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ABSTRACT: 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.
The Journal of Physical Chemistry A 02/2009; 113(8):1653-62. · 2.95 Impact Factor
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Journal of Raman Spectroscopy 09/2008; 40(2):197 - 204. · 3.09 Impact Factor
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ABSTRACT: 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.
The Journal of Physical Chemistry A 04/2008; 112(11):2268-81. · 2.95 Impact Factor
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ABSTRACT: 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.
Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy 12/2007; 68(3):783-95. · 2.10 Impact Factor
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ABSTRACT: 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.
The Journal of Physical Chemistry A 08/2006; 110(29):9057-70. · 2.95 Impact Factor
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ABSTRACT: The microwave spectra of (methylamino)thiophosphoryl difluoride, CH(3)NHP(=S)F(2), and two deuterated species, CH(3)NDP(=S)F(2) and CD(3)NHP(=S)F(2), have been investigated in the region from 26.5 to 39.0 GHz. The rotational constants of the ground vibrational state have been determined and have been shown to be only consistent with the trans conformer (CH(3) group antiperiplanar to the P=S bond) with C(s) symmetry. The a-type R branch transitions have been assigned for the trans conformer for the three isotopomers on the basis of the rigid rotor model. Near-trans and near-cis forms without molecular planes of symmetry are predicted by all ab initio calculations with the near-trans form being more stable. However, the double-well potentials governing the interchange between the two enantiomeric near-trans as well as the two near-cis forms are too shallow to accommodate the zero-point energies of the nu(24) asymmetric torsion. Thus, the trans conformation with C(s) symmetry may be more accurate in explaining the microwave experimental data. The "adjusted" r(0) structural parameters have been obtained by systematically adjusting the ab initio MP2(full)/6-311+G(d,p) structure of the trans conformer with C(s) symmetry to fit the microwave rotational constants. The determined heavy atom distances are r(C-N) = 1.459(5), r(P-N) = 1.621(5), r(P=S) = 1.879(5), and r(P-F) = 1.550(5) A, and the heavy atom angles are angleCNP = 124.7(5) degrees , angleNPS = 118.3(5) degrees , angleNPF = 103.2(5) degrees , angleFPS = 117.0(5) degrees , and angleFPF = 94.6(5) degrees . The adjusted r(0) parameters have also been obtained for aminodifluorophosphine, H(2)NPF(2), with a slightly pyramidal -PNH(2) moiety. The results indicate that the previously reported short distance of 0.981(5) A for the N-H(o)(outer) bond from the microwave study is too short, and the adjusted r(0) value of 1.007(3) A is obtained from the combined data. Adjusted r(0) parameters are also reported for (dimethylamino)difluorophosphine, (CH(3))(2)NPF(2), with C(s) symmetry with the PNC(2) portion of the molecule being planar. The previously reported C-H distances from the electron diffraction study are too long, and the anglePNC(i) and angleC(o)NC(i) angles are also found to be in error. These results provide a reasonable explanation why the microwave and electron diffraction results differ for the structures of these latter two molecules.
The Journal of Physical Chemistry A 08/2006; 110(26):8037-43. · 2.95 Impact Factor
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ABSTRACT: Variable temperature (-55 to -145 degrees C) studies of the infrared spectra (3500 to 100 cm(-1)) of ethylamine, CH(3)CH(2)NH(2), dissolved in liquid krypton and/or xenon have been recorded. From these data, the enthalpy differences have been determined to be 54 +/- 4 cm(-1) (0.65 +/- 0.05 kJ/mol), with the trans conformer (methyl group relative to the lone pair of electrons on nitrogen) being the more stable form. It is estimated that there is 61 +/- 1% of the doubly degenerate gauche form present at ambient temperature. The conformational energetics have been calculated with the Møller-Plesset perturbation method to the second order (MP2(full)) and the fourth order (MP4(SDTQ)) as well as with density functional theory by the B3LYP method utilizing a variety of basis sets. Basis sets with diffuse functions lead to incorrect prediction of the conformational stability. On the basis of the frequencies of the torsional transitions along with the determined experimental enthalpy difference and gauche dihedral angle, the potential function governing conformational interchange has been obtained, and the determined Fourier cosine coefficients are V(1) = -207 +/- 48, V(2) = 320 +/- 67, V(3) = 1072 +/- 25, V(4) = 55 +/- 11, and V(5) = -96 +/- 28 cm(-1), with a trans-to-gauche barrier of 1286 cm(-1), and a gauche-to-gauche barrier of 715 cm(-1). The 3-fold methyl rotational barriers have been determined to be 1241 +/- 4 and 1281 +/- 10 cm(-1) for the gauche and trans conformers, respectively. By utilizing the previously reported microwave rotational constants combined with the structural parameters predicted at the MP2(full)/6-311+ G(d,p) level, adjusted r(0) structural parameters have been obtained. A complete vibrational assignment is given for the trans conformer, which is supported by normal coordinate calculations utilizing scaled force constants from ab initio B3LYP/6-311++G(3df,3pd) calculations. Proposed assignments are also made for the fundamentals of the gauche conformer. The results of these spectroscopic and theoretical studies are discussed and compared to the corresponding results for similar molecules.
