Intensity Control During Block-Periodized High-Intensity Training: Heart Rate and Lactate Concentration During Three Annual Seasons in World-Class Cross-Country Skiers.

Purpose: To describe heart rate (HR) and blood lactate (Bla-) responses during high-intensity interval training (HIT) in a long-term block-periodized HIT regimen in world-class cross-country (XC) skiers. Methods: Data were collected in 14 world-class female XC skiers (aged 25 ± 5 years; body mass, 60.4 ± 6.5 kg; and maximal HR, 194 ± 8 beats · min-1) throughout three entire seasons. The HR and Bla- values were determined at the end of 572 intervals performed during 63 sessions and 17 HIT blocks utilizing different exercise modes: running, running with poles, and skiing (on-snow and roller ski) with classic and skating techniques. Results: The mean HR was 91 ± 3% of HRmax with a corresponding Bla- of 7.3 ± 2.1 mmol · L-1. The average HR and Bla- values were relatively similar across the different exercise modes, except for a lower HR (~90 vs. 92% of HRmax) for on-snow and roller ski classical skiing and lower Bla- values (5.9 vs. 7.0-7.8 mmol · L-1) for on-snow classical skiing compared to the other modes, both P < 0.05. An increase in HR and Bla- was observed from interval working periods 1 to 3 (90-92% of HRmax and 6.5-7.7 mmol · L-1) and further from 3 to 5 (92-93% of HRmax and 7.7-9.0 mmol · L-1), all P < 0.05. Conclusions: We describe long-term use of HIT-block periodization among world-class XC skiers who achieved target HR and Bla- levels in all six exercise modes employed. According to athletes and coaches, the key to successful blocks was intensity control to allow for high-quality HIT sessions throughout the entire HIT block.

Microwave and Quantum Chemical Study of Intramolecular Hydrogen Bonding in 2-Propynylhydrazine (HC≡CCH2NHNH2).

The microwave spectrum of 2-propynylhydrazine (HC≡CCH2NHNH2) was investigated in the 23-124 GHz spectral interval. The spectra of two conformers denoted I and II were assigned. I is the lower-energy form, and relative intensity measurements yielded an internal energy difference of 3.0(4) kJ/mol between I and II. The spectra of the ground and five vibrationally excited states were assigned for I, whereas only the spectrum of the ground vibrational state was assigned for II. Both I and II are each stabilized simultaneously by two intramolecular hydrogen bonds. The first of these hydrogen bonds is formed between the hydrogen atom of the -NH- part of the hydrazino group, and the second internal hydrogen bond is formed between one of the hydrogen atoms of the -NH2 part. The π-electrons of the triple bond is thus shared by these two hydrogen atoms. The shortest contact between a hydrogen atom of the hydrazino group and the π-electrons of the ethynyl group is found in lower-energy conformer I. The conformational properties of 2-propynylhydrazine were explored by MP2/cc-pVTZ and CCSD/cc-pVQZ calculations. The CCSD method predicts that seven rotameric forms exist for this compound. Five of these rotamers are stabilized by internal hydrogen bonding. The simultaneous sharing of the π-electrons of the triple bond by two hydrogen atoms occurs only in Conformers I and II, which are predicted to be the two forms with the lowest energies, with I 2.52 kJ/mol lower in energy than II. The effective rotational constants of the ground vibrational states of I and II were predicted by a combination of MP2 and CCSD calculations, whereas centrifugal distortion constants and vibration-rotation constants were calculated by the MP2 method. The theoretical spectroscopic constants are compared with the experimental counterparts. It is concluded that more refined calculations are necessary to obtain complete agreement.

Rotational Spectrum, Conformational Composition, Intramolecular Hydrogen Bonding, and Quantum Chemical Calculations of Mercaptoacetonitrile (HSCH2C≡N), a Compound of Potential Astrochemical Interest.

