Identification of Two Stable Side-Chain Orientations of Valine Methyl Ester by Microwave Spectroscopy.

The rotational spectra of two valine methyl ester (ValOMe) conformers have been measured using a cavity-based Fourier-transform microwave spectrometer in the range of 9-18 GHz. Ten conformers of ValOMe were modeled using the ωB97XD/6-311++G(d,p) level of theory, and separate spectra arising from two lowest-energy conformations were observed and assigned. 44 rotational transitions were assigned to conformer I, the lowest-energy configuration, and were fit to Watson's A-reduced Hamiltonian: A = 2552.0145(5) MHz, B = 1041.8216(3) MHz, and C = 938.54890(22) MHz. 14N nuclear quadrupole hyperfine splittings were resolved, and 231 hyperfine components were fit to χaa = -4.187(7) MHz, and χbb-χcc = 1.269(5) MHz. The spectrum of conformer I also reveals tunneling splittings arising from the methyl rotor. XIAM was used to fit the barrier to the internal rotation of the methyl rotor, and the best-fit V3 barrier was found to be 401.64(19) cm-1. 47 rotational transitions were assigned for conformer II (ΔE = 2.08 kJ mol-1), and the fitted rotational constants are A = 2544.2837(3) MHz, B = 1092.3654(15) MHz, and C = 896.3131(12) MHz. 264 hyperfine components were fit to χaa = -4.187(7) MHz and χbb-χcc = 1.518(6) MHz, and the best-fit V3 barrier was found to be 409.74(16) cm-1.

Theoretical and Microwave Spectroscopic Characterization of Cyclobutenone: Planar or Puckered?

Cyclobutenone was characterized by high-resolution Fourier transform microwave spectroscopy for the first time. High-level, first-principles quantum chemical calculations at the B3LYP, CISD, MP2, and CCSD levels of theory were implemented to better understand the molecular structure and obtain model rotational and centrifugal distortion constants to aid in spectral assignment, and the results at the different levels of theory are compared. The assignment of the experimental spectrum provided fits of 2.7 kHz using Watson A-reduced and Watson S-reduced Hamiltonians. No tunneling splittings were observed, suggesting that cyclobutenone is not undergoing ring-puckering tunneling.

Fourier Transform Microwave Spectrum of Propene-3-d1 (CH2═CHCH2D), Quadrupole Coupling Constants of Deuterium, and a Semiexperimental Equilibrium Structure of Propene.

The ground-state rotational spectrum of propene-3-d1, CH2═CHCH2D, was measured by Fourier transform microwave spectroscopy. Transitions were assigned for the two conformers, one with the D atom in the symmetry plane (S) and the other with the D atom out of the plane (A). The energy difference between the two conformers was calculated to be 6.5 cm-1, the S conformer having lower energy. The quadrupole hyperfine structure due to deuterium was resolved and analyzed for both conformers. The experimental quadrupole coupling and the centrifugal distortion constants compared favorably to their ab initio counterparts. Ground-state rotational constants for the S conformer are 40582.157(9), 9067.024(1), and 7766.0165(12) MHz. Ground-state rotational constants for the A conformer are 43403.75(3), 8658.961(2), and 7718.247(2) MHz. For the A conformer, a small tunneling splitting (19 MHz) due to internal rotation was observed and analyzed. Using the new rotational constants of this work as well as those previously determined for the 13C species and for some deuterium-substituted species from the literature, a new semiexperimental equilibrium structure was determined and its high accuracy was confirmed. The difficulty in obtaining accurate coordinates for the out-of-plane hydrogen atom is discussed.

Probing the Electronic Environment of Methylindoles using Internal Rotation and (14)N Nuclear Quadrupole Coupling.

High-resolution rotational spectra were recorded in the 10.5-21.0 GHz frequency range for seven singly methylated indoles. (14)N nuclear quadrupole hyperfine structure and spectral splittings arising from tunneling along the internal rotation of the methyl group were resolved for all indole species. The nuclear quadrupole coupling constants were used to characterize the electronic environment of the nitrogen atom, and the program XIAM was used to fit the barrier to internal rotation to the measured transition frequencies. The best fit barriers were found to be 277.1(2), 374.32(4), 414.(5), 331.6(2), 126.8675(15), 121.413(4), and 426(3) cm(-1) for 1-methylindole through 7-methylindole, respectively. The fitted barriers were found to be in good agreement with barriers calculated at the ωB97XD/6-311++G(d,p) level. The complete set of experimental barriers is compared to theoretical investigations of the origins of methyl torsional barriers and confirms that the magnitude of these barriers is an overall effect of individual hyperconjugative and structural interactions of many bonding/antibonding orbitals.

