Microwave, r0 Structural Parameters, Conformational Stability, and Vibrational Assignment of (Chloromethyl)fluorosilane.

The FT-microwave spectrum (6.5-26 GHz) of (chloromethyl)fluorosilane (ClCH2-SiH2F) has been recorded and 250 transitions for the parent species along with (13)C, (37)Cl, (29)Si, and (30)Si isotopologues have been assigned for trans conformer. Infrared spectra (3100 to 400 cm(-1)) of gas, solid, and the variable temperature (-100 to -60 °C) studies of the infrared spectra of the sample dissolved in xenon have been recorded. Additionally, the variable temperature (-153 to -133 °C) studies of the Raman spectra of the sample dissolved in krypton have been recorded. The enthalpy difference between the trans and gauche conformers in xenon solutions has been determined to be 109 ± 15 cm(-1) (1.47 ± 0.16 kJ mol(-1)), and in krypton solution, the enthalpy difference has been determined to be 97 ± 16 cm(-1) (1.16 ± 0.19 kJ mol(-1)) with the trans conformer as the more stable form. Approximately 46 ± 2% of the trans form is present at ambient temperature. By utilizing the microwave rotational constants of five isotopologues for trans and the structural parameters predicted from MP2(full)/6-311+G(d,p) calculations, adjusted r0 parameters have been obtained for trans conformer. The r0 structural parameter values for the trans form are for the heavy atom distances (Å): Si-F = 1.608 (3); C-Cl = 1.771 (3); Si-C = 1.884 (3); and angles (deg): ∠FSiC = 108.9 (5); ∠ClCSi = 104.9 (5). The results are discussed and compared to some related molecules.

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, infrared and Raman spectra, r0 structural parameters, ab initio calculations and vibrational assignment of 1-fluoro-1-silacyclopentane.

The microwave spectrum (6500-18 ,500 MHz) of 1-fluoro-1-silacyclopentane, c-C(4)H(8)SiHF has been recorded and 87 transitions for the (28)Si, (29)Si, (30)Si, and (13)C isotopomers have been assigned for a single conformer. Infrared spectra (3050-350 cm(-1)) of the gas and solid and Raman spectrum (3100-40 cm(-1)) of the liquid have also been recorded. The vibrational data indicate the presence of a single conformer with no symmetry which is consistent with the twist form. Ab initio calculations with a variety of basis sets up to MP2(full)/aug-cc-pVTZ predict the envelope-axial and envelope-equatorial conformers to be saddle points with nearly the same energies but much lower energy than the planar conformer. By utilizing the microwave rotational constants for seven isotopomers ((28)Si, (29)Si, (30)Si, and four (13)C) combined with the structural parameters predicted from the MP2(full)/6-311+G(d,p) calculations, adjusted r(0) structural parameters have been obtained for the twist conformer. The heavy atom distances in Å are: r(0)(SiC(2)) = 1.875(3); r(0)(SiC(3)) = 1.872(3); r(0)(C(2)C(4)) = 1.549(3); r(0)(C(3)C(5)) = 1.547(3); r(0)(C(4)C(5)) = 1.542(3); r(0)(SiF) = 1.598(3) and the angles in degrees are: [angle]CSiC = 96.7(5); [angle]SiC(2)C(4) = 103.6(5); [angle]SiC(3)C(5) = 102.9(5); [angle]C(2)C(4)C(5) = 108.4(5); [angle]C(3)C(5)C(4) = 108.1(5); [angle]F(6)Si(1)C(2) = 110.7(5); [angle]F(6)Si(1)C(3) = 111.6(5). The heavy atom ring parameters are compared to the corresponding r(s) parameters. Normal coordinate calculations with scaled force constants from MP2(full)/6-31G(d) calculations were carried out to predict the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization values, and infrared band contours. These experimental and theoretical results are compared to the corresponding quantities of some other five-membered rings.

Conformational stability from variable-temperature infrared spectra of xenon solutions, r0 structural parameters, and vibrational assignment of pyrrolidine.

