Electronic structure of arsabenzene: Microwave spectrum,dipole moment,and nuclear quadrupole coupling constants

The microwave spectrum of arsabenzene was analyzed; a dipole transitions were observed. The following rotational constants were obtained; A = 4871.03 ± 0.18 MHz, B = 2295.87 ± 0.01 MHz, C = 1560.10 ± 0.01 MHz. The dipole moment was 1.10 ± 0.04 D. The nuclear quadrupole coupling constants due to the ⁷⁵As nucleus were χ_aa = ?186.4 ± 0.1 MHz, χ_bb = 43.5 ± 0.2 MHz, χ_cc = 142.9 ± 0.2 MHz, and the asymmetry parameter, η = 0.533 ± 0.002. Analysis of the quadrupole coupling constants indicated that the population of the 4p orbitals on arsenic decrease in the order n_a > n_b > n_c.     

Microwave spectrum,structure, quadrupole coupling constants,dipole moment,and barrier to internal rotation of N-methylhydroxylamine

The microwave spectrum has been observed and analyzed for five isotopic species of N-methylhydroxylamine. For the normal species the rotational constants (in Megahertz) are A = 38 930.771 ± 0.005, B = 3939.607 ± 0.002, and C = 8690.716 ± 0.001. These data show that the molecule exists in the trans conformation, with structural parameters that include the following: CN = 1.460, NO = 1.461, NH = 1.007, and OH = 0.962. Hyperfine structure analyses have yielded the complete inertial axis ¹⁴N quadrupole coupling constant tensor, and thus the tensor values in the electric field-gradient principal axis system as follows: χ_xx = 4.41 ± 0.30, χ_yy = 1.93 ± 0.45, and χ_zz = ?6.34 ± 0.30 MHz. The total electric dipole moment has been found to have the value μ_T = 0.71 D, and the barrier to internal rotation of the methyl group is 3.55 kcal/mole.     

Microwave spectrum,structure, dipole moment,quadrupole coupling constant,and internal motion of thioformamide

The r_s structure of thioformamide has been determined from the microwave spectra of the normal as well as isotopic species of the molecule. The structural parameters obtained assuming the planarity of the molecule are $\text{NH}{}_{\mathrm{c}}\text{= 1.001}{}_8\text{± 0.006}\text{A}\text{?}\text{,}\text{NH}{}_{\mathrm{t}}\text{= 1.006}{}_5\text{± 0.003}\text{A}\text{?}\text{,}\text{CN}\text{= 1.358}{}_2\text{± 0.003}\text{A}\text{?}\text{,}\text{CS}\text{= 1.626}{}_2\text{± 0.002}\text{A}\text{?}\text{,}\text{CH}{}_{\mathrm{a}}\text{= 1.09}{}_6\text{± 0.08}\text{A}\text{?}\text{, ?}\text{H}{}_{\mathrm{c}}\text{NH}{}_{\mathrm{t}}\text{, = 121°42′ ± 40′, ?}\text{H}{}_{\mathrm{c}}\text{NC}\text{= 117°55′ ± 40′, ?}\text{H}{}_{\mathrm{t}}\text{NC}\text{= 120°22′ ± 30′, ?}\text{NCS}\text{= 125°16′ ± 15′ ?}\text{NCH}{}_{\mathrm{a}}\text{= 108°}{}_{\mathrm{5\prime }}\text{± 5°,}\text{and}\text{?}\text{SCH}{}_{\mathrm{a}}\text{= 126°}{}_{\mathrm{39\prime }}\text{± 5°}$.The dipole moment is calculated from the Stark effects of the three transitions to be μ_a = 3.99 ± 0.02 D, μ_b = 0.13 ± 0.25 D, and μ_total = 4.01 ± 0.03 D, where the c component is assumed to be zero.The quadrupole coupling constant of the ¹⁴N nucleus is estimated using the doublet splittings observed for six Q-branch transitions; χ_cc - χ_bb = ?5.39 ± 0.15 MHz and χ_aa = 2.9 ± 1.2 MHz.Two sets of vibrational satellites are observed and assigned to the first excited state of the amino wagging and the NCS bending vibrations, respectively. The relative intensity measurement gives the vibrational energies of 393±40 cm^?1 and 457 ± 50 cm^?1 for NH₂CHS and 293 ± 30 cm^?1 and 393 ± 40 cm^?1 for ND₂CHS. The amino wagging inversion vibration in the molecule is discussed in comparison with that in formamide. It is most probable that the thioformamide molecule is also planar without any potential hump to the amino inversion at the planar configuration.     