Microwave, structural, conformational, vibrational studies and ab initio calculations of fluoroacetyl chloride.

The infrared and Raman spectra (3200-50 cm(-1)) of the gas, liquid or solution, and solid of fluoroacetyl chloride, FCH2COCl have been recorded. FT-microwave studies have also been carried out and 22 transitions were recorded for the trans conformer. Variable temperature (-50 to -105 °C) studies of the infrared and Raman spectra (3200-50 cm(-1)) of xenon solutions have been carried out. From these data, the trans, cis and gauche conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 159±11 cm(-1) (1.90±0.14 kJ mol(-1)) with the trans conformer the more stable form than the cis. The energy difference between the cis and gauche form is 222±18 cm(-1) (2.66±0.21 kJ/mol) and the energy difference between the trans and gauche forms is 386±13 cm(-1) (4.61±0.16 kJ/mol). Vibrational assignments have been made for the observed bands for the three conformers with initial predictions by MP2(full)/6-31G(d) ab initio calculations to obtain harmonic force constants, wavenumbers, infrared intensities, and Raman activities for the three conformers. By utilizing the microwave rotational constants of two isotopomers for trans, combined with the structural parameters predicted from MP2(full)/6-311+G(d,p) calculations, adjusted r0 parameters have been obtained for the trans conformer. The results are discussed and compared to the corresponding properties of some related molecules.

Microwave, structural, conformational, vibrational studies and ab initio calculations of isocyanocyclopentane.

The infrared and Raman spectra (3200-50 cm(-1)) of the gas, liquid or solution, and solid have been recorded of isocyanocyclopentane, c-C5H9NC. FT-microwave studies have also been carried out and 23 transitions were recorded for the envelope-axial (Ax) conformer. Variable temperature (-65 to -100 °C) studies of the infrared spectra (3200-400 cm(-1)) dissolved in liquid xenon have been carried out. From these data, both the Ax and envelope-equatorial (Eq) conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 102±10 cm(-1) (1.21±0.11 kJ mol(-1)) with the Ax conformer the more stable form. The percentage of the Eq conformer is estimated to be 38±1% at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by utilizing several different basis sets up to aug-cc-pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been made for the observed bands for both conformers with initial predictions by MP2(full)/6-31G(d) ab initio calculations to obtain harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. The structural parameter values for the Ax form are; for the heavy atom distances (Å): C≡N = 1.176 (3); Cα-N=1.432 (3); Cα-Cß,Cß'=1.534 (3); Cß-Cγ,Cγ'=1.542 (3); Cγ-Cγ'=1.554 (3) and angles (°):∠Cα-N≡C=177.8 (5); ∠CßCα-N=110.4 (5);

Microwave and infrared spectra, adjusted r0 structural parameters, conformational stabilities, vibrational assignments, and theoretical calculations of cyclobutylcarboxylic acid chloride.

The FT-microwave spectrum of cyclobutylcarboxylic acid chloride, c-C4H7C(O)Cl, has been recorded and 153 transitions for the (35)Cl and (37)Cl isotopologues have been assigned for the gauche-equatorial (g-Eq) conformation. The ground state rotational constants were determined for (35)Cl [(37)Cl]: A = 4349.8429(25) [4322.0555(56)] MHz, B = 1414.8032(25) [1384.5058(25)] MHz, and C = 1148.2411(25) [1126.3546(25)] MHz. From these rotational constants and ab initio predicted parameters, adjusted r0 parameters are reported with distances (Å) rCα-C = 1.491(4), rC═O = 1.193(3), rCα-Cß = 1.553(4), rCα-Cß' = 1.540(4), rCγ-Cß = 1.547(4), rCγ-Cß' = 1.546(4), rC-Cl = 1.801(3) and angles (deg) τCγCßCß'Cα = 30.9(5). Variable temperature (-70 to -100 °C) infrared spectra (4000 to 400 cm(-1)) were recorded in liquid xenon and the g-Eq conformer was determined the most stable form, with enthalpy differences of 91 ± 9 cm(-1) (1.09 ± 0.11 kJ/mol) for the gauche-axial (g-Ax) form and 173 ± 17 cm(-1) (2.07 ± 0.20 kJ/mol) for the trans-equatorial (t-Eq) conformer. The relative amounts at ambient temperature are 54% g-Eq, 35 ± 1% g-Ax, and 12 ± 1% t-Eq forms. Vibrational assignments have been provided for the three conformers and theoretical calculations were carried out. The results are discussed and compared to corresponding properties of related molecules.

Microwave spectra of the deuterium isotopologues of cis-hexatriene and a semiexperimental equilibrium structure.