The infrared spectra of gaseous and variable-temperature liquid xenon solutions of pyrrolidine have been recorded. The enthalpy difference has been determined to be 109 ± 11 cm(-1) (1.30 ± 0.13 kJ mol(-1)) with the envelope-equatorial conformer more stable than the twist form with 37 ± 3% present at ambient temperature. Ab initio calculations utilizing various basis sets up to MP2(full)/aug-cc-pVTZ have been used to predict the conformational stabilities, energy at the equatorial-axial saddle point, and barriers to planarity. From previously reported microwave rotational constants along with MP2(full)/6-311+G(d,p) predicted structural values, adjusted r(0) parameters have been obtained for both conformers. Heavy atom distances (Å) of equatorial[twist] conformer are as follows: N(1)-C(2) = 1.469(3)[1.476(3)], N(1)-C(3) = 1.469(3)[1.479(3)], C(2)-C(4) = 1.541(3)[1.556(3)], C(3)-C(5) = 1.541(3)[1.544(3)], C(4)-C(5) = 1.556(3)[1.543(3)]; and angles (deg)∠N(1)C(2)C(4) = 102.5(5)[107.6(5)], ∠N(1)C(3)C(5) = 102.5(5)[105.4(5)], ∠C(2)C(4)C(5) = 104.3(5)[104.6(5)], ∠C(3)C(5)C(4) = 104.3(5)[103.7(5)], ∠C(2)N(1)C(3) = 104.1(5)[103.9(5)], τC(2)C(4)C(5)C(3) = 0.0(5)[13.5(5)]. A complete vibrational assignment is proposed for both conformers.

Conformational stability from variable temperature infrared spectra of xenon solutions, r0 structural parameters, and ab initio calculations of cyclopropylisocyanate.

Infrared spectra (4000 to 400 cm(-1)) of the gas and variable temperature xenon solutions, and the Raman spectrum of the liquid have been recorded for cyclopropylisocyanate. The enthalpy difference has been determined to be 77 ± 8 cm(-1) (0.92 ± 0.10 kJ/mol) with the trans form more stable than the cis conformer with 59 ± 2% present at ambient temperature. By utilizing three rotational constants for each conformer, combined with structural parameters predicted from MP2(full)/6-311+G(d,p) calculations, the adjusted r(0) parameters have been obtained. Heavy atom structural parameters for the trans [cis] conformers are the following: distances (Å) (C-C(2,3)) = 1.509(3) [1.509(3)], (C(2)-C(3)) = 1.523(3) [1.521(3)], (C-N) = 1.412(3) [1.411(3)], (N═C) =1.214(3) [1.212(3)], (C═O) = 1.163(3) [1.164(3)]; angles (°) ∠CCN = 116.7(5) [120.1(5)], ∠CNC = 136.3(5) [137.6(5)]. The centrifugal distortion constants have been predicted from ab initio and DFT calculations and are compared to the experimentally determined values.

Microwave spectrum, r(0) structure, dipole moment, barrier to internal rotation, and Ab initio calculations for fluoromethylsilane.

The microwave spectra of seven isotopomers of fluoromethylsilane, CH(2)FSiH(3), in the ground vibrational state were measured and analyzed in the frequency range 18-40 GHz. The rotational and centrifugal distortion constants were evaluated by the least-squares treatment of the observed frequencies of a- and b-type R- and b-type Q-transitions. The values for the components of the dipole moment were obtained from the measurements of Stark effects from both a- and b-type transitions and the determined values are: |mu(a)| = 1.041(5), |mu(b)| = 1.311(6), and |mu(t)| = 1.674(4) D. Structural parameters have been determined and the heavy atom distances (r(0)) in Angstroms are: Si-C = 1.8942(57) and C-F = 1.4035(55) and the angle in degree, angleSiCF = 109.58(14). A semi-experimental r(e) structure was also determined from experimental ground state rotational constants and vibration-rotation constants derived from ab initio force fields. The internal torsional fundamental, SiH(3), was observed at 149.2 cm(-1) with two accompanying hot bands at 138.8 and 127.5 cm(-1). The barrier to internal rotation was obtained as 717.3(16) cm(-1) (2.051(46) kcal mol(-1)) by combining the analysis of the microwave A and E splittings and the torsional fundamental and hot band frequencies. Ab initio calculations have been carried out with full electron correlation by the second-order perturbation method with several different basis sets up to MP2/6-311+G(d,p) to obtain geometrical parameters, barriers to internal rotation, and centrifugal distortion constants. Adjusted r(0) structural parameters have been obtained by combining the ab initio MP2/6-311+G(d,p) predicted values with the determined rotational constants for the fluoride as well as with the previously reported microwave data for the chloro- and bromo- compounds. These experimental results are compared to the corresponding parameters for the carbon analogues.