The microwave spectra of mercaptoacetonitrile (HSCH2C≡N) and one deuterated species (DSCH2C≡N) were investigated in the 7.5-124 GHz spectral interval. The spectra of two conformers denoted SC and AP were assigned. The H-S-C-C chain of atoms is synclinal in SC and anti-periplanar in AP. The ground state of SC is split into two substates separated by a comparatively small energy difference resulting in closely spaced transitions with equal intensities. Several transitions of the parent species of SC deviate from Watson's Hamiltonian. Only slight improvements were obtained using a Hamiltonian that takes coupling between the two substates into account. Deviations from Watson's Hamiltonian were also observed for the parent species of AP. However, the spectrum of the deuterated species, which was investigated only for the SC conformer, fits satisfactorily to Watson's Hamiltonian. Relative intensity measurements found SC to be lower in energy than AP by 3.8(3) kJ/mol. The strength of the intramolecular hydrogen bond between the thiol and cyano groups was estimated to be ∼2.1 kJ/mol. The microwave work was augmented by quantum chemical calculations at CCSD and MP2 levels using basis sets of minimum triple-ζ quality. Mercaptoacetonitrile has astrochemical interest, and the spectra presented herein should be useful for a potential identification of this compound in the interstellar medium. Three different ways of generating mercaptoacetonitrile from compounds already found in the interstellar medium were explored by quantum chemical calculations.

Microwave and Quantum Chemical Study of Intramolecular Hydrogen Bonding in 2-Propenylhydrazine (H2C═CHCH2NHNH2).

The microwave spectrum of 2-propenylhydrazine (H2C═CHCH2NHNH2) was studied in the 12-61 and 72-123 GHz spectral regions. A variety of intramolecular hydrogen bonds between one or more of the hydrogen atoms of the hydrazino group and the π-electrons are possible for this compound. Assignments of the spectra of four conformers, all of which are stabilized with intramolecular hydrogen bonds are reported. One hydrogen bond exists in two of these conformers, whereas the π-electrons are shared by two hydrogen atoms in the two other rotamers. Vibrationally excited-state spectra were assigned for three of the four conformers. The internal hydrogen bonds are weak, probably in the 3-6 kJ/mol range. A total of about 4400 transitions were assigned for these four forms. The microwave work was guided by quantum chemical calculations at the B3LYP/cc-pVTZ and CCSD/cc-pVTZ levels of theory. These calculations indicated that as many as 18 conformers may exist for 2-propenylhydrazine and 11 of these have either one or two intramolecular hydrogen bonds. The four conformers detected in this work are among the rotamers with the lowest CCSD electronic energies. The CCSD method predicts rotational constants that are very close to the experimental rotational constants. The B3LYP calculations yielded quartic centrifugal distortion constants that deviated considerably from their experimental counterparts in most cases. The calculation of vibration-rotation constants and sextic centrifugal distortion constants by the B3LYP method were generally found to be in poor agreement with the corresponding experimental constants.

Microwave and Quantum Chemical Study of the Hydrazino Group as Proton Donor in Intramolecular Hydrogen Bonding of (2-Fluoroethyl)hydrazine (FCH2CH2NHNH2).

The microwave spectrum of (2-fluoroethyl)hydrazine (FCH2CH2NHNH2) was studied in the 11-123 GHz spectral region to investigate the ability of the hydrazino group to form intramolecular hydrogen bonds acting as a proton donor. This group can participate both in five-member and in six-member internal hydrogen bonds with the fluorine atom. The spectra of four conformers were assigned, and the rotational and centrifugal distortion constants of these rotameric forms were determined. Two of these conformers have five-member intramolecular hydrogen bonds, while the two other forms are without this interaction. The internal hydrogen bonds in the two hydrogen-bonded forms are assumed to be mainly electrostatic in origin because the N-H and C-F bonds are nearly parallel and the associated bond moments are antiparallel. This is the first example of a gas-phase study of a hydrazine where the hydrazino functional group acts as a proton donor in weak intramolecular hydrogen bonds. Extensive quantum chemical calculations at the B3LYP/cc-pVTZ, MP2/cc-pVTZ, and CCSD/cc-pVQZ levels of theory accompanied and guided the experimental work. These calculations predict the existence of no less than 18 conformers, spanning a CCSD internal energy range of 15.4 kJ/mol. Intramolecular hydrogen bonds are predicted to be present in seven of these conformers. Three of these forms have six-member hydrogen bonds, while four have five-member hydrogen bonds. The three lowest-energy conformers have five-member internal hydrogen bonds. The spectrum of the conformer with the lowest energy was not assigned because it has a very small dipole moment. The CCSD relative energies of the two hydrogen-bonded rotamers whose spectra were assigned are 1.04 and 1.62 kJ/mol, respectively, whereas the relative energies of the two conformers with assigned spectra and no hydrogen bonds have relative energies of 6.46 and 4.89 kJ/mol.