The Journal of Physical Chemistry A 06/2006; 110(17):5674-84. · 2.95 Impact Factor
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ABSTRACT: Variable temperature (−55 to −145 °C) studies of the infrared spectra (3500 to 100 cm-1) of ethylamine, CH3CH2NH2, dissolved in liquid krypton and/or xenon have been recorded. From these data, the enthalpy differences have been determined to be 54 ± 4 cm-1 (0.65 ± 0.05 kJ/mol), with the trans conformer (methyl group relative to the lone pair of electrons on nitrogen) being the more stable form. It is estimated that there is 61 ± 1% of the doubly degenerate gauche form present at ambient temperature. The conformational energetics have been calculated with the Møller−Plesset perturbation method to the second order (MP2(full)) and the fourth order (MP4(SDTQ)) as well as with density functional theory by the B3LYP method utilizing a variety of basis sets. Basis sets with diffuse functions lead to incorrect prediction of the conformational stability. On the basis of the frequencies of the torsional transitions along with the determined experimental enthalpy difference and gauche dihedral angle, the potential function governing conformational interchange has been obtained, and the determined Fourier cosine coefficients are V1 = −207 ± 48, V2 = 320 ± 67, V3 = 1072 ± 25, V4 = 55 ± 11, and V5 = −96 ± 28 cm-1, with a trans-to-gauche barrier of 1286 cm-1, and a gauche-to-gauche barrier of 715 cm-1. The 3-fold methyl rotational barriers have been determined to be 1241 ± 4 and 1281 ± 10 cm-1 for the gauche and trans conformers, respectively. By utilizing the previously reported microwave rotational constants combined with the structural parameters predicted at the MP2(full)/6-311+ G(d,p) level, adjusted r0 structural parameters have been obtained. A complete vibrational assignment is given for the trans conformer, which is supported by normal coordinate calculations utilizing scaled force constants from ab initio B3LYP/6-311++G(3df,3pd) calculations. Proposed assignments are also made for the fundamentals of the gauche conformer. The results of these spectroscopic and theoretical studies are discussed and compared to the corresponding results for similar molecules.
04/2006;
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ABSTRACT: The Raman spectrum (4000–200 cm−1) of liquid and infrared spectra (4000–400 cm−1) of gaseous and liquid 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane, c-OSi(CH3)2CH2CH2Si(CH3)2, have been recorded. Ab initio and density functional theory (DFT) calculations with several different basis sets including diffuse functions have been carried out to predict the conformational stabilities with comparisons to disiloxane (H3SiOSiH3)and 2,5-disila-1-oxacyclopentane (c-OSiH2CH2CH2SiH2). These calculations predict the twistedC2 conformer as the most stable form of the ring compounds, with the planar C2v conformer a transition state and the envelope Cs conformer not a stable form. These predicted stabilities are supported by the vibrational data. Additionally, force constants, infrared intensities, Raman activities, depolarization ratios and scaled vibrational wavenumbers have been determined from MP2(full)/6–31G(d) calculations for all three molecules and compared with experimental values when available. Predicted r0 structural parameters have been obtained for dimethyl ether, methyl silyl ether and disiloxane, which are compared with the experimentally determined values. On the basis of these data, estimated r0 parameters are provided for both five-membered rings with the expectation that these values are as accurate as could be measured experimentally in the gas phase. The results are discussed and compared with corresponding quantities for some similar molecules. Copyright © 2006 John Wiley & Sons, Ltd.
