Conformational stability from variable temperature infrared spectra of krypton solutions, ab initio calculations, vibrational assignment, and r0 structural parameters of 1,3-difluoropropane

The infrared spectra (3200-400 cm(-1)) of krypton solutions of 1,3-difluoropropane, FCH2CH2CH2F, at variable temperatures (-105 to -150 degrees C) have been recorded. Additionally, the infrared spectra (3200-50 cm(-1)) of the gas and solid have been recorded as well as the Raman spectrum of the liquid. From a comparison of the spectra of the fluid phases with that in the solid, all of the fundamental vibrations of the C2 conformer (gauche-gauche) where the first gauche indicates the form for one of the CH2F groups and the second gauche the other CH2F, and many of those for the C1 form (trans-gauche) have been identified. Tentative assignments have been made for a few of the fundamentals of the other two conformers, i.e. C2v (trans-trans) and Cs (gauche-gauche'). By utilizing six pairs of fundamentals for these two conformers in the krypton solutions, an enthalpy difference of 277 +/- 28 cm(-1) (3.31 +/- 0.33 kJ mol(-1)) has been obtained for the C2 versus C1 conformer with the C2 conformer the more stable form. For the C2v conformer, the enthalpy difference has been determined to be 716 +/- 72 cm(-1) (8.57 +/- 0.86 kJ mol(-1)) and for the Cs form 971 +/- 115 cm(-1) (11.6 +/- 1.4 kJ mol(-1)). It is estimated that there is 64 +/- 3% of the C2 form, 34 +/-3% of the C1 form, 1% of the C2v form and 0.6% of the Cs conformer present at ambient temperature. Equilibrium geometries and total energies of the four stable conformers have been determined from ab initio calculations with full electron correlation by the perturbation method to second order as well as by hybrid density functional theory calculations with the B3LYP method using a number of basis sets. The MP2 calculations predict the C1 conformer stability to be slightly higher than the experimentally determined value whereas for the C2v and Cs conformers the predicted energy difference is much larger than the experimental value. The B3LYP calculations predict a better energy difference for both the C1 and C2v as well as for the Cs conformers than the MP2 values. A complete vibrational assignment is proposed for the C2 conformer and many of the fundamentals have been identified for the C1 form based on the force constants, relative intensities and rotational-vibrational band contours obtained from the predicted equilibrium geometry parameters. By combining previously reported rotational constants for the C2 and C1 conformers with ab initio MP2/6-311 + G(d, p) predicted parameters, adjusted r0 parameters have been obtained for both conformers. Comparisons are made with the parameters obtained for some other molecules containing the FCH2 group. The spectroscopic and theoretical results are compared to the corresponding properties for some similar molecules.     

Spectra and structure of silicon containing compounds. XXXIX. Raman and infrared spectra,conformational stability,vibrational assignment and ab initio calculations of n-propyltrifluorosilane

The infrared (3100-40 cm(-1)) spectra of gaseous and solid and Raman (3200-20 cm(-1)) spectra of liquid with qualitative depolarization values and solid n-propyltrifluorosilane, CH(3)CH(2)CH(2)SiF(3), have been recorded. Additionally the infrared spectra of the sample in nitrogen and argon matrices have been recorded. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 degrees C) studies of the infrared spectra of the sample dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 135+/-14 cm(-1) (1.62+/-0.17 kJ mol(-1)) with the anti conformer the more stable form. At ambient temperature it is estimated that there is 51+/-2% of the gauche conformer present. Also the enthalpy difference in the liquid was obtained from variable temperature studies of the Raman spectra and from three conformer pairs an average value of 179+/-18 cm(-1) (2.14+/-0.22 kJ mol(-1)) was obtained again with the anti form the more stable conformer. Relatively complete vibrational assignments are proposed for both conformers based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios which are supported by normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities, depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311+G(d, p) and 6-311+G(2d, 2p) basis sets. By utilizing the previously reported microwave rotational constants for five isotopomers of CH(3)SiF(3) along with ab initio predicted structural values, r(0) parameters have been obtained for methyltrifluorosilane. Similarly, from the ab initio predicted parameters "adjusted r(0)" parameters have been estimated for both conformers of n-propyltrifluorosilane. The results are discussed and compared with those obtained for some similar molecules.     

