bands 3nu(1) and nu(1) + nu(2) + nu(3) are located. Because of the presence of strong local resonance interactions, transitions belonging to the 3nu(2) + nu(3) and 6nu(2) bands were assigned as well. Spectroscopic parameters of all four bands were estimated, which reproduce initial line positions with accuracy close to experimental uncertainties. Copyright 2000 Academic Press.     

Weak Line Water Vapor Spectrum in the 11 787-13 554 cm Region

Long-pathlength Fourier transform spectra of water vapor recorded previously by Schermaul et al. (J. Mole. Spectrosc.211, 169 (2002)) are analyzed in the range 11 787-13 554 cm⁻¹. Wavenumbers, absolute intensities, and self-broadening coefficients, with associated uncertainties, are presented for 2137 lines. Analysis of these lines using variational linelists has been conducted leading to the assignment of 1906 of the new lines to 23 different upper vibrational states in the 3ν+δ, 4ν, and 4ν+δ polyads, a further 19 lines are ascribed to H₂¹⁸O. Comparisons are made with the HITRAN database.     

Weak Line Water Vapor Spectra in the Region 13 200-15 000 cm

New Fourier transform spectra of water vapor are presented in the range 6500-16 400 cm⁻¹ obtained using pathlengths of up to 800 m and long integration times. These spectra have a significantly higher signal-to-noise than previous measurements in this wavenumber range. Wavenumbers, absolute intensities and self-broadening coefficients, all with associated uncertainties, are presented for 3604 lines in the region 13 200-15 000 cm⁻¹. Analysis of these lines using variational linelists, along with other unassigned lines from previous studies, has been conducted. This leads to 952 new line assignments to transitions involving 35 different vibrational states of H₂¹⁶O. A smaller number of lines are assigned to H₂¹⁸O and H₂¹⁷O.     

The High-Resolution Fourier Transform Spectrum of Dideuterated Methane CH2D2in the Region between 1900 and 2400 cm

The infrared spectrum of doubly deuterated methane CH₂D₂has been recorded in the region from 1900 to 2400 cm⁻¹at almost Doppler-limited resolution by using two high-resolution Fourier transform spectrometers. The vibrational bands observed include 2ν₄, ν₄+ ν₇, 2ν₇, ν₂, ν₈, ν₄+ ν₉, and ν₇+ ν₉, which were analyzed by taking into account Coriolis and Fermi interactions among them and also those with ν₄+ ν₅, ν₃+ ν₇, and ν₅+ ν₇. Most of the centrifugal distortion constants were constrained to appropriate values, while the vibrational term value and three rotational constants in each of the seven excited states were adjusted along with Coriolis and Fermi interaction parameters by the least-squares analysis of the observed spectrum. The vibration–rotation interaction constants α_sthus determined for the ν₂and ν₈states were combined with those of other fundamental states already published to calculate the equilibrium C–H distance.     

Extended Analysis of Line Positions and Intensities of Ozone Bands in the 2900-3400 cm Region

The 2900-3400 cm⁻¹ spectral range is revisited for an accurate determination of line positions and line intensities of the 3ν₃, ν₁+2ν₃, 2ν₁+ν₃, and 3ν₁ bands of ozone. The fit on 4520 rotational energy levels of (012), (111), (210), (130), (003), (102), (201), and (300) vibrational states determined from observed transitions of cold and hot bands in the 2400-3400 cm⁻¹ region with J_max=65 and K_{a max}=20 gives a r.m.s.=7×10⁻⁴ cm⁻¹ and provides a satisfactory agreement between calculated and observed line positions (dimensionless standard deviation is χ=1.44). The set of 2580 line intensities of 7 rovibrational bands has been measured and fitted with a r.m.s.=6.9% (χ=1.2), leading to the determination of transition moment parameters for these bands. Using these parameters we have obtained more precise estimation for the integrated band intensities S(3ν₃)=1.41×10⁻¹⁹, S(ν₁+2ν₃)=1.28×10⁻²⁰, S(2ν₁+ν₃)=7.91×10⁻²¹, S(3ν₁)=4.72×10⁻²² cm⁻¹/mol cm⁻² at 296 K, with a cutoff 2×10⁻²⁶ cm⁻¹/mol cm⁻². The interactions of the tetrad (003)/(102)/(201)/(300) with the (130) state and the tetrad (040)/(012)/(111)/(210) are studied.     