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.

Conformational stability from rare gas solutions, r0 structural parameters, barriers to internal rotation, and ab initio calculations for vinyl silyl fluoride.

The Raman (3300-10 cm(-1)) and infrared (3300-40 cm(-1)) spectra of gaseous and solid vinyl silyl fluoride, CH(2)=CHSiH(2)F, have been recorded. Raman spectrum of the liquid has also been recorded and depolarization values obtained. Variable-temperature studies of the infrared spectra of the sample dissolved in liquid krypton (-110 to -150 degrees C) and liquid xenon (-60 to -100 degrees C) have been carried out. From these studies, the enthalpy difference has been determined to be 76 +/- 7 cm(-1) (0.91 +/- 0.08 kJ/mol) from the krypton solutions and 69 +/- 7 cm(-1) (0.82 +/- 0.08 kJ/mol) from the xenon solutions, with the gauche conformer the more stable form. From the far-infrared spectrum of the gas, the asymmetric torsional fundamentals for the cis and gauche conformers have been observed at 102.34 and 86.56 cm(-1), respectively, with each having several "hot bands" falling to lower frequencies. From these frequencies along with the experimentally determined conformational enthalpy difference, as well as the gauche skeletal dihedral angle, the potential function governing the conformational interchange has been determined with the following Fourier cosine potential coefficients: V(1) = -80 +/- 11, V(2) = -42 +/- 15, V(3) = 622 +/- 5, V(4) = 34 +/- 5, and V(6) = -31 +/- 2 cm(-1). The gauche-to-cis and gauche-to-gauche barriers are 664 cm(-1) (7.94 kJ/mol) and 608 cm(-1) (7.27 kJ/mol), respectively. Complete vibrational assignments are provided for both conformers. In addition, equilibrium geometries and electronic energies have been determined for both rotamers from ab initio calculations using restricted Hartree-Fock and Møller-Plesset perturbation method to the second order (MP2), as well as density functional theory by the B3LYP methods, employing a number of basis sets up to 6-311+G(2df,2pd). All levels of calculation predict the gauche conformer to be the more stable form. By systematically adjusting the ab initio predicted structural values to fit the previously reported microwave rotational constants, adjusted r(0) parameters have been obtained for both conformers. These values are compared to those for the corresponding chloride and methyl compounds. The spectroscopic and theoretical results are discussed and compared to the corresponding quantities for some similar molecules.

Conformational stability, r0 structural parameters, ab initio calculations, and vibrational assignment for fluorocyclopentane.

The infrared spectra (3200-50 cm(-1)) of the gas and solid and the Raman spectrum (3200-30 cm(-1)) of liquid and solid fluorocyclopentane, c-C5H9F, have been recorded. Additionally the infrared spectra (3200-400 cm(-1)) of liquid xenon solutions have been recorded at -65 and -95 degrees C. In all of the physical states, only the twisted C(1) conformer was detected. Ab initio calculations utilizing various basis sets up to MP2(full)/6-311+G(2df,2pd) with and without diffuse functions have been used to predict the conformational stabilities. These calculations predict only the twisted C1 conformer as the stable form. The two envelope (C(s) symmetry) forms with axial and equatorial structures were predicted to be first order saddle points with average higher energies of 75 +/- 33 and 683 +/- 44 cm(-1), respectively, from the C1 conformer but lower energies of 2442 and 1812 cm(-1), respectively, than the planar form by MP2 calculations. Similar values were obtained from the corresponding density functional theory calculations by the B3LYP method. A complete vibrational assignment is given for the twisted (C1) conformer which is supported by normal coordinate calculations with scaled force constants from MP2(full)/6-31G(d) calculations. The adjusted r0 structural parameters have been obtained by systematically fitting the MP2(full)/6-311+G(d,p) predicted values with the rotational constants obtained from a microwave study. The determined heavy atom r0 distances in A are (C1C2) = 1.531(3), (C1C3) = 1.519(3), (C2C4) = 1.553(3), (C3C5) = 1.533(3), (C4C5) = 1.540(3), and (C1F6) = 1.411(3) and the angles in degrees are angle C3C1C2 = 105.5(5), angle C1C2C4 = 106.2(5), angle C1C3C5 = 102.9(5), angle F6C1C2 = 108.9(5), and angle F6C1C3 = 107.6(5) with a dihedral angle angle C2C4C5C3 = 25.3(3). These experimental and theoretical results are compared to the corresponding quantities of some similar molecules.