Conformational studies of cyclopropylmethyl isothiocyanate from temperature-dependent FT-IR spectra of rare gas solutions and ab initio calculations

Variable temperature (-55 to -150 degrees C) studies of the infrared spectra (3200-100 cm(-1)) of cyclopropylmethyl isothiocyanate, c-C(3)H(5)CH(2)NCS, dissolved in liquefied rare gases (Xe and Kr), have been carried out. The infrared spectra of the gas and solid, as well as the Raman spectrum of the liquid, have also been recorded from 3200 to 100 cm(-1). By analyzing six conformer pairs in xenon solutions, a standard enthalpy difference of 228 +/- 23 cm(-1) (2.73 +/- 0.27 kJ.mol(-1)) was obtained with the gauche-cis (the first designation indicates the orientation of the CNCS group with respect to the three-membered ring, the second designation indicates the relative orientation of the NCS group with respect to the bridging C-C bond) rotamer the more stable form, and it is also the only form present in polycrystalline solid. Given statistical weights of 2:1 for the gauche-cis and cis-trans forms (the only stable conformers predicted); the abundance of cis-trans conformer present at ambient temperature is 14 +/- 2%. The potential surface describing the conformational interchange has been analyzed, and the corresponding two-dimensional Fourier coefficients were obtained. From MP2 ab initio calculations utilizing various basis sets with diffuse functions, the gauche-cis conformer is predicted to be more stable by 159-302 cm(-1), which is consistent with the experimental results. However, without diffuse functions, the conformational energy differences are nearly zero even with large basis sets. For calculations with density functional theory by the B3LYP method, basis sets without diffuse functions also predict smaller energy differences between the conformers, although not nearly as small as the MP2 results. A complete vibrational assignment for the gauche-cis conformer is proposed, and several fundamentals for the cis-trans conformer have been identified. The structural parameters, dipole moments, conformational stability, vibrational frequencies, and infrared and Raman intensities have been predicted from ab initio calculations and compared to the experimental values when applicable; the r(0) structural parameters are also estimated. The energies for the linear CNCS moiety were calculated. These experimental and theoretical results are compared to the corresponding quantities of some similar molecules.     

Infrared and Raman spectra, conformational stability, ab initio calculations of structure, and vibrational assignment of ethynylmethyl cyclobutane.

The infrared spectra (3200-300 cm(-1)) of the gas and solid and the Raman spectra (3200-30 cm(-1) of the liquid with quantitative depolarization values and the solid have been recorded of ethynylmethyl cyclobutane (cyclobutylmethyl acetylene), c-C4H7CH2C[ triple bond]CH. Both the equatorial and the axial conformers have been identified in the fluid phases and both the gauche and trans conformations of the methyl acetylenic group have been identified for each ring conformer. Variable temperature (-105 to -150 degrees C) studies of the infrared spectra of the sample dissolved in liquid krypton have been carried out. From these data the enthalpy differences have been determined to the 112 +/- 11 cm(-1) (1.34 +/- 0.13 kJ mol) between the most stable equatorial-trans (Et) conformer and the equatorial-gauche (Eg) conformer which is the second most stable conformer and 327 +/- 35 cm(-1) (3.91 + 0.42 kJ/mol) with the axial-gauche (Ag) conformer which is the least stable conformer. The enthalpy difference between the axial-trans (At) and the equatorial-gauche(Eg) is 56 +/- 6 cm(-1). At ambient temperature there is approximately 33% of the Et conformer, 38% of the Eg form, 15% of the At and 14% of the Ag conformer. For the polycrystalline solid the Eg conformer is the only form present which probably results form the packing in the crystal. A complete vibrational assignment is proposed for both equatorial conformers and additionally a few of the fundamentals of the At and Ag conformers have been assigned. The vibrational assignments are supported by normal coordinate calculations utilizing the force constants from ab initio MP2/6-31G(d) calculations. Complete equilibrium geometries have been determined for all four possible rotamers by ab initio calculations employing the 6-31G(d) and 6-311 + + G(d,p) basis sets at levels of restricted Hartree-Fock (RHF) and /or Moller-Plesset (MP2) with full electron correlation by the perturbation method to second order. 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.     