Experimental and Ab Initio Studies of the HDO Absorption Spectrum in the 13 165-13 500 cm(-1) Spectral Region

The HDO absorption spectrum was recorded in the 13 165-13 500 cm(-1) spectral region by intracavity laser absorption spectroscopy. The spectrum (615 lines), dominated by the 2nu(2) + 3nu(3) and nu(1) + 3nu(3) bands, was assigned and modeled leading to the derivation of 196 accurate energy levels of the (103) and (023) vibrational states. Finally, 150 of these levels were reproduced by an effective Hamiltonian involving two vibrational dark states interacting with the (023) and (103) bright states. The rms deviation achieved by variation of 28 parameters is 0.05 cm(-1), compared to an averaged experimental uncertainty of 0.007 cm(-1), indicating the limit of validity of the effective Hamiltonian approach for HDO at high-vibrational excitation. The predictions of previous ab initio calculations of the HDO spectrum (H. Partridge and D. Schwenke, J. Chem. Phys. 106, 4618-4639 (1997)) were extensively used in the assignment process. The particular spectral region under consideration was used to test and discuss the improvements of new ab initio calculations recently performed on the basis of the same potential energy surface but with an improved dipole-moment surface. The improvements concern both the energy levels and the line intensities. In particular, the strong hybrid character of the nu(1) + 3nu(3) band is very well accounted for by the new ab initio calculations. Copyright 2000 Academic Press.     

Infrared Spectra of the OCO and OCO Species of Carbon Dioxide: The Region 500-1500 cm

The effective operator approach is applied to the calculation of the spectra of ¹⁶O¹²C¹⁷O and ¹⁶O¹²C¹⁸O in the far infrared. Using the eigenfunctions of the effective Hamiltonians previously derived for each of these species, parameters of the corresponding effective dipole moment operators have been fitted to more than 400 observed line intensities of cold and hot bands covering the ν₂ and ν₁ spectral regions. New line intensities measurements in the ν₂ band region of ¹⁶O¹²C¹⁸O have been performed. The new observed line intensities have been also included into the corresponding fit. The fittings have been achieved within the experimental errors. A comparison of calculated line parameters with those provided by the HITRAN and GEISA databases is given.     

High-Order Resonance Interactions in HDO: Analysis of the Absorption Spectrum in the 14 980-15 350 cm(-1) Spectral Region

The absorption spectrum of the HDO molecule recorded by intracavity laser absorption spectroscopy in the 14 980-15 350 cm(-1) spectral region was assigned and modeled in the frame of the effective Hamiltonian approach. The spectrum (496 lines) results, mainly, from transitions to the rotational sublevels of the (014) bright state. An important number of transitions involving the (142) and (0 12 0) highly excited bending states could be identified, borrowing their intensities through high-order resonance interactions with the (014) state. An original feature shown by the present analysis is that all the transitions involving unperturbed energy levels of the (014) state are exclusively of A type, while both A- and B-type transitions are observed when the upper states are perturbed by the resonance interactions. One hundred forty-five energy levels of the three interacting states were derived from the spectrum and fitted to the effective rotational Hamiltonian in Pade-Borel approximants form with 29 varied parameters yielding an rms deviation of 0.038 cm(-1). A few energy levels are affected by additional local resonances with perturbers which have been identified. Finally, 48 transitions of the very weak 6nu(1) band were assigned and fitted as an isolated band. Copyright 2000 Academic Press.     

宽波段高分辨率改进型Czerny-Turner成像光谱仪研究

主要针对Czerny-Turner结构在成像光谱仪系统中的应用进行了研究。Czerny-Turner结构主要存在的像差为像散。为了获得了该结构的完善消像散条件,对其进行了理论分析和结构改进。系统的基本结构不变,仍由球面准直镜,平面光栅和球面聚焦镜组成,但在聚焦镜后添加了一个带楔角的柱面镜,该柱面镜解决了子午方向和弧矢方向上存在大像散差的问题,使系统可以在较宽的波段上实现较高的分辨率,同时元件制作成本大大降低。设计了一个工作在可见光波段(380~760 nm)的改进型成像光谱系统,并对设计理论进行了验证。例子成功设计了数值孔径0.05,全视场全波段调制传递函数值在奈奎斯特频率(20 lp·mm-1)下大于0.59的高分辨率成像光谱仪光学系统。这种改进的系统设计理论适用于小型宽波段高分辨率成像光谱仪。     