Rotational Spectrum, Conformational Composition, and Quantum Chemical Calculations of Cyanomethyl Formate (HC(O)OCH2C≡N), a Compound of Potential Astrochemical Interest.

The rotational spectrum of cyanomethyl formate (HC(O)OCH2C≡N) has been recorded in the 12­123 GHz spectral range. The spectra of two conformers were assigned. The rotamer denoted I has a symmetry plane and two out-of plane hydrogen atoms belonging to the cyanomethyl (CH2CN) moiety. In the conformer called II, the cyanomethyl group is rotated 80.3° out of this plane. Conformer I has an energy that is 1.4(6) kJ/mol lower than the energy of II according to relative intensity measurements. A large number of rotational transitions have been assigned for the ground and vibrationally excited states of the two conformers and accurate spectroscopic constants have been obtained. These constants should predict frequencies of transitions outside the investigated spectral range with a very high degree of precision. It is suggested that cyanomethyl formate is a potential interstellar compound. This suggestion is based on the fact that its congener methyl formate (HC(O)OCH3) exists across a large variety of interstellar environments and the fact that cyanides are very prevalent in the Universe. The experimental work has been augmented by high-level quantum chemical calculations. The CCSD/cc-pVQZ calculations are found to predict structures of the two forms that are very close to the Born­Oppenheimer equilibrium structures. MP2/cc-pVTZ predictions of several vibration­rotation interaction constants were generally found to be rather inaccurate. A gas-phase reaction between methyl formate and the cyanomethyl radical CH2CN to produce a hydrogen atom and cyanomethyl formate was mimicked using MP2/cc-pVTZ calculations. It was found that this reaction is not favored thermodynamically. It is also conjectured that the possible formation of cyanomethyl formate might be catalyzed and take place on interstellar particles.

Ring planarity problem of 2-oxazoline revisited using microwave spectroscopy and quantum chemical calculations.

In a previous infrared, Raman, and microwave spectroscopic work,1 it was claimed that 2-oxazoline has a planar ring equilibrium conformation, and the ring-puckering potential function V(z) = 22.2(z(4) + 1.31z(2)) cm(-1), where z is a dimensionless reduced coordinate, was derived. This function poorly reproduces the rotational constants of the lowest and most important puckering states. The microwave spectrum has been reinvestigated and largely extended to include more than 4600 transitions of the ground state and six excited states of the ring-puckering vibration allowing accurate centrifugal distortion constants to be obtained for the first time. A new potential function V(z) = 38.8(z(4) - 0.65z(2)) cm(-1) has been determined. This function yields much better agreement between calculated and observed rotational constants, especially for the lowest puckering states, than the previous function and predicts a nonplanar ring equilibrium conformation. The barrier to ring planarity is determined to be 49(8) J/mol. The ground-state energy level is 35 cm(-1) above the barrier maximum. Theory predicts that three of the five Watson centrifugal distortion constants, ΔJK, ΔK, and δK, should vary with the puckering state, whereas ΔJ and δJ should be unaffected. It was found that ΔJK and ΔK indeed behave in the expected manner, while deviations were seen for the three other centrifugal distortion constants. The ab initio methods HF, MP2, CCSD, CCSD(T), and CCSD(T)-F12 with large basis sets as well as several DFT methods were used in an attempt to reproduce the low experimental barrier to the planar ring. Only the MP2 method yielded a satisfactory prediction of the barrier. The CCSD and the CCSD(T) calculations predict a planar ring, whereas the energy differences between a planar and a nonplanar ring obtained in the CCSD(T)-F12 computations are so small that a definite conclusion cannot be drawn.

Conformational properties of cis- and trans-N-Cyclopropylformamide studied by microwave spectroscopy and quantum chemical calculations.

