The molecular structure and curious motions in 1,1-difluorosilacyclopent-3-ene and silacyclopent-3-ene as determined by microwave spectroscopy and quantum chemical calculations.

The molecules 1,1-difluorosilacyclopent-3-ene (3SiCPF2) and silacyclopent-3-ene (3SiCP) have been synthesized and studied using chirped pulse, Fourier transform microwave (CP-FTMW) spectroscopy. For 3SiCP this is the first ever microwave study of the molecule and, for 3SiCPF2, the spectra reported in this work have been combined with that of previous work in a global fit. The spectra of each contain splitting which has been fit using a Hamiltonian consisting of semirigid and Coriolis coupling parameters. A refit of the original 3SiCPF2 work was also carried out. All fits and approaches are reported. Analyses of the spectra provide evidence that the molecule is planar which is in agreement with the high-level calculations, but the source of the splitting in the spectra has not been determined.

Anomeric Effect in Five-Membered Ring Molecules: Comparison of Theoretical Computations and Experimental Spectroscopic Results.

As demonstrated in previous spectroscopic studies of 1,3-dioxole [ J. Am. Chem. Soc., 1993, 115, 12132-12136] and 1,3-benzodioxole [ J. Am. Chem. Soc., 1999, 121, 5056-5062], analysis of the ring-puckering potential energy function (PEF) of a "pseudo-four-membered ring" molecule can provide insight into understanding the magnitude of the anomeric effect. In the present study, high-level CCSD/cc-pVTZ and somewhat lower-level MP2/cc-pVTZ ab initio computations have been utilized to calculate the PEFs for 1,3-dioxole and 1,3-benzodioxole and 10 related molecules containing sulfur and selenium atoms and possessing the anomeric effect. The potential energy parameters derived for the PEFs directly provide a comparison of the relative magnitudes of the anomeric effect for molecules possessing OCO, OCS, OCSe, SCS, SCSe, and SeCSe linkages. The torsional potential energies produced by the anomeric effect for these linkages were estimated to range from 5.97 to 1.91 kcal/mol. The ab initio calculations also yielded the structural parameters, barriers to planarity, and ring-puckering angles for each of the 12 molecules studied. Based on the refined structural parameters for 1,3-dioxole and 1,3-benzodioxole, improved PEFs for these molecules were also calculated. The calculations also support the conclusion that the relatively low barrier to planarity of 1,3-benzodioxole results from competitive interactions between its benzene ring and the oxygen atom p orbitals.

Spectroscopic and Theoretical Study of the Intramolecular π-Type Hydrogen Bonding and Conformations of 2-Cyclopenten-1-ol.

The conformations of 2-cyclopenten-1-ol (2CPOL) have been investigated by high-level theoretical computations and infrared spectroscopy. The six conformational minima correspond to specific values of the ring-puckering and OH internal rotation coordinates. The conformation with the lowest energy possesses intramolecular π-type hydrogen bonding. A second conformer with weaker hydrogen bonding has somewhat higher energy. Ab initio coupled-cluster theory with single and double excitations (CCSD) was used with the cc-pVTZ (triple-ζ) basis set to calculate the two-dimensional potential energy surface (PES) governing the conformational dynamics along the ring-puckering and internal rotation coordinates. The two conformers with the hydrogen bonding lie about 300 cm-1 (0.8 kcal/mole) lower in energy than the other four conformers. The lowest energy conformation has a calculated distance of 2.68 Å from the hydrogen atom on the OH group to the middle of the C=C double bond. For the other conformers, this distance is at least 0.3 Å longer. The infrared spectrum in the O-H stretching region agrees well with the predicted frequency differences between the conformers and shows the conformers with the hydrogen bonding to have the lowest values. The infrared spectra in other regions arise mostly from the two hydrogen-bonded species.

Spectroscopic and Theoretical Study of the Intramolecular π-Type Hydrogen Bonding and Conformations of 3-Cyclopentene-1-amine.

The infrared and Raman spectra of 3-cyclopentene-1-amine (3CPAM) have been recorded and analyzed, and the experimental investigations have been complemented by theoretical calculations. Ab initio coupled cluster theory with single and double excitations (CCSD) was used with the cc-pVTZ (triple-ζ) basis set to calculate the conformational energy and geometrical parameters for each of the six conformers of this molecule. MP2/cc-pVTZ and B3LYP/cc-pVTZ computations were utilized to calculate the vibrational frequencies of the conformers. Both the spectra and theoretical calculations verify the presence of the conformers and show that the conformer at the lowest energy has intramolecular π-type hydrogen bonding involving the NH2 group. The hydrogen bonded conformer is about 2 kJ/mol lower in energy than the other conformers. The potential energy topographical contour map for the ring-puckering and NH2 internal rotation coordinates has been calculated, and this shows how the different conformers can interconvert into each other. The far-infrared spectrum in the 190 to 280 cm-1 region shows several NH2 internal rotation bands for each of the different conformers, and these are consistent with one-dimensional representations for their torsional motions.