Microwave spectra and barrier to internal rotation in cyclopropylmethylsilane.

Rotational spectra for 3 silicon isotopologues (28Si, 29Si, 30Si) of cyclopropylmethylsilane (c-C3H5SiH2CH3) have been observed in natural abundance using Fourier-transform microwave spectroscopy, and the dipole moment of the most abundant (28Si) isotopologue has been determined using the Stark effect. The observed rotational constants (A = 8800.5997(9) MHz; B = 2238.6011(3) MHz; C = 2001.0579(3) MHz) and dipole moment components (mu(a) = 0.195(2) D, mu(b) = 0.674(11) D, mu(c) = 0.362(19) D, mu(total) = 0.790(13) D) for the 28Si species are consistent with ab initio predictions (MP2/6-311+G(d)) for a gauche conformation about the Si-cyclopropyl bond. All of the observed transitions were split into doublets due to internal rotation of the methyl group, allowing a determination of the V3 barrier to internal rotation of 6.671(9) kJ mol(-1) for the most abundant isotopologue. This barrier will be compared to those for other Si-CH(3) containing compounds and will be related to a partial structure determination from the available microwave and ab initio data.

Conformational stability from variable temperature FT-IR spectra of krypton solutions, r0 structural parameters, vibrational assignment, and ab initio calculations of 4-fluoro-1-butene.

Variable temperature (-115 to -155 degrees C) studies of the infrared spectra (3200-400 cm-1) of 4-fluoro-1-butene, CH2=CHCH2CH2F, dissolved in liquid krypton have been carried out. The infrared spectra of the gas and solid as well as the Raman spectra of the gas, liquid, and solid have also been recorded from 3200 to 100 cm-1. From these data, an enthalpy difference of 72 +/- 5 cm-1 (0.86 +/- 0.06 kJ x mol-1) has been determined between the most stable skew-gauche II conformer (the first designation refers to the position of the CH2F group relative to the double bond, and the second designation refers to the relative positions of the fluorine atom to the C-C(=C) bond) and the second most stable skew-trans form. The third most stable conformer is the skew-gauche I with an enthalpy difference of 100 +/- 7 cm-1 (1.20 +/- 0.08 kJ x mol-1) to the most stable form. Larger enthalpy values of 251 +/- 12 cm-1 (3.00 +/- 0.14 kJ x mol-1) and 268 +/- 17 cm-1 (3.21 +/- 0.20 kJ x mol-1) were obtained for the cis-trans and cis-gauche conformers, respectively. From these data and the relative statistical weights of one for the cis-trans conformer and two for all other forms, the following conformer percentages are calculated at 298 K: 36.4 +/- 0.9% skew-gauche II, 25.7 +/- 0.1% skew-trans, 22.5 +/- 0.2% skew-gauche I, 10.0 +/- 0.6% cis-gauche, and 5.4 +/- 0.2% cis-trans. The potential surface describing the conformational interchange has been analyzed and the corresponding two-dimensional Fourier coefficients were obtained. Nearly complete vibrational assignments for the three most stable conformers are proposed and some fundamentals for the cis-trans and the cis-gauche conformers have been identified. The structural parameters, dipole moments, conformational stability, vibrational frequencies, infrared, and Raman intensities have been predicted from ab initio calculations and compared to the experimental values when applicable. The adjusted r0 structural parameters have been determined by combining the ab initio predicted parameters with previously reported rotational constants from the microwave data. These experimental and theoretical results are compared to the corresponding quantities of some similar molecules.

Conformations of allyl amine: theory vs experiment.