The microwave spectra of cis- and trans-N-cyclopropylformamide, C3H5NHC(═O)H, have been investigated in the 31-123 GHz spectral region at room temperature. Rotational isomerism about the Cring-N bond is possible for both cis and trans. MP2/cc-pVTZ and CCSD/cc-pVTZ calculations indicate that there are two conformers in the case of cis, called Cis I and Cis II, while only one rotamer, denoted Trans, exists for trans-N-cyclopropylformamide. The quantum chemical methods predict that Cis I has an electronic energy that is 8-9 kJ/mol higher than the energy of Cis II. The CCSD H-Cring-N-H dihedral angle is 0.0° in Cis I, 93.0° in Cis II and 79.9° in Trans. The CCSD and MP2 calculations predict a slightly nonplanar structure for the amide moiety in both Trans and Cis II, whereas Cis I is computed to have a planar amide group bisecting the cyclopropyl ring. Surprisingly, the MP2 and CCSD methods predict practically the same energy for Trans and Cis II. The spectra of Cis II in the ground state and in two vibrationally excited states were assigned, while the spectrum of Cis I was not found presumably because of a low Boltzmann population due to a relatively large energy difference (8-9 kJ/mol). The spectra of the ground vibrational state and seven vibrationally excited states of Trans, were assigned. Vibrational frequencies of several of the excited state of both Cis II and Trans were determined by relative intensity measurements. The experimental and CCSD rotational constants are in satisfactory agreement. The MP2 values of the quartic centrifugal distortion constants of both species are in relatively poor agreement with their experimental counterparts. The MP2 vibration-rotation constants and sextic centrifugal distortion constants have little resemblance with the corresponding experimental values.

Microwave and quantum-chemical study of conformational properties and intramolecular hydrogen bonding of 2-hydroxy-3-butynenitrile (HC≡CCH(OH)C≡N).

The microwave spectra of 2-hydroxy-3-butynenitrile, HC≡CCH(OH)C≡N, and a deuterated species, HC≡CCH(OD)C≡N, have been investigated in the 38-120 GHz spectral region. Three rotameric forms, each stabilized by intramolecular hydrogen bonds, are possible for this compound. The hydrogen atom of the hydroxyl group is hydrogen-bonded to the π electrons of the alkynyl group in one of these conformers, to the π electrons of the cyano group in the second rotamer, and to both of these groups simultaneously in the third conformer. The microwave spectra of the parent and deuterated species of last-mentioned form have been assigned, and accurate values of the rotational and quartic centrifugal distortion constants of these species have been determined. The spectra of two vibrational excited states of this conformer have also been assigned, and their frequencies have been determined by relative intensity measurements. Quantum-chemical calculations at the MP2/cc-pVTZ and CCSD/cc-pVQZ levels were performed to assist the microwave work. The theoretical predictions were generally found to be in good agreement with observations.

Synthesis, microwave spectrum, quantum chemical calculations, and conformational composition of the novel compound cyclopropylethylidynephosphine (C3H5CH2C≡P).

The synthesis of the novel compound cyclopropylethylidynephosphine (C3H5CH2C≡P) and its microwave spectrum are reported together with quantum chemical calculations. The spectrum, which reveals the existence of two conformers, has been recorded in the 38-109 GHz spectral range at room temperature. The H-C-CH2-C chain of atoms is synclinal in one rotamer denoted sc, and antiperiplanar in the second conformer called ap. The spectra of the ground vibrational state and two vibrationally excited states were assigned for each rotamer. The vibrational frequencies of these excited states were determined by relative intensity measurements. Relative intensity measurements were also conducted to determine the energy difference between ap and sc. The latter conformer was found to be the lower-energy form and E(ap) - E(sc) was determined to be 0.9(4) kJ/mol. The microwave study has been augmented by quantum chemical calculations at the CCSD/cc-pVQZ and MP2/cc-pVTZ levels of theory. The CCSD predictions were generally in good agreement with experiment, while somewhat mixed results were obtained in the MP2 calculations.

Microwave spectrum and conformational composition of (azidomethyl)cyclopropane (C3H5CH2N3).

The microwave spectrum of (azidomethyl)cyclopropane, C3H5CH2N3, has been investigated in the 26-90 GHz spectral range at a temperature of about -30 °C. Five rotameric forms of this compound, whose spectra can be distinguished by microwave spectroscopy, may exist. The spectra of three of them denoted III, IV, and V were assigned. The ground vibrational state spectra of III and V were assigned, while the ground and six vibrationally excited states were assigned for IV. These three rotamers all have a synclinal orientation of the H-C-C-N chain of atoms, while the C-C-N-N link is either + or - synclinal or antiperiplanar. Conformer IV, having synclinal orientation of the two said dihedral angles, was found to have the lowest energy by relative intensity measurements. Rotamer V has an energy that is 1.6(6) kJ/mol higher than the energy of IV, while the energy of III is 2.1(6) kJ/mol higher than the energy of IV. Quantum chemical calculations were performed at the MP2/cc-pVTZ and CCSD/cc-pVTZ levels of theory. The rotational constants obtained in the CCSD calculations are in good agreement with the experimental rotational constants, while the MP2 centrifugal distortion constants are generally in poorer agreement with their experimental counterparts.