Theoretical Calculations, Microwave Spectroscopy, and Ring-Puckering Vibrations of 1,1-Dihalosilacyclopent-2-enes.

High-level theoretical CCSD/cc-pVTZ computations have been carried out to calculate the structures and ring-puckering potential energy functions (PEFs) for 1,1-difluorosilacyclopent-2-ene (2SiCPF2) and 1,1-dichlorosilacyclopent-2-ene (2SiCPCl2). The structure and PEF for 1,1-dibromosilacyclopent-2-ene (2SiCPBr2) were obtained by ab initio MP2/cc-pVTZ computations. The parent silacyclopent-2-ene (2SiCP) is puckered with a 49 cm-1 barrier to planarity, 2SiCPF2 has a planar ring system, 2SiCPCl2 has a calculated tiny 4 cm-1 barrier but is essentially planar, and the dibromide has a calculated barrier of 36 cm-1. Microwave spectra of seven isotopic species of 2SiCPF2 were recorded on a chirped pulse, Fourier transform microwave (CP-FTMW) spectrometer in the 6-18 GHz region. The a-type and b-type transitions were observed. The rotational constants and three quartic centrifugal distortion constants were determined for the parent, 29Si, 30Si, and all singly substituted 13C isotopologues in natural abundance. This allowed for the determination of the heavy-atom structure of the ring and showed the ring to be planar. The experimentally determined rotational constants and geometrical parameters agree very well with the theoretical values and confirm the planarity of the five-membered ring. A comparison of the PEFs for the silane and the three dihalides shows the silane to have the stiffest puckering motion and the dibromide to be the least rigid.

Theoretical Study of Structures and Ring-Puckering Potential Energy Functions of Bicylo[3.1.0]hexane and Related Molecules.

Ab initio computations using the MP2/cc-pVTZ method have been carried out to calculate the structures and relative energies of the different conformations of five bicyclic molecules including bicyclo[3.1.0]hexane, 3-oxabicyclo[3.1.0]hexane, 6-oxabicyclo[3.1.0]hexane, 3,6-oxabicyclo[3.1.0]hexane, and bicyclo[3.1.0]hexan-3-one. Theoretical ring-puckering potential energy functions (PEFs) in terms of the ring-puckering coordinate have been calculated for each of the molecules and these were compared to those determined experimentally from spectroscopic data. Each potential function is asymmetric and has an energy minimum corresponding to where the five-membered ring is puckered in the same direction as the attached three-membered ring. In contrast to the experimental result, the calculations predict that bicyclo[3.1.0]hexane has a second shallow energy minimum. All of the other molecules have a single conformational minimum and their experimental and theoretical PEFs agree very well. The wave functions for the lower ring-puckering energy levels have been computed.

Ring-Puckering Potential Energy Functions for Trimethylene Sulfide and Its Monovalent Cation.

The spectra and ring-puckering potential energy function for trimethylene sulfide cation (TMS+) from vacuum ultraviolet mass-analyzed threshold ionization spectra have recently been reported. To provide an in-depth comparison of the potential function with that of trimethylene sulfide (TMS) itself, we have used ab initio MP2/cc-pVTZ calculations and DFT B3LYP/cc-pVTZ calculations to predict the structures of both TMS and TMS+ and then used these to calculate coordinate-dependent ring-puckering kinetic energy functions for both species. These kinetic energy functions allowed us to calculate refined potential energy functions of the puckering for both molecules based on the previously published spectra. TMS has an experimental barrier of 271 cm-1 and energy minima at ring-puckering angles of ±29°. For TMS+ the barrier is 60 cm-1 and the energy minima correspond to ring-puckering angles of ±21°. The lower barrier for the cation reflects the smaller amount of angle strain in the ring angles for TMS+.

Spectroscopic and Theoretical Study of the Intramolecular π-Type Hydrogen Bonding and Conformations of 2-Cyclohexen-1-ol.

The infrared and Raman spectra of 2-cyclohexen-1-ol have been recorded and analyzed. The experimental work has been complemented by ab initio and density functional theory computations. The calculations show that in the vapor phase the conformations with the π-type hydrogen bonding are the lowest in energy, and these findings are supported by the experimental spectra, which agree well with the theoretical predictions. The six conformers predicted result from differences between the direction on the ring-twisting angle and the -OH internal rotation angle. The lowest-energy conformer has the hydrogen of the OH group pointing to the middle of the C═C double bond. The other conformers are calculated to be 72 cm(-1) (0.21 kcal/mol) to 401 cm(-1) (1.15 kcal/mol) higher in energy. In the liquid phase, only two conformers can be identified in the spectra, and these correspond to different directions of the ring-twisting.