Journal of Raman Spectroscopy 01/2006; 37(1‐3):52 - 67. · 3.09 Impact Factor
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ABSTRACT: 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.
Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy 06/2005; 61(7):1357-73. · 2.10 Impact Factor
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ABSTRACT: 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.
The Journal of Physical Chemistry A 04/2005; 109(8):1650-61. · 2.95 Impact Factor
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ABSTRACT: 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.
Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy 07/2004; 60(7):1659-76. · 2.10 Impact Factor
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ABSTRACT: Fifty different carbon–hydrogen distances have been predicted from ab initio MP2/6-311+G(d,p) calculations, which range from a short value of 1.0611 for HCNO to a long value of 1.1044 for H2CO. The values include those predicted for a series of methyl (CH3) moieties where the two different C–H distances vary by as much as 0.005 . These predicted values are compared to r
0(C–H) distances obtained from the isolated carbon–hydrogen stretching frequencies, as well as to r
0 or r
s
parameters obtained from microwave data. Except for the very short C–H bonds, the ab initio values from the MP2/6–311+G(d,p) calculations can be used for the carbon–hydrogen distances with error limits of 0.003 . By utilizing the spectral data from CD3CClO, it is shown that combination bands in the C–H stretching region could cause problems in the identification of the isolated C–H stretching frequency from the CD2HCClO isotopomer. The value of the ab initio predicted C–H distances for checking unusually long or short r
s
(C–H) or r
0 values is demonstrated.
Structural Chemistry 03/2004; 15(2):149-157. · 1.85 Impact Factor
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ABSTRACT: The infrared spectra (3500–400 cm–1) of krypton solutions of chlorocyclopentane, c-C5H9Cl, at variable temperatures (–101 to –150C) have been recorded and the fundamental vibrations of the axial conformer and several of those for the equatorial form have been assigned. Utilizing two pairs of fundamentals for the two conformers in the krypton solution, an enthalpy difference of 14515 cm–1 (1.730.18 kJ-mol–1) has been obtained with the axial conformer the more stable form. It is estimated that there is 672% of the axial conformer present at ambient temperature. Convincing spectroscopic evidence shows that a significant percentage of the chlorocyclopentane molecules are undergoing pseudorotation at ambient temperature. The conformational stabilities, harmonic force constants, fundamental frequencies, infrared intensities, and Raman activities have been obtained from MP2/6-31G(d) calculations with full electron correlation and these quantities have been compared to the experimental values when appropriate. The optimized geometries and conformational stabilities have also been obtained from ab initio MP2 calculations as well as by density functional theory (DFT) by the B3LYP method with several different basis sets. The adjusted r
0 structural parameters have been obtained for both conformers by combining the ab initio data with the previously reported microwave rotational constants. These new values of the structural parameters for both conformers are compared to those previously reported from electron diffraction and microwave studies. These results are compared to the corresponding quantities of some similar molecules.
Structural Chemistry 11/2003; 14(6):617-635. · 1.85 Impact Factor
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ABSTRACT: Infrared (3500−50 cm-1) spectra of gaseous and Raman (3500−50 cm-1) spectra of liquid aminomethyl cyclopropane (cyclopropyl methylamine), c−C3H5CH2NH2 have been recorded. Additional variable temperature (−55 to −100 °C) studies of the mid-infrared (3500−400 cm-1) spectra of the sample dissolved in liquid xenon as well as variable temperature (−79 to −112 °C) studies of the far-infrared spectra (600−50 cm-1) of krypton solutions have been obtained. From these data the enthalpy difference has been determined to be 109 ± 11 cm-1 (1.30 ± 0.13 kJ/mol) between the most stable gauche−gauche-1 (Gg-1) conformer (the first gauche designation, capital G, for the heavy atom conformation along the C−C bond, and the second gauche designation, lower case g, for the amino torsion along C−N bond) and the second most stable conformation, gauche-trans (Gt). The third most stable conformer is the cis-gauche (Cg) form with an enthalpy difference of 267 ± 28 cm-1 (3.19 ± 0.33 kJ/mol) to the most stable conformer. Larger enthalpy values of 400 ± 40 cm-1 and 480 ± 48 cm-1 were obtained for the Gg-2 and Ct conformers, respectively. From these data, the following conformer percentages are estimated at ambient temperature: 49% Gg-1, 29% Gt, 13% Cg, 7% Gg-2, and 2% Ct. Ab initio calculations have been carried out with several different basis sets up to MP2/6-311G(2df,2pd) as well as with diffuse functions to determine the conformational stability. Without diffuse functions, the Gt conformer is predicted as the most stable conformer, whereas with diffuse functions, the Gg-1 form is predicted to be the most stable rotamer, and the density functional calculations by the B3LYP method with the same corresponding basis sets all predict the Gt form as the most stable conformer. Additionally, force constants, infrared intensities, Raman activities, depolarization ratios, and scaled vibrational frequencies have been determined from MP2/6-31G(d) calculations. Vibrational assignments are provided for most of the fundamentals for the Gg-1 and Gt conformers. Adjusted r0 structural parameters have been obtained by combining ab initio MP2/6-311+G(d,p) predicted values and previously reported microwave data for the Gg-1 and Gt forms. Many of the determined results are compared to the corresponding parameters for some other similar organoamines.