Synthesis, microwave spectrum, quantum chemical calculations, and conformational composition of a novel primary phosphine, cyclopropylethynylphosphine, (C3H5C≡CPH2).

The microwave spectrum of cyclopropylethynylphosphine, C3H5C≡CPH2, has been investigated in the 26-120 GHz spectral region. The spectrum is dominated by very rich and complex a-type R-branch pile-ups. There must be insignificant steric interaction between the phosphino group and the cyclopropyl ring due to the long distance between these two groups. However, the phosphino group does not undergo free or nearly free internal rotation. Instead, the spectra of two distinct conformers were assigned. Both these two forms have CS symmetry. The symmetry plane bisects the cyclopropyl ring and the phosphino group in both conformers, and the lone electron pair of the phosphino group points in opposite directions in the two rotamers. The energy difference between the two forms was determined to be 1.9(6) kJ/mol. A simple model that takes into consideration the interaction of the lone electron pair of the phosphino group with the π-electrons of the ethynyl group and the Walsh electrons of the cyclopropyl ring is able to give a qualitative explanation of the observation of two conformers and the nonexistence of free rotation of the phosphino group. The MW work was augmented by quantum chemical calculations using second-order Møller-Plesset perturbation and coupled cluster theory with results that are in good agreement with the experiments.

Microwave spectrum and intramolecular hydrogen bonding of 2-isocyanoethanol (HOCH(2)CH(2)N≡C).

The microwave spectrum of 2-isocyanoethanol (HOCH2CH2NC) has been investigated in the 12-120 GHz spectral range. The assignment of this spectrum was severely complicated by the rapid transformation of 2-isocyanoethanol into its isomer 2-oxazoline, which has a rich and strong spectrum. This process appeared both in a gold-plated microwave cell and in a brass cell and is presumed to be catalyzed by metals or traces of base. The spectrum of one conformer was ultimately assigned. This form is stabilized by an intramolecular hydrogen bond between the hydroxyl group and the isocyano group and is the first gas-phase study ever of this kind of hydrogen bonding. The distance between the hydrogen atom of the hydroxyl group and the nitrogen and carbon atoms are as long as 256 and 298 pm, respectively, indicating that covalent contribution to the hydrogen bond is minimal. Electrostatic forces are much more important because the O-H and N≡C bonds are almost parallel and the corresponding bond moments are practically antiparallel. The microwave work has been augmented by quantum chemical calculations at the CCSD(T)/cc-pVTZ and MP2/cc-pVTZ levels of theory. Results of these calculations are generally in good agreement with experimental findings.

Microwave spectrum, conformational composition, and dipole moment of (fluoromethyl)cyclopropane (C3H5CH2F).

The microwave spectrum of (fluoromethyl)cyclopropane, C3H5CH2F, has been investigated in the whole 12-75.6 GHz spectral range. Many measurements were also performed in the 75.6-120 GHz region. The spectra of two conformers were assigned. The H-C-C-F chain of atoms is antiperiplanar in the conformer denoted ap and synclinal in the sc rotamer. The sc conformer has a lower energy than ap. The internal energy difference was determined to be E(ap) - E(sc) = 1.7(8) kJ/mol from relative intensity measurements. The spectra of the ground vibrational state and seven vibrationally excited states belonging to two different normal modes were assigned for sc. The frequencies of these two modes were determined by relative intensity measurements. The dipole moment of this conformer was determined to be µ(a) = 5.520(17), µ(b) = 3.475(29), µ(c) = 0.35(13), and µ(TOT) = 6.532(40) × 10(-30) C m [1.958(12) D]. The spectrum of the ground vibrational state was assigned for ap. The microwave work was supported by quantum chemical calculations at the CCSD/cc-pVQZ, MP2/cc-pVTZ, and B3LYP/cc-pVTZ levels of theory.

