The microwave spectrum of methyl chlorodifluoroacetate: Methyl internal rotation and chlorine nuclear electric quadrupole coupling

A chirped pulse microwave spectrometer has been used to record microwave spectra of the ³⁵Cl and ³⁷Cl isotopologues of methyl chlorodifluoroacetate, CClF₂C(O)OCH₃, between 8 GHz and 16 GHz. The target compound was spectroscopically examined as it participated in a supersonic expansion of argon. Only one conformer was observed. The rotational spectra were recorded with sufficient resolution to observe (i) splittings due to the internal rotation of the methyl group, and (ii) splittings from the coupling of the chlorine quadrupolar nucleus. A total of 785 transitions have had quantum numbers assigned. Analysis of the spectra observed has produced an experimental barrier to the methyl group internal rotation, V₃, of 370(2) cm⁻¹. It is noted that this barrier is a little lower than that determined for methyl acetate [V₃ = 425 cm⁻¹, J. Sheridan, W. Bossert and A. Bauder, J. Mol. Spectrosc., 80 (1980) 1-11], and this is rationalized through a comparison of molecular structures. Lastly, all components of both the ³⁵Cl and ³⁷Cl chlorine nuclear electric quadrupolar coupling tensor have been determined.     

Microwave spectrum and structure of methyl phosphonic difluoride

The rotational spectrum of methyl phosphonic difluoride has been reinvestigated using a pulsed-molecular-beam Fabry-Perot cavity microwave spectrometer. The enhanced resolution of the Fourier transform microwave (FTMW) spectrometer (compared to the original work done in a conventional Stark spectrometer) has allowed the measurement of small A-E splittings of many of the rotational transitions caused by the internal rotation of the methyl top. The barrier to internal rotation, V₃ = 676 (25) cm⁻¹, has been determined experimentally from the A-E splittings of the rotational transitions in the ground vibrational state. This barrier height is substantially lower than the previously determined value for the barrier, which was 1252 (14) cm⁻¹. High-level ab initio calculations at the MP2/aug-cc-pVTZ level predict a barrier to internal rotation of 638 cm⁻¹, in agreement with the experimentally determined value found here. The high sensitivity of the FTMW spectrometer has also permitted the measurement of the ¹³C and ¹⁸O isotopomers in natural abundance. The addition of these two isotopomers has allowed an improved structural determination.     

Rotationally resolved spectroscopy of the ν8 band of cis-methyl nitrite

The 770-880 cm⁻¹ region of the methyl nitrite spectrum has been recorded at a resolution of 0.0015 cm⁻¹ in a static cell. Consistent with published determinations of the barrier to internal rotation of the methyl group, bands belonging to the trans isomer are very congested while those belonging to the cis isomer are more tractable. A total of 634 lines have been assigned in the ν₈ vibrational band of the cis isomer. These lines and 32 microwave lines have been globally fit to a Watson-type Hamiltonian with an rms deviation of 0.00044 cm⁻¹. An additional 150 lines were also assigned but were not included in the fit because they were split by 0.001-0.005 cm⁻¹, much larger than previously reported torsional or hyperfine splittings.     

Rotational spectrum of trifluoroacetone

The rotational spectra of 5 isotopologues of 1,1,1-trifluoroacetone have been assigned using pulsed-jet Fourier-transform microwave spectroscopy. All rotational transitions appear as doublets, due to the internal rotation of the methyl group. Analysis of the tunneling splittings using both the principal axis method (PAM) and the combined axis method (CAM) methods allows to determine accurately the height of the threefold barrier to internal rotation of the methyl group, and its orientation, leading to V₃ = 3.28 and 3.10 kJ mol⁻¹, respectively. The r_s geometry of the molecular skeleton, a partial r₀ structure of the molecule and supporting ab initio calculations are also reported.     

High resolution FTIR study on NH2Br molecule: amino wagging band

The amino wagging band of NH₂Br molecule has been observed in the region from 800 to 1200 cm⁻¹ with the resolution of 0.006 cm⁻¹ by a Fourier transform spectrometer. The rotational and centrifugal distortion constants have been determined which reproduce the rotational structures of K^′_a<6 for both isotopomers of ⁷⁹Br and ⁸¹Br. The spectral splittings as much as 0.07 cm⁻¹ due to the amino inversion motion have been observed and some discussions on the inversion potential have been made.     