Infrared and Raman spectra,conformational stability,vibrational assignment and ab initio calculations of methylvinyl silyl chloride

The infrared spectra (3200-50 cm(-1)) of gaseous and solid and Raman spectra (3200-10 cm(-1)) of the liquid and solid methylvinyl silyl chloride, CH(2)=CHSiH(CH(3))Cl, and the Si-d isotopomer have been recorded. The three expected stable conformers (the three different groups eclipsing the double bond) have been identified in the fluid phase, but it was not possible to obtain an annealed solid with a single conformer. Variable temperature (-105 to -150 degrees C) studies of the infrared spectra of the sample dissolved in liquid krypton has been carried out. From these data the enthalpy differences between the most stable conformer with the hydrogen atom (HE) eclipsing the double bond to that with the chlorine atom (ClE) and the methyl group (ME) eclipsing the double bond have been determined to be 17+/-4 cm(-1) (203+/-48 Jmol(-1)) and 80+/-12 cm(-1) (957+/-144 Jmol(-1)), respectively. However in the liquid state the ME conformer is the most stable form with enthalpy differences of 13+/-4 and 27+/-7 cm(-1) to the HE and ClE rotamers, respectively. It is estimated that there is 39% of the HE conformer, 35% of the ClE conformer, and 26% of the ME conformer present at ambient temperature. A complete vibration assignment is proposed for the HE conformer which is based on infrared band contours and group frequencies, which is supported by normal coordinate calculations utilizing the force constants from ab initio MP2/6-31G(d) calculations. Additionally, several of the fundamentals for the other two conformers have been assigned. The optimal geometries, conformational stabilities, harmonic force fields, infrared intensities, Raman activities, depolarization ratios, and vibrational frequencies are reported for all three conformers from MP2/6-31G(d,p) ab initio calculations with full electron correlation. Optimized geometrical parameters and conformational stabilities have been obtained from MP2/6-311+G(d,p) calculations. At this highest level of calculations, the HE conformer is predicted to be more stable by 62 and 84 cm(-1) than the ME and ClE conformers, respectively. The coefficients from the potential function governing the conformational interchange have been obtained from the MP2/6-31G(d) ab initio calculations. By utilizing the frequency of the SiH stretching mode, the r(0)-H distance has been determined to be 1.481 A for the HE conformer. The ab initio calculated quantities are compared to the experimentally determined values where applicable, as well as to some corresponding results for some similar molecules.     

Infrared and Raman spectra, conformational stability, barriers to internal rotation, normal-coordinate calculations and vibrational assignments for vinyl silyl bromide

The infrared (3200-30 cm(-1) spectra of gaseous and solid, the Raman spectra (3200-30 cm(-1)) of the liquid and solid vinyl silyl bromide, CH2CHSiH2Br, have been recorded. Additionally, quantitative depolarization values have been obtained. Both the gauche and cis conformers have been identified in the fluid phases but only the gauche conformer remains in the solid. Variable temperature studies from 0 to -87 degrees C of the Raman spectrum of the liquid was carried out. From these data, the enthalpy difference has been determined to be 22 +/- 6 cm(-1) (0.26 +/- 0.08 kJ/mol), with the gauche conformer being the more stable form. The predictions from the ab initio calculations up to MP2/6-311 + + G(2d,2p) basis set favor the gauche as the more stable form. A complete vibrational assignment is proposed for both the gauche and cis conformers based on infrared band contours, relative intensities, depolarization values and group frequencies. The vibrational assignments are supported by normal coordinate calculations utilizing the force constants from ab initio MP2/6-31G(d) calculations and the potential energy terms for the conformer interconversion have been obtained from the same calculations. Complete equilibrium geometries have been determined for both rotamers by ab initio calculations employing a variety of basis sets up to 6-311 + + G(2d,2p) at levels of restricted Hartree-Fock (RHF) and/or Moller-Plesset (MP) to second order. The results are discussed and compared to those obtained for some similar molecules.     

Thermochemistry of methyl and ethyl nitro, RNO2, and nitrite, RONO, organic compounds