The relative stabilities of the five conformers of allyl amine, a medium-size aliphatic molecule, were estimated by applying ab initio quantum mechanical methods at several levels of theory. The second-order Møller-Plesset perturbation method (MP2), quadratic configuration interaction including single and double excitations (QCISD), coupled-cluster with single and double excitations (CCSD) and CCSD plus perturbative triple excitations [CCSD(T)] were applied. The Dunning correlation consistent basis sets (through aug-cc-pVQZ and cc-pV5Z) were employed. The MP2 energies relative to the energy of the cis-trans conformer reported here appear to approach the basis set limit. The predicted allyl amine conformer energies approaching the Hartree-Fock basis set limit are 158 cm-1 (cis-gauche), -5 cm-1 (gauche-trans), and -146 cm-1 (gauche-gauche). The same three relative energies near the MP2 basis set limit are 135, 103, and 50 cm-1, respectively. The analogous energies deduced from experiment are 173 +/- 12, 92 +/- 8, and 122 +/- 5 cm-1. The theoretical results obtained in the present study suggest that satisfactory predictions of the conformer energetics of allyl amine may be achieved only by theoretical methods that incorporate consideration of correlation effects in conjunction with large basis sets. Evaluation of the zero-point vibrational energy corrections is critical, due to the very small classical energy differences between the five conformers of allyl amine. Agreement between theory and experiment for the gauche-gauche conformational energy remains problematical.

Vibrational spectrum, conformational stability, structural parameters and ab initio calculations of dimethylaminodifluorophosphine.

From analysis of the infrared and Raman spectra along with support from the ab initio predictions it is concluded that there is only one stable conformer of dimethylaminodifluorophosphine, (CH(3))(2)NPF(2), in the gaseous and liquid phases which has a planar PNC(2) moiety with C(s) symmetry. The adjusted r(0) structural parameters have been obtained by combining the MP2(full)/6-311+G(d) predicted values with the previous reported rotational constants for four isotopomers obtained from previously reported microwave studies. The difference in the two NC distances is 0.002A whereas, these two parameters were previously assumed to have the same values from the microwave and electron diffraction studies but a reported difference of 0.025A from the structural parameters of the crystal. The adjusted r(0) heavy atom distances and angles are: r(PF)=1.593(3); r(NP)=1.654(3); r(NC(i))=1.455(3); r(NC(o))=1.453(3) A; angleFPF=93.5(5); angleNPF=100.8(5); angleCNC=116.0(5); angleC(i)NP=124.1(5); angleC(o)NP=120.0 degrees . The planar bonding around the nitrogen atom is consistent with the previously reported structural information from the microwave study but differs from the slightly pyramidal bonding obtained in the electron diffraction investigation. To support the vibrational assignment MP2(full) ab initio calculations with the 6-31G(d) basis set were carried out to predict the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization values, infrared band contours, and centrifugal distortion constants. Vibrational assignments are given for (CH(3))(2)NPF(2) and (CD(3))(2)NPF(2) and comparisons are made with the predicted intensities, frequencies and centrifugal distortion constants. Frequencies of some of the lattice modes are reported from both the infrared and Raman spectra with suggested assignments based on the factor group symmetry of the crystal of D(2h)(16) (Pnma) with four molecules per primitive cell. These results are compared to the corresponding quantities of some similar molecules.

Conformational stability of cyclobutanol from temperature dependent infrared spectra of xenon solutions, r0 structural parameters, ab initio calculations and vibrational assignment.

Variable temperature (-55 to -100 degrees C) studies of the infrared spectra (4000-400 cm(-1)) of cyclobutanol, c-C4H7OH dissolved in liquid xenon have been carried out. The infrared spectrum (4000-100 cm(-1)) of the gas has also been recorded. From these data two of the four possible stable conformers have been confidently identified and their order of stabilities has been experimentally determined where the first indicator is for the position of attachment of the hydroxyl group on the bent cyclobutyl ring (Eq=equatorial or Ax=axial) and the second one (t=trans, g=gauche) is the relative position of the hydroxyl rotor, i.e. rotation around the ring C-O bond. The enthalpy difference between the most stable Eq-t conformer and the second most stable rotamer, Eq-g, has been determined to be 200+/-50 cm(-1) (2.39+/-0.60 kJ/mol). This experimentally determined order is consistent with the order of stability predicted by ab initio calculations Eq-t>Eq-g>Ax-g>Ax-t. Evidence was obtained for the third conformer Ax-g which is predicted by ab initio calculations to be less stable by more than 650cm(-1) than the Eq-t form. The percentage of each conformer at ambient temperature is estimated to be Eq-t (50%), Eq-g (47%) and Ax-g (3%). The conformational stabilities, harmonic force fields, infrared intensities, Raman activities, depolarization ratios and vibrational frequencies have been obtained for all of the conformers from MP2(full)/6-31G(d) ab initio calculations. The optimized geometries and conformational stabilities have been obtained from ab initio calculations utilizing several different basis sets up to MP2(full)/aug-cc-pVTZ and from density functional theory calculations by the B3LYP method. By utilizing previously reported microwave rotational constants for the Eq-t conformer combined with ab initio MP2(full)/6-311+G(d,p) predicted structural values, adjusted r0 parameters have been obtained. The determined heavy atom structural parameters for the Eq-t conformer are: the distances C1-C4=1.547(5) angstroms, C4-C6=1.552(5)angstroms, C-O=1.416(5) angstroms and angles angleC6C4C1=86.6(5) degrees , angleC4C1C5=88.9(5) degrees and angleC6C5C1C4=22.8(5) degrees . The results are discussed and compared to the corresponding properties of some similar molecules.