08/2003;
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ABSTRACT: Infrared spectra (3500-50 cm(-1)) of gaseous and solid, and Raman spectrum (3500-30 cm(-1)) of liquid vinyldifluorosilane, CH(2)z.dbnd6;CHSiF(2)H, are reported. Both the cis and gauche rotamers have been identified in the fluid phases. From temperature-dependent FT-infrared spectra of krypton solutions, it is shown that the cis conformer is more stable than the gauche form by 119+/-12 cm(-1) (1.42+/-0.14 kJ mol(-1)). At ambient temperature there is 53+/-2% of the gauche conformer present. Complete vibrational assignments are provided for the cis conformer and several modes are identified for the gauche form. Harmonic force constants, fundamental frequencies, infrared intensities, and Raman activities have been obtained from MP2/6-31G(d) calculations with full electron correlation. The optimized geometries and conformational stabilities have also been obtained from ab initio MP2/6-31G(d), MP2/6-311+G(d,p), and MP2/6-311+G(2d,2p) calculations with full electron correlation as well as from density functional theory calculations (DFT) by the B3LYP method. The SiH bond distances (r(0)) of 1.472 and 1.471 A have been obtained for the cis and gauche conformers, respectively, from the silicon-hydrogen stretching frequencies. These results are compared to the corresponding quantities of the corresponding carbon analogue as well as with some similar molecules.
Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy 08/2003; 59(9):2099-114. · 2.10 Impact Factor
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ABSTRACT: The Raman spectrum of liquid ethyldibromosilane, CH3CH2SiHBr2, was recorded at various temperatures between 298 and 218 K, and the spectrum of the crystal was obtained at 210 K from a sample sealed in a capillary. Additional spectra of the amorphous and annealed crystals, which were deposited on a copper finger cooled with boiling liquid nitrogen, were recorded. The infrared spectra were recorded of the vapor and amorphous and crystalline solid in the range 4000–50 cm−1 and mid-infrared spectra isolated at 4.8 K in argon and nitrogen matrices were also observed. These vibrational spectra show that two conformers, anti and gauche, are present in the vapor and in the liquid, but only the anti conformer remains in the crystalline solid. Three conformer pairs in the Raman spectrum of the liquid phase were used to obtain the enthalpy difference, which gave an average value of 128 ± 17 cm−1 (1.53 ± 0.2 kJ mol−1) with the anti form lower in energy. At ambient temperature it is estimated that there is 52 ± 2% of the gauche conformer present in the liquid. The optimized geometries, infrared and Raman intensities, and scaled vibrational wavenumbers for the anti and gauche conformers were obtained from ab initio MP2/6–31G(d) calculations with full electron correlation. The conformational energy difference was also obtained from ab initio MP2/6–311 + G(d,p) calculations which gave a predicted energy difference of 97 cm−1 with the anti form the conformer of lower energy. These spectroscopic and theoretical results are discussed and compared with the corresponding quantities for some similar molecules. Copyright © 2003 John Wiley & Sons, Ltd.