Computational quantum theory is employed to determine the thermochemical properties of n-alkyl nitro and nitrite compounds: methyl and ethyl nitrites, CH3ONO and C2H5ONO, plus nitromethane and nitroethane, CH3NO2 and C2H5NO2, at 298.15 K using multilevel G3, CBS-QB3, and CBS-APNO composite methods employing both atomization and isodesmic reaction analysis. Structures and enthalpies of the corresponding aci-tautomers are also determined. The enthalpies of formation for the most stable conformers of methyl and ethyl nitrites at 298 K are determined to be -15.64 +/- 0.10 kcal mol-1 (-65.44 +/- 0.42 kJ mol-1) and -23.58 +/- 0.12 kcal mol-1 (-98.32 +/- 0.58 kJ mol-1), respectively. DeltafHo(298 K) of nitroalkanes are correspondingly evaluated at -17.67 +/- 0.27 kcal mol-1 (-74.1 +/- 1.12 kJ mol-1) and -25.06 +/- 0.07 kcal mol-1 (-121.2 +/- 0.29 kJ mol-1) for CH3NO2 and C2H5NO2. Enthalpies of formation for the aci-tautomers are calculated as -3.45 +/- 0.44 kcal mol-1 (-14.43 +/- 0.11 kJ mol-1) for aci-nitromethane and -14.25 +/- 0.44 kcal mol-1 (-59.95 +/- 1.84 kJ mol-1) for the aci-nitroethane isomers, respectively. Data are evaluated against experimental and computational values in the literature with recommendations. A set of thermal correction parameters to atomic (H, C, N, O) enthalpies at 0 K is developed, to enable a direct calculation of species enthalpy of formation at 298.15 K, using atomization reaction and computation outputs.     

Spectra and structure of silicon containing compounds. XXXII. Raman and infrared spectra,conformational stability,vibrational assignment and ab initio calculations of n-propylsilane-d0 and Si-d3

The infrared (3100-40 cm(-1)) and Raman (3100-20 cm(-1)) spectra of gaseous and solid n-propylsilane, CH(3)CH(2)CH(2)SiH(3) and the Si-d(3) isotopomer, CH(3)CH(2)CH(2)SiD(3), have been recorded. Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values obtained. Both the anti and gauche conformers have been identified in the fluid phases but only the anti conformer remains in the solid. Variable temperature (-105 to -150 degrees C) studies of the infrared spectra of n-propylsilane dissolved in liquid krypton have been recorded and the enthalpy difference has been determined to be 220+/-22 cm(-1) (2.63+/-0.26 kJ mol(-1)) with the anti conformer the more stable form. A similar value of 234+/-23 cm(-1) (2.80+/-0.28 kJ mol(-1)) was obtained for deltaH for the Si-d(3) isotopomer. At ambient temperature it is estimated that there is 30+/-2% of the gauche conformer present. The potential function governing the conformation interchange has been estimated from the far infrared spectral data, the enthalpy difference, and the dihedral angle of the gauche conformer, which is compared to the one predicted from ab initio MP2/6-31G(d) calculations. The barriers to conformational interchange are: 942, 970 and 716 cm(-1) for the anti to gauche, gauche to gauche, and gauche to anti conformers, respectively. Relatively complete vibrational assignments are proposed for both the n-propylsilane-d(0) and Si-d(3) molecules based on the relative infrared and Raman spectral intensities, infrared band contours, depolarization ratios, and normal coordinate calculations. The geometrical parameters, harmonic force constants, vibrational frequencies, infrared intensities, Raman activities and depolarization ratios, and energy differences have been obtained for the anti and gauche conformers from ab initio MP2/6-31G(d) calculations. Structural parameters and energy differences have also been obtained utilizing the larger 6-311 + G(d,p) and 6-311 + G(2d,2p) basis sets. From the isolated Si-H stretching frequency from the Si-d(2) isotopomer the r(0) distances of 1.484 and 1.485 A have been determined for the SiH(s) and SiH(a) bonds, respectively, for the anti conformer, and 1.486 A for the SiH bond for the gauche conformer. Utilizing previously reported microwave rotational constants for the anti conformer and the determined SiH distances along with ab initio predicted parameters 'adjusted r(0)' parameters have been obtained for the anti conformer. The results are discussed and compared to those obtained for some similar molecules.     

Conformational stability from variable temperature infrared spectra of rare gas solutions of 2-chloro-3-fluoropropene

Variable temperature (-55 to -155 degrees C) infrared spectra of rare gas solutions of 2-chloro-3-fluoropropene, H2C=C(Cl)CH2F, have been recorded from 3500 to 400 cm(-1). The relative intensities of 16 conformer pairs at ten different temperatures of a krypton solution have been measured and from these data an enthalpy difference of 271+/-27 cm(-1) (3.17+/-0.32 kJ x mol(-1)) has been obtained with the cis conformer the more stable form. Similar studies were also carried out in xenon and an enthalpy difference of 334+/-33 cm(-1) (4.00+/-0.39 kJ x mol(-1)) was obtained again with the cis conformer the more stable form. It is estimated that there is 35+/-2% of the gauche conformer present at ambient temperature. However, in the crystalline solid the gauche conformer is the stable rotamer. Extensive ab initio calculations with full electron correlation by the perturbation method at the MP2 level with a variety of basis sets as well as density functional theory calculations (DFT) by the B3LYP method have been carried out. Several of these calculations predict an energy difference in the range of 400 cm(-1) with the cis form the more stable conformer but most of the predicted energy differences are significantly larger than the experimentally determined value. The spectroscopic and theoretical results are discussed and compared with the corresponding quantities for some similar molecules.     