Dynamical structure of peptide molecules: Fourier transform microwave spectroscopy and ab initio calculations of N-methylformamide

Rotational spectra of both trans and cis forms of the N-methylformamide normal as well as deuterated (HCONDCH₃, referred to as N-D) species were observed by Fourier transform microwave spectroscopy in the frequency region from 5 to 118 GHz. Samples were prepared in the form of a beam by a pulsed jet valve maintained at 50 °C and were introduced in a high-vacuum cavity cell, with either Ne or Ar as a carrier gas at a backing pressure of 100 kPa. The observed spectra were analyzed to yield molecular parameters including rotational constants and barrier, V₃, to CH₃ internal-rotation: 53.9 (6) and 301 (4) cm⁻¹ for the trans and cis forms of the normal species, respectively, and 41.9 (6) and 309 (4) cm⁻¹ for the trans and cis forms of the N-D species, respectively. Spectra of four trans isotopologues with ¹³C, ¹⁵N, or ¹⁸O singly-substituted in the internal-rotation A state were observed and analyzed to derive the r_s structure of the trans form. For comparison with the experimental data, ab initio calculations were carried out at MP2/6-31G∗∗ level to derive molecular structure, potential barrier to CH₃ internal rotation, and the energy difference between the cis and trans forms. An extensive coupling was found between the CH₃ internal rotation and N-H out-of-plane bending, suggesting that the potential function for the CH₃ internal-rotation deviates considerably from a simple cos(3α) form. The effects of the V₆ term is briefly discussed.     

Fourier-transform microwave spectroscopy of N-methylaniline

The jet-cooled Fourier-transform microwave spectrum of N-methylaniline (C₆H₅-NHCH₃) was recorded in the region of 10-26 GHz, and was analyzed to determine rotational constants and nuclear quadrupole coupling constants. Furthermore, a Coriolis-like coupling parameter characterizing an interaction between an internal rotation of a methyl group and an overall rotation was also determined from A-E splittings observed in pure rotational transitions with high K_a values. The Coriolis-like coupling parameter permitted the determination of the barrier to internal rotation of the methyl group which was found to be 975 cm⁻¹.     

Torsional analysis of 2-butynol

The microwave spectrum of 2-butynol, CH₃CCCH₂OH, has been investigated in the frequency range of 6-26.5 GHz. The spectra of the A and E torsional states were observed using Fourier transform microwave spectroscopy. Due to the presence of the cylindrically symmetric CC “spacer” between the methyl group and the rest of the molecule, the barrier to internal rotation, V₃, is only 7 cm⁻¹. One conformer of 2-butynol was observed and assigned. The spectrum was analyzed with the ρ-axis method using a very flexible Hamiltonian which gives a fit an order of magnitude better than that obtained with more standard code for internal rotation. The spectroscopic constants are: 23744.(18), 2093.429(1), 1966.358(1), and −400.34(2) MHz for A, B, C, and D_ab; 0.48(1) kHz, −30.3(4) kHz, and 4.5(5) MHz for Δ_J, Δ_JK, and Δ_K; and 0.1406(6), 6.93(9) cm⁻¹, −33.4(7) kHz, and 192.0(9) GHz for ρ, V₃, L_V, and F, respectively. The root mean squared error of the fit is 14 kHz. The angles between the internal rotor axis and principal axes are θ_a=12°, θ_b=78°, with θ_c held fixed at 90°.     

Methyl torsional state analysis of the jet-cooled microwave spectrum of N-acetylglycine

The microwave spectrum of N-acetylglycine was obtained using a NIST Fourier-transform microwave spectrometer equipped with a heated, pulsed-nozzle source. One conformer has been identified and its spectrum assigned. The conformer has C_S point group symmetry and an intramolecular hydrogen bond between the carbonyl and amide groups of the 5-membered glycine unit. Internal rotation of the methyl rotor group leads to splitting of the rotational lines into A and E symmetry tunneling states. The ¹⁴N nuclear-quadrupole hyperfine structure verifies the rotational and internal-rotor state assignments. The V₃ barrier of 57.5(1) cm⁻¹ and the angles between the C₃ axis of the methyl rotor and the principal inertial axes are in best agreement with the calculated values for the lowest energy conformer of the four conformers predicted at the MP2/6-311++G(d,p) level of theory.     