Internal Rotation of Methylcyclopropane and Related Molecules: Comparison of Experiment and Theory.

The internal rotation about the single bond connecting a cyclopropyl ring to a CH3, SiH3, GeH3, NH2, SH, or OH group was investigated. Both CCSD/cc-pVTZ and MP2/cc-pVTZ ab initio calculations were performed to predict the structures of these molecules and their internal rotation potential energy functions in terms of angles of rotation. The barriers to internal rotation for the CH3, SiH3, and GeH3 molecules from the calculations agree well with the experimental ones, within -11% to +1% for CCSD/cc-pVTZ and -4% to +9% for MP2/cc-pVTZ. Comparisons between theory and experiment were also performed for propylene oxide and propylene sulfide, and the agreements were very good. Theoretical calculations were performed to compute the internal rotation potential energy function for cyclopropanol, and these were used to guide the determination of a potential function based on experimental data. This molecule has two equivalent synclinal (gauche) conformers with an estimated barrier of 759 cm(-1) (9.1 kJ/mol) between them. The minima are at internal rotation angles of the OH group of 109° and 251°. The theoretical potential functions for cyclopropanethiol and cyclopropylamine were also calculated, and these agree reasonably well with previous experimental studies.

Vapor-Phase Raman Spectra and the Barrier to Planarity of Cyclohexane.

The vapor-phase Raman spectra of an atmosphere of cyclohexane vapor heated to 90 and 110 °C collected over a large period of time and utilizing a high laser power of 4 W show hot band series starting at 380.8 cm-1 and corresponding to the v6(A1g) ring-inversion vibration. Fitting this data with a one-dimensional potential energy function allows the barrier to planarity of 8600 cm-1 (24.6 kcal/mol) to be calculated. Ab initio calculations (MP2/cc-pVTZ) predict a value of 10 377 cm-1 (29.7 kcal/mol), while DFT (B3LYP/cc-pVTZ) calculations predict 8804 cm-1 (25.2 kcal/mol).

Microwave Spectra, Structure, and Ring-Puckering Vibration of Octafluorocyclopentene.

The rotational spectra of octafluorocyclopentene (C5F8) has been measured for the first time using pulsed jet Fourier transform microwave spectroscopy in a frequency range of 6 to 16 GHz. As in the molecule cyclopentene, the carbon ring is nonplanar, and inversion through the plane results in an inversion pair of ground state vibrational energy levels with an inversion splitting of 18.4 MHz. This large amplitude motion leads to the vibration-rotation coupling of energy levels. The symmetric double minimum ring-puckering potential function was calculated, resulting in a barrier of 222 cm-1. The rotational constants A0 = 962.9590(1) MHz, B0 = 885.1643(4) MHz, C0 = 616.9523(4) MHz, A1 = 962.9590(1) MHz, B1 = 885.1643(4) MHz, C1 = 616.9528(4) MHz, and two centrifugal distortion constants for each state were determined for the parent species and all 13C isotopologues. A mixed coordinate molecular structure was determined from a least-squares fit of the ground state rotational constants of the parent and each 13C isotopologue combined with the equilibrium bond lengths and angles from quantum chemical calculations.

Infrared and Raman spectra, theoretical calculations, conformations, and two-dimensional potential energy surface of 2-cyclopenten-1-one ethylene ketal.

The infrared and Raman spectra of the bicyclic spiro molecule 2-cyclopenten-1-one ethylene ketal (CEK) have been recorded. Density functional theory (DFT) calculations were used to compute the theoretical spectra, and these agree well with the experimental spectra. The structures and conformational energies for the two pairs of conformational minima, which can be defined in terms of ring-bending (x) and ring-twisting (τ) vibrational coordinates, have also been calculated. Utilizing the results from ab initio MP2/cc-PVTZ computations, a two-dimensional potential energy surface (PES) was calculated. The energy levels and wave functions for this PES were then calculated, and the characteristics of these were analyzed. At lower energies, all of the quantum states are doubly degenerate and correspond to either the lower-energy conformation L or to conformation H, which is 154 cm(-1) higher in energy. At energies above the barrier to interconversion of 264 cm(-1), the wave functions show that the quantum levels have significant probabilities for both conformations.

Vibrational spectra, theoretical calculations, and two-dimensional potential energy surface for the ring-puckering vibrations of 2,4,7-trioxa[3.3.0]octane.