Spectra and structure of silicon containing compounds. XXVII. Raman and infrared spectra, conformational stability, vibrational assignment and ab initio calculations of vinyldichlorosilane

The infrared (3200-30 cm(-1) spectra of gaseous and solid and the Raman spectra of liquid (3200-30 cm(-1), with quantitative depolarization values, and solid vinyldichlorosilane, CH2=CHSiHCl2, have been recorded. Both the gauche and the cis conformers have been identified in the fluid phases. Variable temperature (105-150 degrees C) studies of the infrared spectra of the sample dissolved in liquid krypton have been carried out. From these data the enthalpy difference has been determined to be 20 +/- 5 cm(-1) (235 +/- 59 J mol(-1) with the gauche conformer the more stable rotamer. It was not possible to obtain a single conformer in the solid even with repeated annealing of the sample. The experimental enthalpy difference is in agreement with the prediction from MP2/6-311 + G(2d,2p) ab initio calculations with full electron correlation. However, when smaller basis sets, i.e. 6-31G(d) and 6-311 + G(d,p) were utilized the cis conformer was predicted to be the more stable form. Complete vibrational assignments are proposed for both conformers based on infrared contours, relative infrared and Raman intensities, depolarization values and group frequencies, which are supported by normal coordinate calculations utilizing the force constants from ab initio MP2/6-31G(d) calculations. From the frequencies of the Si-H stretches, the Si-H bond distance of 1.474 A has been determined for both the gauche and the cis conformers. Complete equilibrium geometries have been determined for both rotamers by ab initio calculations employing the 6-31G(d), 6-311 + G(d,p) and 6-311 + (2d,2p) basis sets at level of Hartree-Fock (RHF) and/or Moller Plesset to the second order (MP2) with full electron correlation. The potential energy terms for the conformer interconversion have been obtained from the MP2/6-31G(d) calculations. The results are discussed and compared with those obtained for 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 M?ller-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.     

Infrared and Raman spectra, conformational stability, ab initio calculations and vibrational assignment of 2-fluorobutane

The infrared spectra (3500-50 cm-1) of gas and solid and the Raman spectrum (3500-50 cm-1) of liquid 2-fluorobutane, CH3CHFCH2CH3, have been recorded. Variable temperature studies over the range -105 to -150 degrees C of the infrared spectra (3500-400 cm-1) of the sample dissolved in liquid krypton have also been recorded. By utilizing the relative intensities of six conformer pairs each for both Me-trans/F-trans and Me-trans/H-trans, the Me-trans conformer is found to be the lowest energy form with an enthalpy difference to the F-trans conformer of 102 +/- 10 cm-1 ( 1.21+/- 0.12 kJmol-1) whereas the H-trans conformer is the highest energy form with an enthalpy difference of 208 +/- 21 cm-1 ( 2.49 +/- 0.25 kJmol-1) higher than the Me-trans form. At ambient temperature, it is estimated that there is 50 +/- 2% of the Me-trans form, 31 +/- 1% of the F-trans form, and 19 +/- 1% of the H-trans conformer present. Equilibrium geometries and total energies of the three conformers have been determined by ab initio calculations with full electron correlation by the perturbation method to second order using a number of basis sets. A complete vibrational assignment is proposed for the Me-trans conformer and many of the fundamentals have been identified for the other two forms based on the force constants, relative infrared and Raman intensities, and depolarization ratios obtained from MP2/6-31Gd ab initio calculations. The spectroscopic and theoretical results are compared to the corresponding properties for some similar molecules.     