Conformational stability, structural parameters and vibrational assignment from variable temperature infrared spectra of krypton solutions and ab initio calculations of ethylisothiocyanate.

Variable temperature (-105 to -150 degrees C) studies of the infrared spectra (3500-400 cm(-1)) of ethylisothiocyanate, CH(3)CH(2)NCS, dissolved in liquid krypton have been recorded. Additionally the infrared spectra of the gas and solid have been re-investigated. These spectroscopic data indicate a single conformer in all physical states with a large number of molecules in the gas phase at ambient temperature in excited states of the CN torsional mode which has a very low barrier to conformational interchange. To aid in the analyses of the vibrational and rotational spectra, ab initio calculations have been carried out by the perturbation method to the second order (MP2) with valence and core electron correlation using a variety of basis sets up to 6-311+G(2df,2pd). With the smaller basis sets up to 6-311+G(d,p) and cc-PVDZ, the cis conformer is indicated as a transition state with all larger basis sets the cis conformer is the only stable form. The predicted energy difference from these calculations between the cis form and the higher energy trans conformer is about 125 cm(-1) which represents essentially the barrier to internal rotation of the NCS group (rotation around NC axis). Density functional theory calculation by the B3LYP method with the same basis sets predicts this barrier to be about 25 cm(-1). By utilizing the previously reported microwave rotational constants with the structural parameters predicted by the ab initio MP2(full)/6-311+G(d,p) calculations, adjusted r(0) structural parameters have been obtained for the cis form. The determined heavy atom parameters are: r(NC)=1.196(5), r(CS)=1.579(5), r(CN)=1.439(5), r(CC)=1.519(5)A for the distances and angles of angleCCN=112.1(5), angleCNC=146.2(5), angleNCS=174.0(5) degrees . The centrifugal distortion constants, dipole moments, conformational stability, vibrational frequencies, infrared intensities and Raman activities have been predicted from ab initio calculations and compared to experimental quantities when available. These results are compared to the corresponding quantities of some similar molecules.

On the vibrational spectra and structural parameters of methyl, silyl, and germyl azide from theoretical predictions and experimental data.

The infrared and Raman spectra of methyl, silyl, and germyl azide (XN3 where X=CH3, SiH3 and GeH3) have been predicted from ab initio calculations with full electron correlation by second order perturbation theory (MP2) and hybrid density function theory (DFT) by the B3LYP method with a variety of basis sets. These predicted data are compared to previously reported experimental data and complete vibrational assignments are provided for all three molecules. It is shown that several of the assignments recently proposed [J. Mol. Struct. (Theochem.) 434 (1998) 1] for methyl azide are not correct. Structural parameters for CH3N3 and GeH3N3 have been obtained by combining the previously reported microwave rotational constants with the ab initio MP2/6-311+G(d,p) predicted values. These "adjusted r0" parameters have very small uncertainties of +/-0.003 A for the XH distances and a maximum of +/-0.005 A for the heavy atom distances and +/-0.5 degrees for the angles. The predicted distance for the terminal NN bond which is nearly a triple bond is much better predicted by the B3LYP calculations, whereas the fundamental frequencies are better predicted by the scaled ab initio calculations. The results are discussed and compared to those obtained for some similar molecules.