The microwave spectrum of the trans conformer of ethyl acetate

The Fourier transform microwave spectrum of ethyl acetate has been measured under molecular beam conditions. The trans conformer, where all heavy atoms are located within a mirror plane, was identified after analyzing the spectrum by comparison with theoretical calculations. The barrier to internal rotation of the acetate methyl group was found to be only 99.57(11) cm⁻¹ whereas for methyl torsion in the ethyl group a barrier of 1112.3(37) cm⁻¹ was determined. A comparison between two theoretical approaches treating the internal rotation, the so-called RAM (Rho Axis Method) and CAM (Combined Axis Method), is also performed.     

Structural and Torsional Properties of o-Cresol and o-Cresol-OD as Obtained from Microwave Spectroscopy and ab Initio Calculations

The microwave spectra of o-cresol and of o-cresol-OD were assigned using molecular beam Fourier transform microwave (MB-FTMW) spectrometers in the frequency range of 3-40 GHz. Two conformers of o-cresol were measured where the hydroxy group is syn with respect to the methyl group in one case and anti in the other. The transitions of both conformers were split due to internal rotation of the methyl group. For syn-o-cresol we found the rotational constants A=3249.45242(18) MHz, B=2202.02546(18) MHz, C=1323.66277(16) MHz, and the barrier to internal rotation of the methyl group V₃=7.912(46) kJ mol⁻¹. In the case of anti-o-cresol A=3273.80084(18) MHz, B=2196.26747(18) MHz, C=1325.36424(22) MHz, and V₃=4.4256(14) kJ mol⁻¹ was obtained. Moreover we were able to determine the quartic centrifugal distortion constants, the angle between the internal rotor axes, and the inertial a axes, and, for the deuterated species, additionally the deuterium nuclear quadrupole coupling constants.     

Torsional barrier and equilibrium structure of ethyl cyanide

The quadratic, cubic and semi-diagonal quartic force field of ethyl cyanide has been calculated at the B3LYP level of theory employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quadruple-ζ quality and a core correlation correction. The empirical structures are also determined and their accuracy is discussed. The potential barrier V₃ hindering internal rotation of the methyl group has been calculated from 23 rotational transitions of CH₃CH₂C¹⁵N which were found split into doublets, giving V₃ = 3074(27) cal mol⁻¹.     

Millimeter-wave investigation, simplified interpretation of the fourfold rotational spectrum, and dynamics of the internal motions of acetaldehyde-argon

The rotational spectra of the acetaldehyde-argon van der Waals complex have been measured by free jet absorption millimeter-wave spectroscopy in the frequency range 60-78 GHz. Each rotational transition is split into four hyperfine component lines, which is evidence of the occurring of two different internal motions. The splittings have been interpreted in terms of a coupled Hamiltonian that precisely determines the separation of energy levels due to the tunneling of the rare gas atom between two equivalent minima, while the information on the barrier to internal rotation of the methyl group is obtained from the pattern of the component A-E lines due to this motion. The interaction of the rare gas atom with the acetaldehyde moiety is reflected in a reduction of the V₃ barrier to internal rotation in going from the molecule to the weakly bound complex of about 20%. The barrier to the Ar tunnelling has been estimated to be 26 cm⁻¹.     

Galvanomagnetic properties of air-stable and highly conductive potassium-intercalated graphite sheet