Microwave transitions and ground state rotational constants are reported for five newly synthesized deuterium isotopologues of cis-1,3,5-hexatriene (cHTE). These rotational constants along with those of the parent and the three (13)C species are used with vibration-rotation constants calculated from an MP2/cc-pVTZ model to derive an equilibrium structure. That structure is improved by the mixed estimation method. In this method, internal coordinates from good-quality quantum chemical calculations (with appropriate uncertainties) are fit simultaneously with moments of inertia of the full set of isotopologues. The new structure of cHTE is confirmed to be planar and is stabilized by an interaction between the hydrogen atoms H2 and H5, which form a bond and participate in a six-membered ring. cHTE shows larger structural effects of π-electron delocalization than does butadiene with the effects being magnified in the center of the molecule. Thus, strong structural evidence now exists for an increase in π-electron delocalization as the polyene chain lengthens.

Semiexperimental equilibrium structure of the lower energy conformer of glycidol by the mixed estimation method.

Rotational constants were determined for (18)O-substituted isotopologues of the lower energy conformer of glycidol, which has an intramolecular inner hydrogen bond from the hydroxyl group to the oxirane ring oxygen. Rotational constants were previously determined for the (13)C and the OD species. These rotational constants have been corrected with the rovibrational constants calculated from an ab initio cubic force field. The derived semiexperimental equilibrium rotational constants have been supplemented by carefully chosen structural parameters, including those for hydrogen atoms, from medium level ab initio calculations. The combined data have been used in a weighted least-squares fit to determine an equilibrium structure for the glycidol H-bond inner conformer. This work shows that the mixed estimation method allows us to determine a complete and reliable equilibrium structure for large molecules, even when the rotational constants of a number of isotopologues are unavailable.

Microwave, infrared, and Raman spectra, r0 structural parameters, conformational stability, and vibrational assignment of allyl thiol.

FT-microwave spectrum of allyl thiol, H(2)CCHCH(2)SH, has been recorded, and 19 transitions have been assigned for the most abundant isotopologue of Gg conformer, and the rotational constants have been determined; A=20,041.439 (4), B=2795.830 (1), C=2701.084 (1). From the determined microwave rotational constants and ab initio MP2(full)/6-311+G(d,p) predicted structural values, adjusted r(0) parameters are reported with distances (Å): rCC=1.343 (3), rC-C=1.496 (3), rC-S=1.827 (3) and angles (°) ∠CCC=123.4 (5), ∠CCS=112.5 (5), and τC(γ)C(ß)C(α)S=118.7 (5). Variable temperature (-55 to -100°C) infrared spectra (3600-400cm(-1)) were recorded of allyl thiol in liquid xenon and the Gg conformer was determined to be the most stable form. The enthalpy differences relative to the Gg form are for Cg 120±9cm(-1) (1.44±0.11kJ/mol), for Gg' 337±34cm(-1) (4.03±0.41kJ/mol), and for Gt 360±36cm(-1) (4.31±0.43kJ/mol). The relative amounts present at ambient temperature are Gg 52±1%, Cg 29±1%, Gg' 10±1%, and Gt 9±1%. The conformational stabilities have been predicted from ab initio calculations with many basis sets up to aug-cc-pVTZ and the predicted stabilities are in agreement with the experimentally determined order. Vibrational assignments are reported with support by ab initio predictions and results are discussed.

Rotational spectra and computational analysis of two conformers of leucinamide.

Rotational spectra were recorded for two isotopic species of two conformers of the amide derivative of leucine in the range of 10.5-21 GHz and fit to a rigid rotor Hamiltonian. Ab initio calculations at the MP2/6-311++G(d,p) level identified the low energy conformations with different side chain configurations; the rotational spectra were assigned to the two lowest energy ab initio structures. We recorded 16 a- and b-type rotational transitions for conformer 1; the rotational constants of the normal species are A = 2275.6(2), B = 1033.37(2) and C = 911.71(5) MHz. We recorded 23 a- and b-type rotational transitions for conformer 2; the rotational constants of the normal species are A = 2752.775(8), B = 843.502(1) and C = 796.721(1) MHz. The rotational spectra of the (15)N(amide) isotopomer of each conformer were recorded and the atomic coordinates of the amide nitrogen were determined by Kraitchman's method of isotopic substitution. The experimentally observed structures are significantly different from the crystal structures of leucinamide and the gas-phase structures of leucine, and a natural bond orbital analysis revealed the donor-acceptor interactions governing side chain configuration.

Microwave, Raman, and infrared spectra; adjusted r(0) structural parameters; conformational stability; and vibrational assignment of germylcyclohexane.