改进型高分辨率宽波段Schwarzschild成像光谱仪研究

针对Schwarzschild结构在成像光谱仪系统中的应用进行了研究。以Schwarzschild结构的像散分析为基础,获得了该结构的完善消像差条件;之后,对该结构进行了改进,由准直镜和凸面镜,以及凸面镜和聚焦镜分别组成了两个消像散的Schwarzschild结构,从而构成了Schwarzschild成像光谱系统。并给出了这种系统的各个光学参数的计算条件。以一工作波段为340~500 nm的紫外-可见成像光谱系统为例进行了设计,从而对设计理论进行了验证。根据优化理论计算了初始结构最优解并进行光线追迹模拟,成功设计了数值孔径0.125,全视场全波段调制传递函数值在奈奎斯特频率(20 lp·mm-1)下大于0.58的高分辨率成像光谱仪光学系统。这种结构的不同变形分别可以作为Czerny-Turner系统,Ebert-Fastie系统或者Offner系统应用,设计结果也表明这种改进的系统设计理论适用于小型宽波段高分辨率成像光谱仪。     

A High Resolution Study of the Shock Excited Spectrum of Yttrium Oxide

Abstract

The blue-green (B²? X²?) and orange (A²? –X²?) systems of yttrium oxide have been shock excited at temperatures of about 4000°K and photographed at high dispersion (～ 1.2Å/mm) in the first order of a 21 ft. grating spectrograph. The high dispersion shock excited spectra were recorded using multiple exposures and latensification of extremely high speed film. Over 50 new bands have been observed and assigned to specific vibrational transitions for the systems. New molecular constants have been derived from the A, B and X states. Provisional calculations have been made of Franck-Condon factors and r-centroids for the systems appropriate to new constants.     

现代高分辨拉曼光谱仪的配置及应用研究

拉曼光谱分辨率是关系到从光谱中提取出样品结构信息的关键参数,高分辨拉曼光谱能够提供更多、更精细的样品有关信息。在此全面分析了现代高分辨拉曼光谱仪中决定光谱分辨率的各参数,辨析了易于混淆的分辨率和色散度概念。用理论分析和实验结果说明光栅密度与光谱分辨率的关系以及采用高密度光栅增进光谱分辨率所受到的限制、如何利用长焦长光栅增进光谱分辨率而不损害仪器通光效率、入射狭缝宽度对光谱分辨率及灵敏度的影响,在此基础上如何求得一个合理的平衡选择;并且用不同配置的现代新型拉曼光谱仪实验研究了多层硅结构中的应力分布和单壁碳纳米管管径分布,实验结果清晰地佐证了以上分析,并充分说明了拉曼光谱测量中选择分辨率的重要性。     

High resolution Fourier transform spectrum of HDO in the 7500-8200 cm region: revisited

The HDO absorption FT spectrum is recorded and analyzed in the 7500-8200 cm⁻¹ spectral region. The high accuracy ab initio calculation of Schwenke and Partridge was successfully applied for spectrum assignment that resulted in derivation of 508 precise rovibrational energy levels for the (3 0 0), (0 3 1), (1 1 1), (0 6 0), (2 2 0), and (0 0 2) states, with 295 of them being reported for the first time. In particular, eight new energy levels, including the band center at 7914.3170 cm⁻¹, were derived for the highly excited bending (0 6 0) state from transitions borrowing their intensities through local high-order resonance coupling with the (3 0 0) and (0 3 1) states.     

硫化氢在金属-有机骨架材料中吸附与分离的计算模拟

摘 要: 采用优化的DREIDING力场参数,通过巨正则系综蒙特卡洛(GCMC)模拟方法对天然气中的两种气体CH4和H2S在Cu6(BTTC)4(H2O)6·xS (1)和[(CH3)2NH2]3[(Cu4Cl)3(BTTC)8]·yS (2)两种金属有机骨架(MOFs)材料中的吸附与分离性能进行了比较研究.结果证明了聚合物2的吸附量和分离性能相比之下高于聚合物1,且两种材料的吸附机理存在差异,聚合物1中金属Cu和有机基团对于吸附两种气体没有明显的作用,主要分布在小孔道和大孔道;然而聚合物2中H2S和CH4主要吸附在有机基团、金属Cu和-Cl基团周围.则含有-Cl基团的聚合物2展现了优越的吸附能力和稳定性.总而言之,本文获得的结果可以应用于此类研究领域,因此在环境范围中吸附去除污染物可以产生更深层次定性和定量的作用.     