The microwave spectrum, structure, chlorine nuclear quadrupole coupling constants, dipole moment, and centrifugal distortion constants of dichlorosilane

The microwave spectra of three isotopic species of dichlorosilane, SiH₂Cl₂, in its ground vibrational state, have been measured in the frequency region 8–40 GHz. The spectra have yielded values for the rotational constants, centrifugal distortion constants, and chlorine nuclear quadrupole coupling constants, as well as the molecular dipole moment, 1.13 ± 0.02 D. The molecule has C_2v symmetry, and the bond lengths and angles r(Si---Cl=2.033±Å, r(Si---H)=1.480±0.015Å, (Cl---Si---Cl)=109°43′±20±, (H---Si---H)=111°18′±40′ The centrifugal distortion constants have been compared with those calculated using a published force field.     

Microwave spectrum,molecular structure,and nuclear quadrupole coupling constants of 3-bromopropene

The microwave spectra of the two ⁷⁹Br and ⁸¹Br isotopic species of 3-bromopropene were measured in the frequency region 14–23 GHz. The R and Q branches for a- and b-type rotational transitions of one conformer, skew, have been assigned and the rotational constants of the ground state have been determined to be A = 19 247.56 MHz, B = 1975.339 MHz, and C = 1914.761 MHz for ⁷⁹Br species, and A = 19 234.26 MHz, B = 1961.417 MHz, and C = 1901.563 MHz for ⁸¹Br species, respectively. By the analysis of the second-order perturbation treatment of the quadrupole interaction, it is found that the χ_ab element of the χ tensor primarily contributes to the anomalous hyperfine splittings. The matrix elements of products of direction cosines in terms of the symmetric top wavefunctions have been derived. The nuclear quadrupole coupling constants have been determined χ_aa = 384.2 MHz, χ_bb = ?71.9 MHz, χ_cc = ?276.3 MHz, and |χ_ab| = 358.7 MHz for ⁷⁹Br species and χ_aa = 283.2 MHz, χ_bb = ?55.6 MHz, χ_cc = ?227.6 MHz, and |χ_ab| = 296.0 MHz for ⁸¹Br species.     

Microwave spectrum,centrifugal distortion constants,and quadrupole coupling constants of 3-chloropyridine

The microwave spectrum of 3-chloropyridine has been measured in the frequency region of 8.2 to 18 GHz. The rotational constants, centrifugal distortion constants, and the quadrupole coupling constants for the ³⁵Cl species are A = 5839.448 ± 0.027 MHz, B = 1604.152 ± 0.005 MHz, C = 1258.327 ± 0.004 MHz, Δ_J = 0.10 ± 0.01 KHz, Δ_JK = 0.36 ± 0.09 KHz, Δ_K = 1.18 ± 0.07 KHz, δ_J = ?0.008 ± 0.005 KHz, δ_K = 0.88 ± 0.20 KHz, χ_aa = ?70.04 ± 0.38 MHz, χ_bb = 36.68 ± 0.19 MHz. The values of rotational constants and quadrupole coupling constants for the ³⁷Cl species are A = 5840.052 ± 0.034 MHz, B = 1559.354 ± 0.01 MHz, C = 1230.739 ± 0.016 MHz, χ_aa = ?54.20 ± 1.26 MHz, χ_bb = 29.49 ± 0.48 MHz. The double bond character in the CCl bond is found to be 2%. The smaller than expected value of rotational constant A points to a “fattening” of the pyridine ring about the a-axis in contrast to 2-chloropyridine, where no such substitution effect was observed.     