Microwave spectrum and conformational properties of 4-isocyano-1-butene (H2C═CHCH2CH2N≡C).

The microwave spectrum of 4-isocyano-1-butene (H2C═CHCH2CH2NC) has been investigated in the 35-80 GHz spectral region. Selected measurements have also been made outside this spectral range. Rotation about the -CH-CH2- and -CH2-CH2- single bonds may produce rotational isomerism resulting in five conformers. The spectra of three of them, denoted I, III, and IV, have been assigned. In conformer I, the C═C-C-C link of atoms is +anticlinal and the C-C-C-N chain is antiperiplanar. In III, the two links of atoms are +anticlinal and +synclinal, whereas in IV, the two chains are synperiplanar and antiperiplanar, respectively. Conformer I was found to have the lowest energy of the three forms by relative intensity measurements. These measurements yielded EIII - EI = 1.1(7) kJ/mol, and EIV - EI = 2.9(7) kJ/mol for the internal energy differences. The microwave study was augmented by quantum chemical calculations at the CCSD/cc-pVQZ and MP2/cc-pVTZ levels of theory. Good agreement between experimental and theoretical results was seen in most cases.

Microwave spectrum and conformational properties of 4-isocyano-1-butyne (HC≡CCH2CH2N≡C).

The microwave spectrum of 4-isocyano-1-butyne (HC≡CCH2CH2N≡C) has been investigated in the 12.4-77.6 GHz spectral region. The spectra of two rotamers denoted ap and sc were assigned. ap has an antiperiplanar arrangement for the C-C-C-N chain of atoms, whereas sc has synclinal conformation for this link. The ground state spectrum and three vibrationally excited state spectra of the lowest torsional vibration were assigned for ap, while the ground vibrational state spectrum was assigned for sc. The C-C-C-N dihedral angle was found to be 64.5(30)° in sc and exactly 180° in ap. ap was determined to be 2.9(6) kJ/mol lower in energy than sc from relative intensity measurements. The microwave study has been augmented with ab initio and DFT calculations employing the CCSD(T), MP2, and B3LYP methods with the cc-pVTZ basis set. A Natural Bond Order analysis has also been performed. Most, but not all, of the quantum chemical predictions agree satisfactorily with the experimental results.

Microwave spectrum, conformational properties, and dipole moment of cyclopropylmethyl isocyanide (C3H5CH2NC).

The microwave spectrum of cyclopropylmethyl isocyanide, C3H5CH2NC, has been investigated in the 25-75 GHz spectral range. The spectra of two conformers were assigned. The H-C-C-N chain of atoms is antiperiplanar in the conformer denoted ap and synclinal in the sc rotamer. The sc conformer tends to be slightly more stable than the ap form. The internal energy difference was determined to be Eap - Esc = 0.2(7) kJ/mol from relative intensity measurements. The spectra of the ground vibrational state and six vibrationally excited states belonging to two different normal vibrations were assigned for sc. The frequencies of these two modes were determined by relative intensity measurements. The dipole moment of this conformer was determined to be µa = 12.16(6), µb = 5.91(4), µc = 0 (preset), and µtot = 13.52(6) × 10(-30) C m [4.05 (2) debye]. The spectra of the ground and of two vibrationally excited states belonging to the torsion and lowest bending vibration were assigned for ap. The microwave work was supported by quantum chemical calculations at the CCSD/cc-pVTZ and B3LYP/cc-pVTZ levels of theory. Most, but not all, of the theoretical predictions are in good agreement with experiment.

Synthesis, microwave spectrum, and conformational properties of 2-fluoroethyl azide (FCH2CH2N3).

A novel synthesis producing neat 2-fluoroethyl azide (FCH2CH2N3) is described. A conformational analysis using microwave spectroscopy augmented by quantum chemical calculations at the CCSD(T)/cc-pVTZ, B3LYP/aug-cc-pVTZ, and B3LYP/cc-pVTZ levels of theory has been performed for this compound. The spectra of the ground vibrational state and two vibrationally excited states of one rotameric form were assigned. A large number of transitions was assigned, and very accurate values were obtained for the rotational and quartic centrifugal distortion constants. The identified conformer has synclinal orientations for the F-C-C-N and C-C-N-N chains of atoms bringing the fluorine atom and the azido group into close proximity. It is concluded from consideration of absolute intensities that this conformer is indeed the preferred form of the molecule in accord with the theoretical calculations. The experimental and CCSD(T) rotational constants are in very good agreement, whereas much larger discrepancies were seen for the experimental and B3LYP quartic centrifugal distortion constants.