Vibrational analysis of n-butyl, isobutyl, sec-butyl and tert-butyl nitrite

Raman and infrared spectra of n-butyl, isobutyl, sec-butyl and tert-butyl nitrite are reported. Density functional theory and M?eller-Plesset calculations with 6-31G* and 6-311G* basis sets were used to determine ground state molecular geometries and vibrational frequencies of these compounds. Calculations and spectral data of these molecules were used to perform partial vibrational mode assignments for the observed transitions. In agreement with previous investigations of alkyl nitrites, cis and trans rotational conformers of n-butyl, isobutyl and sec-butyl nitrite were observed in the gas phase infrared spectra and the condensed phase Raman and infrared spectra. Among the several predicted geometries of these compounds, the cis-trans geometry (cis with respect to the C-O-N=O dihedral angle and trans with respect to the C-C-O-N dihedral) was calculated to be the most stable conformer of n-butyl and isobutyl nitrite, while the cis-gauche conformer was found to be the most stable geometry of sec-butyl nitrite. The cis-type structures of these three molecules are favored due to formation of a pseudo hydrogen bond between the nitrite group and the alpha-carbon hydrogen atoms. Hindrance with the alkyl moiety, however, causes the trans conformer (trans with respect to the C-O-N=O dihedral) of tert-butyl nitrite to lie lower than its cis conformer, a result that was supported by our spectroscopic measurements. The characteristic N=O stretch frequency for the trans conformers of all the compounds examined was observed to decrease with increasing branching at the alpha-carbon, while the same mode for the cis conformers shows no change among the primary and secondary nitrites. Evidence is also provided that suggests that the relative number of cis conformers to trans conformers decreases as the alpha-carbon branching increases.     

Energetics of C-F, C-Cl, C-Br, and C-I bonds in 2-haloethanols. enthalpies of formation of XCH(2)CH(2)OH (X = F, Cl, Br, I) compounds and of the 2-hydroxyethyl radical

The energetics of the C-F, C-Cl, C-Br, and C-I bonds in 2-haloethanols was investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of 2-chloro-, 2-bromo-, and 2-iodoethanol, at 298.15 K, were determined as Delta(f)H(degree)m(CH2CH2OH, l) = -315.5 +/- 0.7 kJ.mol-1, Delta(f)H(degree)mBrCH2CH2OH, l) = -275.8 +/- 0.6 kJ.mol-1, Delta(f)H(degree)m(ICH2CH2OH, l) = -207.3 +/- 0.7 kJ.mol-1, by rotating-bomb combustion calorimetry. The corresponding standard molar enthalpies of vaporization, Delta(vap)H(degree)m(ClCH2CH2OH) = 48.32 +/- 0.37 kJ.mol-1, Delta(vap)H(degree)m(BrCH2CH2OH) = 54.08 +/- 0.40 kJ.mol-1, and Delta(vap)H(degree)m(ICH2CH2OH) = 57.03 +/- 0.20 kJ.mol-1 were also obtained by Calvet-drop microcalorimetry. The condensed phase and vaporization enthalpy data lead to Delta(f)H(degree)m(ClCH2CH2OH, g) = -267.2 +/- 0.8 kJ.mol-1, Delta(f)H(degree)m(BrCH2CH2OH, g) = -221.7 +/- 0.7 kJ.mol-1, and Delta(f)H(degree)m(ICH2CH2OH, g) = -150.3 +/- 0.7 kJ.mol-1. These values, together with the enthalpy of selected isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3LYP/cc-pVTZ) and CBS-QB3 calculations were used to derive the enthalpies of formation of gaseous 2-fluoroethanol, Delta(f)H(degree)m(FCH2CH2OH, g) = -423.6 +/- 5.0 kJ.mol-1, and of the 2-hydroxyethyl radical, Delta(f)H(degree)m(CH2CH2OH, g) = -28.7 +/- 8.0 kJ.mol-1. The obtained thermochemical data led to the following carbon-halogen bond dissociation enthalpies: DHo(X-CH2CH2OH) = 474.4 +/- 9.4 kJ.mol-1 (X = F), 359.9 +/- 8.0 kJ.mol-1 (X = Cl), 305.0 +/- 8.0 kJ.mol-1 (X = Br), 228.7 +/- 8.1 kJ.mol-1 (X = I). These values were compared with the corresponding C-X bond dissociation enthalpies in XCH2COOH, XCH3, XC2H5, XCH=CH2, and XC6H5. In view of this comparison the computational methods mentioned above were also used to obtain Delta(f)H(degree)m-594.0 +/- 5.0 kJ.mol-1 from which DHo(F-CH2COOH) = 435.4 +/- 5.4 kJ.mol-1. The order DHo(C-F) > DHo(C-Cl) > DHo(C-Br) > DHo(C-I) is observed for the haloalcohols and all other RX compounds. It is finally concluded that the major qualitative trends exhibited by the C-X bond dissociation enthalpies for the series of compounds studied in this work can be predicted by Pauling's electrostatic-covalent model.     