Microwave spectrum,conformation, and quadrupole coupling constants of cyclopentyl chloride

The microwave spectra of the normal and two isotopic species of cyclopentyl chloride have been observed and analyzed. For the normal isotopic species the rotational constants (in MHz) are A = 4547.77 ± 0.01, B = 2290.22 ± 0.01, and C = 2073.34 ± 0.01. From the rotational constant data, it has been shown that the stable molecular conformation is the bent axial form. Quadrupole coupling constants have been measured for the ³⁵Cl nucleus, the values being (in MHz) χ_aa = ?23.70 ± 0.10, χ_bb = 32.33 ± 0.36, and χ_cc = ?8.63 ± 0.37. When transformed to the CCl bond axis system, the coupling constants confirm the axial structure. Extensive vibrational satellite structure, presumably arising from the pseudorotational ring mode with a fundamental frequency of 52 ± 5 cm^?1, has been observed and assigned. No spectral evidence has been observed for a second stable molecular conformer.     

Microwave spectrum,conformation, and quadrupole coupling constants of 1-iodopropane

The molecular rotational spectrum of 1-iodopropane (n-propyl iodide) has been investigated in the frequency region 9–33 GHz. The 1-iodopropane molecule has been confirmed to exist in two rotational isomers, trans and gauche. The rotational constants of the ground state were determined to be A = 10 595.450(60) MHz, B = 1781.669(8) MHz, and C = 1614.200(7) MHz for gauche, and B = 1305.247(8) MHz and C = 1269.365(7) MHz for trans. The nuclear quadrupole coupling constants were determined to be χ_aa = −1020(3) MHz, χ_bb = 193(2) MHz, χ_cc = 827(4) MHz, χ_ab = 1173(2) MHz, χ_ac = −369(7) MHz, and χ_bc = 230(5) MHz for gauche, and χ_aa = −1509(8) MHz, χ_bb = 610(9) MHz, χ_cc = 899(12) MHz, and χ_ab = −789(9) MHz for trans. The centrifugal distortion constants were also determined using all of the assigned transitions. From the relative intensity measurements the skeletal torsional frequencies for the gauche and trans forms were estimated to be 117 and 108 cm⁻¹, respectively.     

Microwave spectrum,dipole moment,and structure of 3-aminopropanol

The microwave spectra of 3-aminopropanol and three of its deuterium substituted isotopic species have been investigated in the 26.5 to 40 GHz frequency region. The rotational spectrum of only one conformer has been assigned in which presumably a hydrogen bond of the OH---N type exists. The rotational spectra of a number of excited vibrational states have been observed and assignments made for some of these excited states. The average intensity ratio for the rotational transitions between the ground and excited vibrational states indicates that the first excited state is about 120 cm^?1 above the ground state.and the next higher state is roughly 200 cm^?1 above the ground vibrational state. The dipole moment was determined from the Stark effect measurements to be 3.13 ± 0.04 D with its principal axes components as |μ_a| = 2.88 ± 0.03 D, |μ_b| = 1.23 ± 0.04 D and |μ_c| = 0.06 ± 0.01 D. The possibility of another conformer where the hydrogen bond could be of NH---O type was explored, but the spectra of such a conformer could not be identified.     

Microwave spectrum,quadrupole hyperfine interaction,and electric dipole moment of the BrF molecule

The measurements of the microwave spectrum of BrF were carried out on the hyperfine components of J = 1 ← 0 and J = 2 ← 1 rotational transitions of ⁷⁹BrF and ⁸¹BrF. A direct diagonalization procedure of the energy matrix of the total Hamiltonian including Stark effect has been used. The following constants were derived:

     

14.

Microwave spectra,nuclear quadrupole coupling constants,dipole moments,and rotational isomers of propargylimine     

Masaaki Sugie  Harutoshi Takeo  Chi Matsumura 《Journal of Molecular Spectroscopy》1985,111(1):83-92

The microwave spectra of the short-lived molecule, propargylimine (CHCCHNH), produced by the pyrolysis of dipropargylamine, have been observed. The spectra are analyzed with the aid of an ab initio MO calculation, and the rotational constants for the two isomers (Z- and E-propargylimines) have been determined as A = 54640.228 MHz, B = 4862.4191 MHz, and C = 4458.1986 MHz, and A = 63099.320 MHz, B = 4766.6104 MHz, and C = 4425.5144 MHz, respectively. The dipole moments, the quadrupole coupling constants, and the relative populations between the two isomers have also been obtained.     