Microwave spectra, planarity, and conformational preferences of cis- and trans-N-vinylformamide.

The microwave spectra of a mixture of cis- and trans-H-N-C-O forms of N-vinylformamide, (H(2)C═CHNHC(═O)H), have been measured at room temperature in the 18-75 GHz spectral range. The spectra of two forms were assigned. The first of these forms has a cis arrangement for the H-N-C-O chain of atoms, whereas the second form has a trans arrangement. The C-C-N-C chain of atoms is antiperiplanar (180°) in both forms. The inertial defect of the ground vibrational state of cis is -0.142(5) × 10(-20) u m(2), whereas this parameter is -0.087098(26) × 10(-20) u m(2) for trans. It is concluded that the equilibrium structures of both cis and trans are completely planar. The dipole moment determined from Stark effect measurements is µ(a) = 9.96(8), µ(b) = 2.22(3), µ(c) = 0 (by symmetry), and µ(tot) = 10.20(8) × 10(-30) C m [3.06(2) D], for cis, and µ(a) = 7.64(16), µ(b) = 9.24(10), µ(c) = 0 (by symmetry), and µ(tot) = 12.0(2) × 10(-30) C m [3.59(5) D] for trans. The spectrum of one vibrationally excited state, presumably the first excited state of the torsion about the C-N bond of cis, was assigned and the frequency of this state was determined to be 76(15) cm(-1) by relative intensity measurements. The spectra of two vibrationally excited states of trans were assigned. These states are assumed to be the first excited state of the torsion about the C-N bond, and a low bending vibration. Relative intensity measurements yielded 101(20) and ca. 300 cm(-1), respectively, for the frequencies of these normal vibrations. Accurate values of the quartic centrifugal distortion constants, the dipole moments, and the vibration-rotation constants have been obtained for both cis and trans. The experimental work has been augmented by high-level quantum chemical calculations at the B3LYP/cc-pVTZ and CCSD(T)/cc-pVTZ levels of theory. The theoretical calculation performed without symmetry restrictions correctly predict that cis and trans are both planar. The CCSD(T) rotational constants are in excellent agreement with their experimental counterparts, whereas the B3LYP quartic centrifugal distortion constants and the vibration-rotation constants are in fairly good agreement with experiments. The CCSD(T) dipole moments deviate more than expected from the experimental dipole moments. It is estimated that further conformers of cis and trans must be at least 4 kJ/mol higher in energy.

Microwave spectra and barriers to internal rotation of Z- and E-1-propenyl isocyanide.

A synthetic procedure yielding a mixture of Z- and E-1-propenyl isocyanide (CH(3)CH═CHNC) is described. The microwave spectrum of this mixture has been recorded in the 12-100 GHz spectral range, and the spectra of the Z and E isomers have been assigned for the first time. Most transitions of the Z form were split into two components of equal intensity due to tunneling of the methyl group, which allowed the barrier to internal rotation of this group to be determined as 4.0124(12) kJ/mol by fitting 568 transitions with a maximum value of J = 46 using the computer program Xiam. This fit had a root-mean-square deviation as large as 4.325. The same transitions were therefore fitted anew using the more sophisticated program Erham. This fit has a rms deviation marginally better (4.136) than the Xiam fit. No split MW lines were found for E-1-propenyl isocyanide. The absence of splittings is ascribed to a barrier to internal rotation of the methyl group that is significantly higher than the barrier of the Z isomer. It is concluded that the barrier must be larger than 6 kJ/mol for the E form. The experimental work was augmented by quantum chemical calculations at CCSD/cc-pVTZ, B3LYP/cc-pVTZ, and MP2/cc-pVTZ levels of theory. The CCSD method predicts rotational constants of the Z and E forms well. The B3LYP barriers to internal rotation of a series of substituted propenes were calculated and found to be in good agreement with experiments. Calculations of the quartic centrifugal distortion constants of the two 1-propenyl isocyanides by the B3LYP and MP2 methods were less successful.