The FT-microwave spectrum of germylcyclohexane, c-C(6)H(11)GeH(3), has been recorded, and more than 40 transitions for the (70)Ge, (72)Ge, and (74)Ge isotopomers (isotopologues) have been assigned for the chair-equatorial conformer. The heavy atom adjusted r(0) structural parameters have been determined [distances, C(gamma)-C(delta) = 1.533(3) A, C(gamma)-C(beta) = 1.532(3) A, C(alpha)-C(beta) = 1.540(3) A, C(alpha)-Ge = 1.957(3) A; angles, angleC(gamma)C(delta)C(beta) = 111.2(5) degrees , angleGeC(alpha)C(beta) = 111.1(5) degrees , with the dihedral angle angleC(gamma)C(delta)C(beta)C(alpha) = 55.6(10) degrees ]. Raman and/or infrared spectra of gas, liquid, and solid germylcyclohexane have been recorded. The temperature dependency of the Raman spectrum of the conformer pair 712 (equatorial)/683 (axial) cm(-1) gives an enthalpy difference of 453 +/- 38 cm(-1) (1.30 +/- 0.11 kcal/mol) with the chair-equatorial conformer the more stable form. At ambient temperature, the abundance of the axial conformer is 11 +/- 1%. Substituent effects on the enthalpy difference and structure of monosubstituted cyclohexanes are discussed for a number of molecules.

Infrared spectra of CF(2)=CHD and CF(2)=CD(2): scaled quantum-chemical force fields and an equilibrium structure for 1,1-difluoroethylene.

Infrared (IR) spectra in the gas phase are reported for CF(2)=CHD and CF(2)=CD(2) in the region 350-4000 cm(-1). Ab initio calculations of an harmonic force-field and anharmonicity constants have been made with an MP2/aug-cc-pVTZ model. These enable a number of Fermi resonances in each species to be analyzed and a complete set of "observed" harmonic frequencies to be derived. The latter are combined with similar data for CF(2)=CH(2) in a scaling of the model harmonic force field to both anharmonic and harmonic frequencies. Inspection of the scale factors reveals minor defects of the model, evident in the out-of-plane wagging modes and in the CF stretch/CF stretch interaction force constant. Fermi resonance treatments involved in all isotopomers studied are compatible with the overall force-field refinement results. The treatment leaves a small anomaly in the (13)C shift on nu(1). Improved microwave spectra are reported for five isotopic species, and a semiexperimental equilibrium structure for F(2)C=CH(2) is determined and compared favorably with the structure obtained from new high-level ab initio calculations. Centrifugal distortion constants are predicted for the five isotopic species, and those for F(2)C=CH(2) are compared with values fit to microwave spectra.

Rotational spectra of o-, m-, and p-cyanophenol and internal rotation of p-cyanophenol.

Rotational spectra of p-, m-, and o-cyanophenol have been measured in the range of 10.5-21 GHz and fit using Watson's A-reduction Hamiltonian coupled with nuclear quadrupole coupling interaction terms for the (14)N nuclei. Ab initio calculations at the MP2/6-311++G(d,p) and CCSD(T)/6-311++G(d,p) levels predict the cis conformers of m- and o-cyanophenol to be more stable than the corresponding trans conformers. A natural bond orbital analysis of the hydrogen bonding interaction in o- and m-cyanophenol revealed an intramolecular hydrogen bond that preferentially stabilizes the cis conformer of o-cyanophenol but there was no evidence of hydrogen bonding interactions in cis m-cyanophenol. We recorded 25 a- and b-type rotational transitions for cis o-cyanophenol; the rotational constants are A = 3053.758(2) MHz, B = 1511.2760(3) MHz, and C = 1010.7989(2) MHz. The trans conformer of o-cyanophenol was not observed. We recorded 14 a- and b-type rotational transitions for cis m-cyanophenol and 16 a- and b-type rotational transitions for trans m-cyanophenol. The rotational constants are A = 3408.9200(2) MHz, B = 1205.8269(2) MHz, and C = 890.6672(1) MHz and A = 3403.1196(3) MHz, B = 1208.4903(2) MHz, and C = 891.7241(2) MHz for the cis and trans species, respectively. Rotational transitions of the p-cyanophenol monomer are split due to the internal rotation of the hydroxyl group with respect to the aromatic ring. We recorded 25 a- and b-type rotational transitions for p-cyanophenol; the b-type transitions are split by 40 MHz. The rotational constants are A = 5612.96(2) MHz, B = 990.4283(6) MHz, and C = 841.9363(6) MHz. The ground state spitting DeltaE is 20.1608(6) MHz and the barrier to internal rotation, V(2), is 1413(2) cm(-1) from a fit of the rotational transitions to an internal axis system Hamiltonian. The barrier to internal rotation was modeled at the MP2/6-311++G(d,p) level and the effects of substituents on the phenolic ring and the barriers to internal rotation are discussed.