Is 2-cyclopropylpropene really gauche?

Infrared spectra of gaseous and solid 2-cyclopropylpropene (2-CPP, c-C3H5C (CH3)CH2) have been recorded from 3500 to 40 cm-1, and Raman spectra (3200-150 cm-1) of the liquid as well as mid-infrared spectra of 2-CPP in liquid krypton solution (from -105 to -150 degrees C) were also obtained. Ab initio calculations, with basis sets up to 6-311+G(2df, 2pd), were carried out for this molecule, using the restricted Hartree-Fock (RHF) approach, with full electron correlation by the perturbation method to second order (MP2(full)) and density functional theory (DFT) by the B3LYP method. The combination of the experimental and computational results (particularly with the higher basis sets) unequivocally identifies the more stable conformer of 2-CPP as the trans form, with the gauche rotamer higher in energy, but also stable. The cis structure of this compound is not observed experimentally, and is predicted by the computational approaches to be a transition state. By studying the temperature variation of two well-resolved sets of conformational doublets of 2-CPP dissolved in liquid krypton, an average enthalpy difference between conformers of 182+/-18 cm-1 (2.18+/-0.22 kJ mol-1) has been determined, with the trans conformation lower in energy in the fluid states, and the sole conformer present in the polycrystalline solid phase. This enthalpy difference corresponds to an ambient temperature conformational equilibrium in the fluid phases of 2-cyclopropylpropene containing approximately 55+/-2% of the more stable trans rotameric form. A complete vibrational assignment for the trans conformer of 2-CPP is given, and many of the bands of the gauche rotamer have also been assigned. Structural parameters, dipole moments, and rotational constants for this molecule have been calculated at the MP2(full)/6-311+G(d,p) level, and these results--as well as the results from the experimental studies--are compared to similar quantities in related compounds.

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.

R0 Structural parameters, conformational, vibrational studies and ab initio calculations of cyanocyclopentane.

The infrared and Raman spectra (3100-50 cm(-1)) of the gas, liquid or solution, and solid have been recorded of cyanocyclopentane, c-C5H9CN. Variable temperature (-60 to -100°C) studies of the infrared spectra (3100-400cm(-1)) of the sample dissolved in liquid xenon have been carried out. From these data, both the envelope-equatorial (Eq) and Ax conformers have been identified and their relative stabilities obtained. The enthalpy difference has been determined to be 55 ± 12 cm(-1) (0.66 ± 0.14 kJ/mol) with the Eq conformer the more stable form. The percentage of the Ax conformer is estimated to be 45±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 r0 structural parameter values for the Eq[Ax] form are; for the heavy atom distances (Å): CN=1.160 [1.160] (3); Cα-C=1.463 [1.463] (3); Cα-Cß, Cß'=1.543 [1.545] (3); Cß-Cγ, Cγ'=1.540 [1.541] (3); Cγ-Cγ'=1.552 [1.553] (3) and angles (°): ∠Cα-CN=179.0 [178.9] (5); ∠CßCα-C=113.1 [110.1] (5); ∠CßCαCß'=103.0 [102.1] (5); ∠CαCßCγ=104.1 [104.8] (5); ∠CßCγCγ'=106.3 [106.0] (5). The results are discussed and compared to the corresponding properties of some related molecules.

Conformational stability, r(0) structural parameters, vibrational assignments and ab initio calculations of ethyldichlorophosphine.

Variable temperature (-60 to -100 °C) studies of ethyldichlorophosphine, CH3CH2PCl2, of the infrared spectra (4000-400 cm(-1)) dissolved in liquid xenon have been carried out. From these data, the two conformers have been identified and the enthalpy difference has been determined between the more stable trans conformer and the less stable gauche form to be 88±9 cm(-1) (1.04±0.11 kJ/mol). The percentage of abundance of the gauche conformer is estimated to be 57% at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by utilizing many different basis sets up to aug-cc-pVTZ for both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been provided for both conformers which have been predicted by MP2(full)/6-31G(d) ab initio calculations to predict harmonic force fields, wavenumbers of the fundamentals, infrared intensities, Raman activities and depolarization ratios for both conformers. Estimated r0 structural parameters have been obtained from adjusted MP2(full)/6-311+G(d,p) calculations. The results are discussed and compared to the corresponding properties of some related molecules.