Molecular structure, infrared spectrum, and photochemistry of squaric acid dimethyl ester in solid argon

Squaric acid dimethyl ester (C(6)O(4)H(6); 3,4-dimethoxycyclobut-3-ene-1,2-dione; DCD) was studied by matrix isolation infrared spectroscopy and by density functional theory (B3LYP) and ab initio (MP2) calculations with the 6-31++G(d,p) and 6-311++G(d,p) basis sets. Three conformers of the compound were theoretically predicted. The two most stable conformers were identified in low-temperature argon matrixes and the energy gap between them was determined. The trans-trans conformer (C(2)(v)) was found to be more stable than the cis-trans form (C(s)) by 4.2 kJ mol(-1), in consonance with the theoretical predictions (MP2 calcd = 3.9 kJ mol(-1)). In situ broadband UV irradiation (lambda > 337 nm) of the matrix-isolated compound was found to induce the ring-opening reaction leading to production of the bisketene, 2,3-dimethoxybuta-1,3-diene-1,4-dione as well as the trans-trans --> cis-trans conformational isomerization. The latter phototransformation allowed separation of the infrared spectra of the two conformers initially trapped into a low-temperature matrix. Upon higher energy irradiation (lambda > 235 nm), the main observed photoproducts were CO and deltic acid dimethyl ester (C(5)O(3)H(6); 2,3-dimethoxycycloprop-2-en-1-one), the latter being obtained in two different conformations (trans-trans and cis-trans). According to the experimental data, deltic acid dimethyl ester is produced by decarbonylation of the initially formed bisketene and not by direct CO extrusion from DCD.     

Vibrational spectrum, ab initio calculations, conformational equilibria and torsional modes of 1,3-dichloropropane

Ab initio calculations are reported for three of four possible conformers of 1,3-dichloropropane. The fourth conformer, with Cs symmetry, has a predicted enthalpy difference of more than 1500 cm(-1) from the most stable conformer from each calculation regardless of the basis set used, so there is little chance of observing it. Thus, there is no evidence in the infrared or Raman spectrum of the presence of a fourth conformer. The order of stability given by the ab initio calculations is C2(GG)>C1(AG)>C2v(AA)>Cs(GG'), where A indicates the anti form for one of the CH2Cl groups and G indicates the gauche conformation for the other CH2Cl group relative to the plane of the carbon atoms. Almost every band observed can be confidently assigned to one or another of the conformers. Many observed bands proved to be of a composite nature, with several nearly coincident vibrations of different conformers contributing to the band contour. Nonetheless, a complete assignment of fundamentals is possible for the most stable C2 conformer, and 5 of the fundamentals of the C2v conformer and 13 those of the C1 conformer can be confidently assigned.     

Thermochemistry and gas-phase ion energetics of 2-hydroxy-4-methoxy-benzophenone (oxybenzone)

We have investigated the thermochemistry and ion energetics of the oxybenzone (2-hydroxy-4-methoxy-benzophenone, C14H12O3, 1H) molecule. The following parameters have been determined for this species: gas-phase enthalpy for the of neutral molecule at 298.15K, (Delta(f)H0(m)(g) = -303.5 +/- 5.1 kJ x mol-1), the intrinsic (gas-phase) acidity (GA(1H) = 1402.1 +/- 8.4 kJ x mol-1), enthalpy of formation for the oxybenzone anion (Delta(f)H0(m)(1-,g) = -402.3 +/- 9.8 kJ x mol-1). We also have obtained the enthalpy of formation of, 4-hydroxy-4'-methoxybenzophenone (Delta(f)H0(m)(g) = -275.4 +/- 10 kJ x mol-1) and 3-methoxyphenol anion (Delta(f)H0(m)(C7H7O2-,g) = -317.7 +/- 8.7 kJ x mol-1). A reliable experimental estimation of enthalpy related to intramolecular hydrogen bonding in oxybenzone has also been obtained (30.1 +/- 6.3 kJ x mol-1) and compared with our theoretical calculations at the B3LYP/6-311++G** level of theory, by means of an isodesmic reaction scheme. In addition, heat capacities, temperature, and enthalpy of fusion have been determined for this molecule by differential scanning calorimetry.     