Magnetoresistance and Hall coefficient of air-stable potassium-intercalated graphite sheets (hereafter abbreviated as K-PGS) were determined at room temperature. The magnitude of the magnetoresistance and the absolute value of Hall coefficient of K-PGS decreased with increasing potassium content of K-PGS, n_K/n_C. Two-carrier model was used for calculating carrier density and mobility. The electron density increased with increasing n_K/n_C: 3.07×10²⁰ cm⁻³ (n_K/n_C=0.005), 5.67×10²⁰ cm⁻³ (n_K/n_C=0.008) and 6.40×10²⁰ cm⁻³ (n_K/n_C=0.011). The value of the electron density of K-PGS with n_K/n_C=0.011 (nominal composition KC₉₁) was about 80% of the reported value, 7.8×10²⁰ cm⁻³, for KC₄₈ (n_K/n_C=0.021) prepared from HOPG (highly oriented pyrolytic graphite). The mobility decreased with increasing n_K/n_C: 2.11×10³ cm² V⁻¹ s⁻¹ (n_K/n_C=0.005), 1.42×10³ cm² V⁻¹ s⁻¹ (n_K/n_C=0.008) and 1.34×10³ cm² V⁻¹ s⁻¹ (n_K/n_C=0.011). The value of the mobility of K-PGS with n_K/n_C=0.011 was about 60% of the reported value (2300 cm² V⁻¹ s⁻¹) for KC₄₈ prepared from HOPG.     

The ground and first excited torsional states of methyl carbamate

A global fit within experimental accuracy of microwave and millimeter-wave transitions in the ground and first excited torsional states of methyl carbamate (H₂NC(O)OCH₃) is presented. The data set consisting of 995 v_t = 0 and 731 v_t = 1 transition frequencies combines 1544 new measurements from Kharkov with previously published v_t = 0 microwave lines. In this study the so-called “rho axis method” that treats simultaneously both A and E species of the ground and first excited torsional states is applied to the methyl carbamate data set for the first time. The final fit requires only 32 parameters to achieve a unitless weighted standard deviation for the whole fit of 0.89 for a total of 1726 transitions with rotational quantum numbers up to J ? 20 and K_a ? 10. The barrier to internal rotation of the methyl group obtained in this study, V₃ = 359.141(24) cm⁻¹, is in good agreement with previously published values but more accurate.     

Assignment, fit, and theoretical discussion of the ν10 band of acetaldehyde near 509 cm

The lowest small-amplitude vibration in acetaldehyde (CH₃CHO) is the in-plane aldehyde scissors mode ν₁₀ at 509 cm⁻¹. This mode lies about 175 cm⁻¹ above the top of the barrier to internal rotation of the methyl group and is relatively well separated from other small-amplitude vibrational states (the next fundamental occurring more than 250 cm⁻¹ higher). It thus provides an excellent example of an isolated small-amplitude fundamental (bright state) embedded in a bath of dark states. Since the bath states at these energies are not too dense, and since they arise purely from states of the large-amplitude torsional vibration of the methyl rotor, a detailed spectroscopic analysis of interactions between the bright state and the bath states should be possible. This paper represents the first step toward that goal. We have assigned several thousand transitions in the ν₁₀ band (J ? 28, K ? 12), and have carried out a simultaneous fit of 2400 of these transitions (J ? 15, K ? 9) with over 8100 transitions to the torsional bath state levels. Three vibration-torsion interactions, which give rise to rather global level shifts of the order of 1 cm⁻¹ in the ν₁₀ levels, have been identified and quantitatively fit. A number of vibration-torsion-rotation interactions, which give rise to localized (avoided-crossing) shifts in ν₁₀ have also been determined. The present analysis indicates the need for reliable spectroscopic information on more of the torsional bath states in the immediate vicinity of the ν₁₀ levels. Possible ways of obtaining such information in future studies are considered.     

