The microwave spectrum,harmonic force field,and structure of formyl chloride

Extensive measurements were made of the microwave spectra of nine isotopic species of formyl chloride, HCOCl. Analysis of these spectra gave accurate rotational constants, chlorine nuclear quadrupole coupling constants, and centrifugal distortion constants. The distortion constants, together with the vibrational wavenumbers, were used to evaluate a valence harmonic force field. Effective, substitution, ground-state average, and estimated equilibrium structures are presented.     

High-order harmonic generation of Li~+ with combined infrared and extreme ultraviolet fields

We investigate high-order harmonic generation(HHG) of Li~+ ion driven by an intense infrared(IR) laser field in combination with a weak XUV pulse. To achieve this, we first construct an accurate single-active electron angular-momentumdependent model potential of Li~+ ion, by which the accurate singlet energy levels of Li~+ for the ground state and excited states with higher quantum numbers can be obtained. Then, we solve numerically the three dimensional time-dependent Schr o¨dinger equation of Li~+ ion by means of the generalized pseudospectral method to obtain HHG. Our results show that the strength of assisted XUV is not amplified during the harmonic generation process, but the yield of HHG power spectrum in the whole plateau has a significant enhancement. Furthermore, the optimal phase delay between the IR and XUV pulses allows the production of ultrabroadband supercontinuum spectra. By superposing some harmonics, a strong new single 27-attosecond ultrashort pulse can be obtained.     

The combined use of SCF-MO calculations and frequency data in the evaluation of general harmonic force fields for molecules containing third row elements

The general harmonic force fields of several small molecules containing third row elements have been evaluated using a semiempirical method which combines SCF-MO calculations and limited frequency data. MOCIC (molecular orbital constraint using interaction coordinates) potential fields have been generated using the SCF-MO MNDO method which has recently been parameterized for third row elements. The general harmonic force field (GHFF) of molecules studied here (SO₂, NOCl, PF₃, PH₃, CCl₄, SiCl₄, SiF₄, SiH₄, and SF₆) are all well defined from spectroscopic data. The MOCIC functions are in excellent agreement with the spectroscopic GHFFs. Comparisons of the MNDO and MOCIC functions show substantial improvement in both primary and interaction valence potential constants when the MOCIC constraint procedure is used.     

The microwave spectrum,harmonic force field,and structure of difluorodichloromethane

Very large numbers of rotational transitions have been accurately measured for ¹²CF₂³⁵Cl₂, ¹²CF₂³⁵Cl³⁷Cl, and ¹³CF₂³⁵Cl₂, and have been analyzed for rotational constants and quartic centrifugal distortion constants. The distortion constants have been combined with vibrational wavenumbers (both from the literature and from the present work), and with ab initio force constants also evaluated in the present work, to give an approximate harmonic force field. The rotational constants and force field have been used to evaluate ground state effective, substitution, and ground state average structures for the molecule.     

The microwave spectrum,harmonic force field,and structure of carbonyl chlorofluoride,OCCIF

Rotational spectra of three isotopic species of carbonyl chlorofluoride, OCCIF, have been extensively measured, and have been analyzed for rotational constants, quartic centrifugal distortion constants, and chlorine nuclear quadrupole coupling constants. Ab initio calculations of the harmonic force field have been made using several different sets of basis functions, and their relative cost efficiency has been assessed. The measured distortion constants have been combined with vibrational wavenumbers (both from the literature and from the present work) and with the ab initio force constants to refine the force field. Ground state effective (r₀) and average (r_z) structures have been evaluated for the molecule.     

原子在双色组合场中产生高次谐波的转换效率与激光波长的关系

利用分裂算符法求解速度规范下的含时薛定谔方程,研究了一维氦原子处于单色红外场、红外场与紫外场形成的双色组合场中产生的高次谐波谱,分析了在截止位置附近高次谐波的转换效率与激光波长(800—2000 nm)的关系,发现在双色组合场驱动下截止位置附近高次谐波的转换效率随波长的变化为η(λ)∝λ^－x,其中〈x〉的数值取决于激光场的强度,但是只要选取合适场强的组合场就能提高截止位置附近高次谐波的转换效率. 关键词： 双色组合场 分裂算符 高次谐波 转换效率     

The microwave spectrum of methylene ketene

The microwave spectrum of methylene ketene has been observed from 8 to 35 GHz and assigned. Rotational constants and centrifugal distortion constants have been determined for CH₂CCO, CHDCCO, and CD₂CCO. The dipole moment was found to be μ_a = 2.14 ± 0.06 D (7.07 ± 0.2 × 10^?30 Cm). We were unable to detect propynal among the pyrolysis products of acrylic anhydride. This pyrolysis proved to be the most convenient route for generating methylene ketene for the present investigation.     