Conformational stabilities of 1,1-dicyclopropylethene determined from variable-temperature infrared spectra of xenon solutions and ab initio calculations

The infrared (3200-40 cm(-1)) spectra of gaseous and solid 1,1-dicyclopropylethene, (c-C3H5)2C=CH2, along with the Raman (3200-40 cm(-1)) spectra of liquid and solid phases, have been recorded. The major trans-gauche (C=C bond trans to one ring with the other ring rotated about 60 degrees from the C=C bond, trivial C(1) symmetry) and gauche-gauche (the two three-membered rings rotated oppositely about 60 degrees from the C=C bond, C2 symmetry) rotamers have been confidently identified in the fluid phases, but no definitive spectroscopic evidence was found for the gauche-gauche' form (the two three-membered rings rotated to the same side about 60 degrees from the C=C bond, Cs symmetry), which is calculated to be present in no more than 6% at ambient temperature. Variable-temperature (-55 to -100 degrees C) studies of the infrared spectra of the sample dissolved in liquid xenon have been carried out. Utilizing six different combinations of pairs of bands from the C1 and C2 conformers, the average enthalpy difference between these two has been determined to be 146 +/- 30 cm(-1) (1.75 +/- 0.36 kJ x mol(-1)), with the C1 form more stable. Given statistical weights of 2:1:1 respectively for the C1, C2, and Cs forms, it is estimated that there are 75 +/- 2% C(1) and 19 +/- 1% C2 conformers present at ambient temperature. By utilizing predicted frequencies, infrared intensities, Raman activities, and band envelopes from scaled MP2(full)/6-31G(d) ab initio calculations, a complete vibrational assignment is made for the C1 form and a number of fundamentals of the C2 conformer have been identified. The structural parameters, dipole moments, and conformational stabilities have been obtained from ab initio calculations at the level of Hartree-Fock (RHF), the perturbation method to second order with full electron correlation (MP2(full)), and hybrid density functional theory (DFT) by the B3LYP method with a variety of basis sets. The predicted conformational stabilities from the MP2 calculations with relatively large basis sets are consistent with the experimental results. Structural parameters are estimated from the MP2(full)/6-311+G(d,p) predictions which are compared to the previously reported electron diffraction parameters. These experimental and theoretical results are compared to the corresponding quantities of some similar molecules.     

Conformational stabilities and structural parameters of (CH3)(n)CH(3-n) CFO molecules

Variable temperature (-60 to -100 degrees C) studies of the infrared spectra (3500-400 cm(-1)) of propionyl fluoride (CH3CH2CFO) and 2-methylpropionyl fluoride ((CH3)2CHCFO), dissolved in liquid xenon have been recorded. From these data, the enthalpy difference has been determined to be 329 +/- 33 cm(-1) (3.94 +/- 0.39 kJ/mol) for propionyl fluoride with the trans conformer (methyl group eclipsing the oxygen atom) more stable than the gauche form. For 2-methylpropionyl fluoride, the enthalpy difference has been determined to be 297 +/- 30 cm(-1) (3.55 +/- 0.36 kJ/mol) with the gauche conformer (methyl group eclipsing the oxygen atom) more stable than the trans form. From these DeltaH values along with assigned torsional fundamentals for both conformers and accompanying "hot bands" the potential functions governing the conformational interchange have been calculated. Utilizing the infrared data from the xenon solution and ab initio frequency predictions from MP2/6-31G* calculations, a few reassignments of the fundamentals have been made. Ab initio calculations have been carried out with several different basis sets up to MP2/6-311 + G** from which structural parameters and conformational stabilities have been determined. Additionally, force constants, infrared intensities, Raman activities, depolarization ratios, and scaled vibrational frequencies have been determined from MP2/6-31G* calculations. Adjusted structural parameters have been obtained from combined ab initio predicted values and previously reported microwave data. These parameters are compared to those obtained from either the earlier microwave and/or electron diffraction studies. Similar ab initio calculations and structural parameter determinations have been carried out for acetyl fluoride (CH3CFO) and trimethylacetyl fluoride ((CH3)3CCFO) and compared to the corresponding experimental results when appropriate.