Journal of Raman Spectroscopy 03/2003; 34(4):322 - 336. · 3.09 Impact Factor
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ABSTRACT: Variable-temperature (−55 to −100 °C) studies of the infrared spectra (3500−400 cm-1) of methylhydrazine, CH3NHNH2, dissolved in liquid xenon have been recorded. From these data the enthalpy difference has been determined to be 323 ± 30 cm-1 (3.86 ± 0.36 kJ/mol) with the inner conformer (methyl group staggered and between the two hydrogens of the NH2 group) the more stable rotamer. A complete vibrational assignment is presented for the inner conformer, and several of the fundamentals of the outer conformer have been assigned. These assignments are consistent with the predicted wavenumbers obtained from ab initio MP2/6-31G(d) calculations utilizing three scaling factors. The optimized geometries, conformational stabilities, harmonic force fields, infrared intensities, Raman activities, and depolarization ratios have been obtained from RHF/6-31G(d) and/or MP2/6-31G(d) ab initio calculations. Hybrid density functional theory (DFT) calculations to obtain the structural parameters and conformational stability by the B3LYP method were also carried out. These quantities are compared to the corresponding experimental quantities when appropriate. Additionally conformational stabilities and structural parameters have also been predicted from MP2 level calculations with full electron correlation with 6-311+G(d,p) and 6-311+G(2d,2p) basis sets. The r0 structural parameters have been obtained from a combination of the previously reported microwave rotational constants and ab initio MP2/6-311+G(d,p) predicted parameters. The results are compared to some corresponding quantities for some similar molecules.
01/2002;
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ABSTRACT: Infrared spectra (3500–50 cm−1) of gaseous and solid and Raman spectra (3500–30 cm−1) of liquid and solid dichloromethyldimethyl silane, CHCl2Si(CH3)2H, are reported. Additionally, the depolarization measurements have been obtained from the Raman spectrum of the liquid. The gauche and anti rotamers have been identified in the fluid phases but only the gauche conformer remains in the polycrystalline solid. From temperature dependent FT-infrared spectra of krypton solutions, it is shown that the gauche conformer is more stable than the anti form by 126±13 cm−1 (1.51±0.16 kJ mol−1). At ambient temperature there is 21±2% of the anti conformer present. Complete vibrational assignments are provided for the gauche conformer and several modes are identified for the anti form. Harmonic force constants, fundamental frequencies, infrared intensities, and Raman activities have been obtained from MP2/6-31G(d) calculations with full electron correlation. The optimized geometries and conformational stabilities have also been obtained from ab initio MP2/6-31G(d), MP2/6-311+G(d,p) and MP2/6-311+G(2d,2p) calculations with full electron correlation. The r0 SiH bond distances of 1.482 and 1.485 Å have been obtained for the anti and gauche conformers, respectively, from the silicon–hydrogen stretching frequencies. These results are compared to the corresponding quantities of some similar molecules.
Journal of Molecular Structure. 649:7-24.
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ABSTRACT: Variable temperature (−60 to −100 °C) studies of the infrared spectra (3200–400 cm−1) of isopropylisothiocyanate, (CH3)2CHNCS, dissolved in liquefied xenon, have been carried out. Additionally the infrared spectra of the gas and solid have been recorded for both isopropylisothiocyanate and tertiary-butylisothiocyanate, (CH3)3CNCS, from 3200 to 100 cm−1. The analyses of these spectral data for the isopropyl molecule and the Raman spectrum of the liquid indicated one stable conformer (trans) in the annealed solid but in the fluid phases most of the molecules have energies above the barriers of the two predicted bound vibrational states i.e., trans and gauche forms. The MP2(full) ab initio calculations, employing a variety of basis sets with and without diffuse functions, have been used to predict the conformational stabilities with the trans conformer, the most stable form, for isopropylisothiocyanate and the second most stable form is predicted to be either the skew or gauche conformer depending in some cases on whether diffuse functions are used. However, even when the energy values indicate the skew form more stable than the gauche rotamer, one imaginary frequency indicates the skew form is a first-order saddle point. These results should be contrasted with the microwave data where the experimental B + C value was previously interpreted to indicate the skew conformer as the most stable form. For t-butylisothiocyanate the staggered conformer is the more stable form with the eclipsed conformer a transition state with a barrier of ∼50 cm−1 so there is nearly free internal rotation of the NCS moiety. For both molecules, the structural parameters, dipole moments, conformational stability, vibrational frequencies, infrared intensities and Raman activities have been predicted from ab initio calculations and complete vibrational assignments are proposed. The r0 structural parameters are estimated by combing the MP2(full)/6-311+G(d,p) predicted values for the CH parameters with some adjustments to the heavy atom distances. These experimental and theoretical results are compared to the corresponding quantities of some similar molecules.
Journal of Molecular Structure. 839:107-124.