High-resolution infrared study on DCCI: harmonic force field of monoiodoacetylene

A high-resolution infrared spectrum of DCCI has been measured in the regions of the bands of 2ν₁, ν₁+ν₂, ν₂+ν₃, ν₂+ν₄, ν₂+ν₅, and ν₄+ν₅. Using these bands together with the spectra measured previously, the rovibrational states of 2ν₁, ν₁+ν₂, ν₁+ν₃, ν₁+ν₄, ν₁+ν₅, ν₁+2ν₅, ν₂+ν₃, ν₂+ν₄, ν₂+ν₅, ν₂+2ν₅, ν₃+ν₄, ν₄+ν₅, and ν₄+2ν₅ have been analyzed. Various l-type and Fermi resonances have been taken into account in the analysis. In addition, the weak Coriolis resonance between the levels υ₃=υ₄=1 and υ₄=2 has been considered. Accurate values for the molecular constants and the appropriate resonance parameters have been obtained. The unperturbed normal vibrational frequencies associated to the equilibrium state have been calculated for both isotopic species HCCI and DCCI. Then the harmonic force constants for monoiodoacetylene have been determined.     

The microwave spectrum,harmonic force field,and ground state average structure of 1,1-dichloroethylene

The microwave spectra of several isotopic species of 1,1-dichloroethylene have been measured up to high J values and have been analyzed for rotational constants and quartic centrifugal distortion constants. An approximate harmonic force field for the molecule has been obtained by combining the centrifugal distortion constants with known vibrational data. The harmonic force field has been used together with the results of the present and other microwave studies to determine the ground state average molecular structure.     

Ground state spectroscopic constants of isothiocyanic acid,HNCS, from its microwave and millimeter wave spectra combined with far infrared data

The microwave and millimeter wave spectra of isothiocyanic acid, HNCS, in the ground vibrational state have been investigated in the frequency region 8–300 GHz. The a-type R-branch transitions have been assigned up to J = 25 and K_a = 4, and the a-type ^qQ₁ branch transitions up to J = 45. No b-type transitions could be identified in the frequency region covered. The far infrared data reported by Krakow, Lord, and Neely [J. Mol. Spectrosc., 27, 148 (1968)] were combined with our millimeter wave data in order to determine reliable spectroscopic constants. The rotational Hamiltonian, Watson's formalism with S reduction, has been extended empirically to higher order to facilitate the fitting of the large centrifugal distortion effects. The obtained constants are:

$\text{A = 1357.3 GHz; B = 5883.4627 MHz; C = 5845.6113 MHz; D}{}_{\mathrm{J}}\text{= 1.19393 kHz; D}{}_{\mathrm{JK}}\text{= ?1025.37 kHz; D}{}_{\mathrm{K}}\text{= 51.57 GHz; d}{}_1\text{= ?13.781 Hz; d}{}_2\text{= ?4.59 Hz.}$

The ¹⁴N quadrupole coupling constant has also been determined: χ_aa = 1.114 MHz.     

The harmonic force field of methanol

A 28-parameter harmonic force field for methanol is calculated from the matrix frequencies and frequency shifts of ten isotopic species of methanol determined by Barnes and Hallam; Mallinson and McKean; and Serrallach, Meyer, and Günthard. This present force field reproduces the observed harmonic frequencies and frequency shifts far better than either of the two most recent force fields. The presence of a 20 cm^?1 Fermi resonance shift on the lower A′ CH₃ stretching mode deduced in an earlier work is confirmed here.     

Molecular structure and harmonic force field of AsCl3 by microwave spectroscopy

The microwave spectrum of four isotopically substituted species of AsCl₃ in the frequency range 100–220 GHz has been investigated. Four r_s structures were determined resulting in the following average values of the bond length and bond angle:The harmonic force field of AsCl₃ has been calculated and compared with that obtained without the aid of the centrifugal distortion constants.     

Calculation of harmonic force constants from Hartree-Fock-Roothaan wavefunctions

Some current methods of non-empirical computation of force constants are discussed; emphasis is given to the complete, analytical evaluation. It is shown that force constants evaluated to the Hartree-Fock limit are correct through first order in the error of the wavefunction. The consequences of using well-optimized wavefunctions are investigated in some detail. Some of the aspects are illustrated by exploratory calculations on H₂.     