15.

Microwave spectrum,structure, dipole moment,and internal rotation of methylpropargylether     

Michiro Hayashi  Jun Nakagawa  Hiroshi Kato 《Journal of Molecular Spectroscopy》1980,84(2):362-374

Microwave spectra of methylpropargylether and its nine isotopically substituted species were measured. The plausible structure of this molecule was determined from the observed moments of inertia. The r_s structural parameters of the OCH₃ part of the molecule could be obtained and were compared with the corresponding parameters of the analogous molecules. The dipole moment and its direction in the molecule were determined by Stark-effect measurements. The barrier to internal rotation of the methyl group was determined from the A-E splittings of the spectra reported by K. M. Marstokk and H. Møllendal (J. Mol. Struct. 32, 191–202 (1976) taking into account the coupling effect of the skeletal torsion.     

16.

Microwave spectrum,structure, dipole moment,and internal rotation of methylsilylsulfide     

《Journal of Molecular Spectroscopy》1987,122(1):1-8

Microwave spectra of methylsilylsulfide and its three isotopically substituted species were measured and their b-type transitions were assigned. The spectra of all the species exhibit doublet structures due to the internal rotation of the methyl group. Using the internal axis method, the potential barriers were determined from the observed A- and E-component frequencies to be 1081.0 ± 3.3, 1073.9 ± 2.0, 1065.1 ± 11.4, and 1076.0 ± 1.9 cal/mol for the normal, CH₃SSiD₃, CD₃SSiH₃, and ¹³CH₃SSiH₃ species, respectively. The analysis also yielded 3°49′ as the tilt angle of the methyl top. From the rotational constants obtained, a plausible structure was estimated. The molecular electric dipole moments were determined from the second-order Stark effect of some A-component transitions with low- J quantum numbers for the normal and SiD₃ species. A comparison of the obtained parameters was made with analogous molecules.     

17.

Microwave spectrum,dipole moment,and structure of anti-vinyl alcohol     

M. Rodler 《Journal of Molecular Spectroscopy》1985,114(1):23-30

The rotational spectra of the anti conformer of vinyl alcohol (ethenol, H₂CCHOH) and its OD modification have been studied by microwave spectroscopy. The compounds have been generated by very-low-pressure pyrolyses of the appropriate isotopic species of 3-thietanol. In both cases the 25 measured μ_a- and μ_b-type transitions allowed the rotational constants and all five quartic centrifugal distortion constants to be determined. Stark effect measurements have yielded the electic dipole moment: μ_a = 0.547(2), μ_b = 1.702(1), and μ = 1.788(1) D. By relative intensity measurements it has been found that the vibrational ground state of the anti conformer lies 4.5±0.6 kJ mol^?1 above the syn conformer. In addition, ab initio calculations at the 6–31G⁷ level have been performed to obtain the structure, relative energy, and dipole moment of both rotamers.     

18.

The microwave spectrum,structure and nuclear quadrupole coupling constants for stibabenzene     

Gerald D Fong  Robert L Kuczkowski  Arthur J Ashe 《Journal of Molecular Spectroscopy》1978,70(2):197-208

The microwave spectrum of 121-SbC₅H₅, 123-SbC₅H₅, β-dideutero 121-SbC₅H₃D₂ and 123-SbC₅H₃D₂ has been assigned in the region 26.5–40.0 GHz. The respective rotational constants and uncertainties are: A = 4512.69 ± 0.42, B = 1738.00 ± 0.01, C = 1254.51 ± 0.01; A = 4512.84 ± 0.30, B = 1729.80 ± 0.01, C = 1250.22 ± 0.01; A = 4176.18 ± 0.33, B = 1660.94 ± 0.01, C = 1188.15 ± 0.01; A = 4176.60 ± 0.61, B = 1652.94 ± 0.03, C = 1184.03 ± 0.03 (in MHz units). The structure is found to be planar, C_2v in symmetry. The $\text{d(}\text{Sb-C}\text{) = 2.050 ± 0.005}\text{A}\text{?}$ and ∠CSbC = 92.9° ± 1.0°. The nuclear quadrupole coupling constants for the 121 and 123 antimony isotopes are χ_aa = 456.4 ± 4.1 MHz, η = 0.396 ± 0.008, and χ_aa = 583.00 ± 5.3 MHz, η = 0.399 ± 0.008, respectively. Several alternate techniques using the coupling constants as data support a σ-donating property for antimony.     