硫化氢在金属-有机骨架材料中吸附与分离的计算模拟

采用优化的DREIDING力场参数,通过巨正则系综蒙特卡洛(GCMC)模拟方法对天然气中的两种气体CH_4和H_2S在Cu_6(BTTC)_4(H_2O)_6·x S(1)和[(CH_3)_2NH_2]_3[(Cu_4Cl)_3(BTTC)_8]·yS(2)两种金属有机骨架(MOFs)材料中的吸附与分离性能进行了比较研究.结果证明了聚合物2的吸附量和分离性能相比之下高于聚合物1,且两种材料的吸附机理存在差异.聚合物1中金属Cu和有机基团对于吸附两种气体没有明显的作用,主要分布在小孔道和大孔道;然而聚合物2中的H_2S和CH_4主要吸附在有机基团、金属Cu和-Cl基团周围.则含有-Cl基团的聚合物2展现了优越的吸附能力和稳定性.总而言之,本文获得的结果可以应用于此类研究领域,因此在环境范围中吸附去除污染物可以产生更深层次定性和定量的作用.     

Wavenumbers,line strengths,and assignments in the Doppler-limited spectrum of formaldehyde from 2700 to 3000 cm−1

The spectrum of H₂CO from 2700 to 3000 cm^?1 has been examined at Doppler-limited resolution using a tunable difference frequency laser spectrometer at Lincoln Laboratory. The wavenumbers and strengths of 4350 absorptions have been determined with an accuracy of 0.001 cm^?1 and 5%, respectively. These data have been incorporated into the analysis of lower-resolution data from Florida State University to assign 72% of the observed absorptions to one of seven bands: ν₃ +ν₄ (a C-type band at 2655 cm^?1), ν₃ + ν₆ (a B-type band at 2719.156 cm^?1), ν₁ (an A-type band at 2782.457 cm^?1), ν₅ (a B-type band at 2843.326 cm^?1), ν₂ + ν₄ (a C-type band at 2905 cm^?1), 2ν₃ (an A-type band at 2999.5 cm^?1) and ν₂ + ν₆ (a B-type band at 3000.066 cm^?1). The band ν₃ + ν₄ has been observed for the first time, and the band center for 2ν₃ has been corrected from a value of 2972 cm^?1 to the value listed above. The effects of strong Fermi and Coriolis resonances on the spectra are discussed.     

High sensitivity ICLAS of H2O in the 12,580-13,550 cm transparency window

High-sensitivity Intracavity Laser Absorption Spectroscopy (ICLAS) is used to measure the high resolution absorption spectrum of H₂¹⁸O between 12,580 and 13,550 cm⁻¹. This spectral region covers the 3v+δ polyad of very weak absorption. Four isotopologues of water (H₂¹⁸O, H₂¹⁶O, H₂¹⁷O, HD¹⁸O) are found to contribute to the observed spectrum. Spectrum analysis is performed with the aid of variational calculations and allowed for assigning 1126 lines belonging to H₂¹⁸O, while only 160 H₂¹⁸O lines are included in the HITRAN-2008 database. Altogether, 823 accurate energy levels of H₂¹⁸O are determined from transitions attributed to 26 upper vibrational states, 438 of them being reported for the first time. New information includes energy levels of four newly observed vibrational states of H₂¹⁸O: (2 4 0), (1 4 1), (0 4 2) and (2 3 1) at 13,167.718, 13,212.678, 13,403.71 and 15,073.975 cm⁻¹, respectively. H₂¹⁸O transitions involving highly excited bending states like (1 6 0), (0 6 1), (0 7 1), (1 7 0), (0 9 0) and even (0 10 0) have been identified as a result of an intensity borrowing from stronger bands via high-order resonance interactions. Thirty-six new energy levels of H₂¹⁷O, present with a 2% relative concentration in our sample, could be determined. The rotational structure of the (0 2 3) state of HD¹⁸O at 13,245.497 cm⁻¹ is also reported for the first time.