The general harmonic force field of fluoroform

Anharmonicity constants and harmonic frequencies of HC¹²F₃ and DC¹²F₃ are obtained for the first time. These data are combined with ζ^z, ζ^x,y and centrifugal distortion constants and carbon-13 frequency shifts to obtain, using the display method, the general harmonic force field (GHFF) of fluoroform. All 12 force constants in the GHFF, including off-diagonal elements in the A₁ block, are determined with significance. The carbon-13 frequency shifts proved to be most important for precise determination of A₁ off-diagonal elements. The GHFF is compared with the predictions of the Hybrid Orbital Force Field (HOFF).     

The microwave spectra of PH2D and PHD2, and the harmonic force field and structure of phosphine

Measurements of the pure rotational spectra of PH₂D and PHD₂ have been extended to include new Q-branch transitions and R-branch transitions. The rotational constants have been independently evaluated for the first time, along with some quartic and sextic centrifugal distortion constants. The spectrum of PD₃ has been reanalyzed to make the constants consistent with those reported for PH₃. The new results have been incorporated in a harmonic force field analysis. Both ground state average (r₂) and equilibrium (r_e) structures have been estimated.     

Power absorption coefficient constants for water, acetonitrile, and methylene chloride at far infrared wavelengths

The problem of multiple internal reflections within the windows of an optical cell is analysed using Abele's matrix method. The Beer-Lambert power law is modified by the standing waves formed in between the cell and the detector. Power absorption coefficient of a material is calculated by a fit to the modified version of the equation. Precise values for water, acetonitrile and methylene chloride are calculated at far infrared wavelengths using a molecular laser source.     

The harmonic force field and structure of chloryl fluoride

The microwave spectra of three isotopic species of chloryl fluoride, FClO₂, previously published by Parent and Gerry (J. Mol. Spectrosc., 49, 343–364 (1974)), have been refit to rotational constants and centrifugal distortion constants using Watson's Hamiltonian in both its A and S reductions. The quartic distortion constants have been combined with the vibrational data of Smith, Begun, and Fletcher (Spectrochim. Acta, 20, 1763–1770 (1964)) to calculate a refined harmonic force field. The rotational constants and force field have been used to calculate a zero-point average structure and an approximate equilibrium structure. Both the force field and structures are in essential agreement with those published earlier.     

The emprical general harmonic force field of ethane

A total of 175 spectroscopic data, accumulated from 10 isotopic species of ethane, are used to define all 22 parameters of the harmonic potential function within narrow limits. Before calculation, numerous Fermi resonances have been identified and quantified through infrared and Raman spectroscopic studies of CH₃CD₃ and its ¹³C isotopic species. This is an essential prerequisite to such an investigation, without which a self-consistent empirical data set cannot be achieved from which to determine physically meaningful force constants. Comparison of the empirical force constants with those predicted by scaled ab initio calculations shows an excellent degree of correspondence in all force constants, and confirms that both approaches can lead to essentially identical results. Calculated values of spectroscopic data of reliable quality are listed. These should be of value to future spectroscopic investigation of isotopic ethanes and for resolving the many resonance perturbations which are present.     

A combined empirical-ab initio determination of the general harmonic force field of ketene

The general harmonic force field (GHFF) of ketene has been determined through a joint empirical-ab initio investigation. Perturbations in the infrared spectra of all isotopic species render experimental frequency data of limited discriminatory value in the empirical determination. Microwave/infrared determined quartic distortion constants are found to be mutually incompatible, both within and between isotopic species. The sensitivity of the distortion constants to truncation and constraints made in their determination is established in order to make a realistic estimate of their reliability in the force constant calculations. Ab initio calculations performed at various different levels of sophistication predict consistent values for interaction constants, some of which are markedly different from previously reported empirical values. The joint empirical-ab initio GHFF reproduces all observed and perturbation-corrected data well over five isotopic species. Coriolis interaction constants are calculated for ketene-H₂, -HD, and -D₂, which will be of assistance to future analyses, particularly of the strongly interacting four-level systems below 1000 cm⁻¹. Scaled ab initio force constants, calculated around the experimental ground state geometry as reference, are in excellent agreement with the empirical values, with one exception, which arises due to neglect of configuration interaction.