19.

Microwave spectrum and dipole moment of pentafluorobenzene     

S Doraiswamy  S D Sharma 《Pramana》1974,2(4):219-225

With the idea of evaluating the dipole moment of pentafluorobenzene from a lowJ transition, its microwave spectrum was investigated in the frequency region of 8,000 to 12,400 MHz. The spectrum had been earlier observed by the authors in the 12,400 to 18,000 MHz region which needs reassignment in the light of present investigations. The rotational constants areA=1480·856±0·003 MHz,B=1030·066±0·003 MHz andC=607·496±0·002 MHz. The dipole moment is 1·44±0·05 D.     

20.

Microwave spectrum,quadrupole coupling constants,and barrier to internal rotation of 2-iodopropene     

P. Groner  A. Bauder 《Journal of Molecular Spectroscopy》1979,74(2):259-281

The microwave spectrum of 2-iodopropene has been investigated between 7.7 and 18 GHz. The measured transition frequencies of the ground and two vibrationally excited states have been analyzed using direct diagonalization of the rotational and quadrupole Hamiltonian. The following rotational and quadrupole coupling constants have been determined in a leastsquares fit for the ground state: A = 9285.153(20) MHz; B = 2337.2198(14) MHz; C = 1887.5871(14) MHz; and χ_cc = ?1820.783(33) MHz; χ_ab = 147.5(10) MHz; χ_bb = 957.018(41) MHz; and χ_cc = 863.765(40) MHz. The quadrupole coupling constants have been transformed to their principal axis system. From the splittings of some transitions of the first torsionally excited state a value of V₃ = 905(3) cm^?1 has been found for the threefold barrier hindering the internal rotation of the methyl group.     

79BrF

81BrF

Be (MHz) 10 667.610 (60)

10 616.522 (70)

eq0Q (MHz) 1086.80 (30)

908.09 (20)

eq1Q (MHz) 1085.66 (60)

907.41

Microwave spectra,nuclear quadrupole coupling constants,dipole moments,and rotational isomers of propargylimine

The microwave spectra of the short-lived molecule, propargylimine (CHCCHNH), produced by the pyrolysis of dipropargylamine, have been observed. The spectra are analyzed with the aid of an ab initio MO calculation, and the rotational constants for the two isomers (Z- and E-propargylimines) have been determined as A = 54640.228 MHz, B = 4862.4191 MHz, and C = 4458.1986 MHz, and A = 63099.320 MHz, B = 4766.6104 MHz, and C = 4425.5144 MHz, respectively. The dipole moments, the quadrupole coupling constants, and the relative populations between the two isomers have also been obtained.     

Microwave spectrum,structure, dipole moment,and internal rotation of methylpropargylether

Microwave spectra of methylpropargylether and its nine isotopically substituted species were measured. The plausible structure of this molecule was determined from the observed moments of inertia. The r_s structural parameters of the OCH₃ part of the molecule could be obtained and were compared with the corresponding parameters of the analogous molecules. The dipole moment and its direction in the molecule were determined by Stark-effect measurements. The barrier to internal rotation of the methyl group was determined from the A-E splittings of the spectra reported by K. M. Marstokk and H. Møllendal (J. Mol. Struct. 32, 191–202 (1976) taking into account the coupling effect of the skeletal torsion.     

Microwave spectrum,structure, dipole moment,and internal rotation of methylsilylsulfide

Microwave spectra of methylsilylsulfide and its three isotopically substituted species were measured and their b-type transitions were assigned. The spectra of all the species exhibit doublet structures due to the internal rotation of the methyl group. Using the internal axis method, the potential barriers were determined from the observed A- and E-component frequencies to be 1081.0 ± 3.3, 1073.9 ± 2.0, 1065.1 ± 11.4, and 1076.0 ± 1.9 cal/mol for the normal, CH₃SSiD₃, CD₃SSiH₃, and ¹³CH₃SSiH₃ species, respectively. The analysis also yielded 3°49′ as the tilt angle of the methyl top. From the rotational constants obtained, a plausible structure was estimated. The molecular electric dipole moments were determined from the second-order Stark effect of some A-component transitions with low- J quantum numbers for the normal and SiD₃ species. A comparison of the obtained parameters was made with analogous molecules.     