Fourier transform microwave spectrum of the CO-dimethyl sulfide complex

The rotational spectrum of the CO-dimethyl sulfide (DMS) complex was measured in the frequency region from 4.8 up to 25 GHz by Fourier transform microwave spectroscopy. For the normal species 27 a-type and 57 c-type transitions were observed, while 16 and 8 c-type transitions were assigned for the species with ³⁴S and ¹³C in the DMS moiety, respectively, in natural abundance. In addition, 7 a-type and 48 c-type transitions were assigned for the complex with the ¹³CO enriched species as a component and 9 a-type and 42 c-type transitions for the complex with enriched C¹⁸O. No splitting was observed, which could be ascribed to the tunneling motion of the CO between two possible potential minima around DMS, while many transitions were split by the internal-rotation of the two methyl tops of the DMS unit. In cases where the K-type splitting was close to the methyl internal-rotation splitting, forbidden transitions were observed which apparently followed b-type selection rules. All of the observed transition frequencies for the normal species were analyzed simultaneously using a two-top internal-rotation and rotation Hamiltonian. The potential barrier height V₃ to internal rotation of the methyl groups of the DMS was determined to be 745.5 (30) cm⁻¹. The transition frequencies observed for all the isotopomers were analyzed using an asymmetric-rotor rotational Hamiltonian, to determine rotational and centrifugal distortion constants. The r_s coordinates calculated from the observed rotational constants led to the conclusion that the CO moiety was located in a plane perpendicular to the skeletal plane of the DMS and bisecting its CSC angle. This structure of the CO-DMS is very much different from that of the CO-DME, in which the CO is located in the DME skeletal plane. The distance between the centers of gravity of the two moieties, R_cm, was calculated to be 3.789 Å for the CO-DMS, which is longer by only 0.11 Å than that in the CO-DME complex: 3.68 Å, in spite of the fact that the van der Waals radius of the S atom is much larger than that of the O atom. The small difference in R_cm is, in part, ascribed to the location of the CO relative to the DMS/DME. The more important reason is that the intermolecular bonding of the CO-DMS is stronger than that of CO-DME; by assuming a Lennard-Jones-type potential, the force constant of the van der Waals stretching mode and the dissociation energy were estimated to be 2.7 Nm⁻¹ and 3.3 kJ mol⁻¹, respectively, which were larger than those of the CO-DME: 1.4 Nm⁻¹ and 1.6 kJ mol⁻¹.     

Analysis of rotational structure in the high-resolution infrared spectrum and assignment of vibrational fundamentals of butadiene-2,3-C2

The 2,3-¹³C₂ isotopomer of butadiene was synthesized, and its fundamental vibrational fundamentals were assigned from a study of its infrared and Raman spectra aided with quantum chemical predictions of frequencies, intensities, and Raman depolarization ratios. For two C-type bands in the high-resolution (0.002 cm⁻¹) infrared spectrum, the rotational structure was analyzed. These bands are for ν₁₁ (a_u) at 907.17 cm⁻¹ and for ν₁₂ (a_u) at 523.37 cm⁻¹. Ground state and upper state rotational constants were fitted to Watson-type Hamiltonians with a full quartic set of centrifugal distortion constants and two sextic ones. For the ground state, A₀ = 1.3545088(7) cm⁻¹, B₀ = 0.1469404(1) cm⁻¹, and C₀ = 0.1325838(2)  cm⁻¹. The small inertial defects of butadiene and two ¹³C₂ isotopomers, as well as for five deuterium isotopomers as previously reported, confirm the planarity of the s-trans rotamer of butadiene.     

S0 and S1 spectroscopy of jet cooled 9-cyano-10-methylanthracene: The methyl group as a molecular rotor

Jet-cooled fluorescence excitation and dispersed fluorescence spectra of 9-methylanthracene (MA), 9-cyanoanthracene (CA) and 9-cyano-10-methylanthracene (CMA) have been measured. The spectra of MA and CMA near the S₀-S₁ origin reveal a prominent torsional progression due to the hindered methyl group rotation and its torsional vibration against the aromatic ring frame. Additionally, the laser induced fluorescence LIF excitation spectrum of CMA shows the splitting of many vibrational modes.Observed positions and relative intensities of the methyl internal rotational bands were interpreted in terms of transitions calculated based on the quantum mechanical one-dimensional rotor. The low-frequency vibrational bands were interpreted also with the all electron quantum mechanical calculations within the RHF/6-31G(d,p), CIS/3-21G and CIS/6-31G(d,p) approximations. It is predicted that in the case of MA the eclipsed geometry (one C-H in the plane of the ring) is most stable in both S₀ and S₁ states. Conformation of the methyl group in CMA is suggested to change upon S₁ ← S₀ excitation (π/12 phase shift of the methyl group). The predicted energy barrier for methyl group rotation in the S₀ state of CMA is considerably higher (72 cm⁻¹) than that in the S₁ state (22 cm⁻¹). Following the present quantum mechanical calculations, the carbon atom of the methyl group belongs to the aromatic plane in the S₀ ground state but it deviates from this plane in the S₁ excited state. These in turn suggest that the calculated barrier for methyl group rotation in CMA has a 6-fold symmetry in the S₀ ground state and roughly a 4-fold symmetry in the S₁ state.