Microwave spectrum,dipole moment,and structure of anti-vinyl alcohol

The rotational spectra of the anti conformer of vinyl alcohol (ethenol, H₂CCHOH) and its OD modification have been studied by microwave spectroscopy. The compounds have been generated by very-low-pressure pyrolyses of the appropriate isotopic species of 3-thietanol. In both cases the 25 measured μ_a- and μ_b-type transitions allowed the rotational constants and all five quartic centrifugal distortion constants to be determined. Stark effect measurements have yielded the electic dipole moment: μ_a = 0.547(2), μ_b = 1.702(1), and μ = 1.788(1) D. By relative intensity measurements it has been found that the vibrational ground state of the anti conformer lies 4.5±0.6 kJ mol^?1 above the syn conformer. In addition, ab initio calculations at the 6–31G⁷ level have been performed to obtain the structure, relative energy, and dipole moment of both rotamers.     

The microwave spectrum,structure and nuclear quadrupole coupling constants for stibabenzene

The microwave spectrum of 121-SbC₅H₅, 123-SbC₅H₅, β-dideutero 121-SbC₅H₃D₂ and 123-SbC₅H₃D₂ has been assigned in the region 26.5–40.0 GHz. The respective rotational constants and uncertainties are: A = 4512.69 ± 0.42, B = 1738.00 ± 0.01, C = 1254.51 ± 0.01; A = 4512.84 ± 0.30, B = 1729.80 ± 0.01, C = 1250.22 ± 0.01; A = 4176.18 ± 0.33, B = 1660.94 ± 0.01, C = 1188.15 ± 0.01; A = 4176.60 ± 0.61, B = 1652.94 ± 0.03, C = 1184.03 ± 0.03 (in MHz units). The structure is found to be planar, C_2v in symmetry. The $\text{d(}\text{Sb-C}\text{) = 2.050 ± 0.005}\text{A}\text{?}$ and ∠CSbC = 92.9° ± 1.0°. The nuclear quadrupole coupling constants for the 121 and 123 antimony isotopes are χ_aa = 456.4 ± 4.1 MHz, η = 0.396 ± 0.008, and χ_aa = 583.00 ± 5.3 MHz, η = 0.399 ± 0.008, respectively. Several alternate techniques using the coupling constants as data support a σ-donating property for antimony.     

Microwave spectrum and dipole moment of pentafluorobenzene

With the idea of evaluating the dipole moment of pentafluorobenzene from a lowJ transition, its microwave spectrum was investigated in the frequency region of 8,000 to 12,400 MHz. The spectrum had been earlier observed by the authors in the 12,400 to 18,000 MHz region which needs reassignment in the light of present investigations. The rotational constants areA=1480·856±0·003 MHz,B=1030·066±0·003 MHz andC=607·496±0·002 MHz. The dipole moment is 1·44±0·05 D.     

Microwave spectrum,quadrupole coupling constants,and barrier to internal rotation of 2-iodopropene

The microwave spectrum of 2-iodopropene has been investigated between 7.7 and 18 GHz. The measured transition frequencies of the ground and two vibrationally excited states have been analyzed using direct diagonalization of the rotational and quadrupole Hamiltonian. The following rotational and quadrupole coupling constants have been determined in a leastsquares fit for the ground state: A = 9285.153(20) MHz; B = 2337.2198(14) MHz; C = 1887.5871(14) MHz; and χ_cc = ?1820.783(33) MHz; χ_ab = 147.5(10) MHz; χ_bb = 957.018(41) MHz; and χ_cc = 863.765(40) MHz. The quadrupole coupling constants have been transformed to their principal axis system. From the splittings of some transitions of the first torsionally excited state a value of V₃ = 905(3) cm^?1 has been found for the threefold barrier hindering the internal rotation of the methyl group.