2,4,7-Trioxa[3.3.0]octane (247TOO) is an unusual bicyclic molecule which can exist in four different conformational forms which are determined by the directions of the two ring- puckering motions. The vibrational assignments of 247TOO have been made based on its infrared and Raman spectra and theoretical density functional theory (DFT) calculations. The two ring-puckering motions (in-phase and out-of-phase) were observed in the Raman spectra of the liquid at 249 and 205 cm(-1) and these values correspond well to the DFT values of 247 and 198 cm(-1). Ab initio calculations were utilized to calculate the structures and conformational energies for the four energy minima and the barriers to interconversion and the data was utilized to generate a two-dimensional potential energy surface (PES) for the two ring-puckering motions. The resulting quantum state energies for this PES were then calculated in order to better understand the patterns that are produced when the PES has four energy minima at different energy values. The wave functions corresponding to the different quantum states were also calculated. The NMR spectrum of 247TOO showed the presence of the two lowest energy conformations, consistent with the results of the ab initio calculations.

Anharmonic Vibrational Analysis of the Infrared and Raman Gas-Phase Spectra of s-trans- and s-gauche-1,3-Butadiene.

A quantum-mechanical (hybrid MP2/cc-pVTZ and CCSD(T)/cc-pVTZ) full quartic potential energy surface (PES) in rectilinear normal coordinates and the second-order operator canonical Van Vleck perturbation theory (CVPT2) are employed to predict the anharmonic vibrational spectra of s-trans- and s-gauche-butadiene (BDE). These predictions are used to interpret their infrared and Raman scattering spectra. New high-temperature Raman spectra in the gas phase are presented in support of assignments for the gauche conformer. The CVPT2 solution is based on a PES and electro-optical properties (EOP; dipole moment and polarizability) expanded in Taylor series. Higher terms than those routinely available from Gaussian09 software were calculated by numerical differentiation of quadratic force fields and EOP using the MP2/cc-pVTZ model. The integer coefficients of the polyad quantum numbers were derived for both conformers of BDE. Replacement of harmonic frequencies by their counterparts from the CCSD(T)/cc-pVTZ model significantly improved the agreement with experimental data for s-trans-BDE (root-mean-square deviation ≈ 5.5 cm(-1)). The accuracy in predicting the rather well-studied spectrum of fundamentals of s-trans-BDE assures good predictions of the spectrum of s-gauche-BDE. A nearly complete assignment of fundamentals was obtained for the gauche conformer. Many nonfundamental transitions of the BDE conformers were interpreted as well. The predictions of multiple Fermi resonances in the complex CH-stretching region correlate well with experiment. It is shown that solving a vibrational anharmonic problem through a numerical-analytic implementation of CVPT2 is a straightforward and computationally advantageous approach for medium-size molecules in comparison with the standard second-order vibrational perturbation theory (VPT2) based on analytic expressions.

Infrared, Raman, and Ultraviolet Absorption Spectra and Theoretical Calculations and Structure of 2,3,5,6-Tetrafluoropyridine in its Ground and Excited Electronic States.

Infrared and Raman spectra of 2,3,5,6-tetrafluoropyridine (TFPy) were recorded and vibrational frequencies were assigned for its S0 electronic ground states. Ab initio and density functional theory (DFT) calculations were used to complement the experimental work. The lowest electronic excited state of this molecule was investigated with ultraviolet absorption spectroscopy and theoretical CASSCF calculations. The band origin was found to be at 35,704.6 cm-1 in the ultraviolet absorption spectrum. A slightly puckered structure with a barrier to planarity of 30 cm-1 was predicted by CASSCF calculations for the S1(π,π*) state. Lower frequencies for the out-of-plane ring bending vibrations for the electronic excited state result from the weaker bonding within the pyridine ring.

Vapor-phase Raman spectra, theoretical calculations, and the vibrational and structural properties of cis- and trans-stilbene.

The vapor-phase Raman spectra of cis- and trans-stilbene have been collected at high temperatures and assigned. The low-frequency skeletal modes were of special interest. The molecular structures and vibrational frequencies of both molecules have also been obtained using MP2/cc-pVTZ and B3LYP/cc-pVTZ calculations, respectively. The two-dimensional potential map for the internal rotations around the two Cphenyl-C(═C) bonds of cis-stilbene was generated by using a series of B3LYP/cc-pVTZ calculations. It was confirmed that the molecule has only one conformer with C2 symmetry. The energy level calculation with a two-dimensional Hamiltonian was carried out, and the probability distribution for each level was obtained. The calculation revealed that the "gearing" internal rotation in which the two phenyl rings rotate with opposite directions has a vibrational frequency of 26 cm(-1), whereas that of the "antigearing" internal rotation in which the phenyl rings rotate with the same direction is about 52 cm(-1). In the low vibrational energy region the probability distribution for the gearing internal rotation is similar to that of a one-dimensional harmonic oscillator, and in the higher region the motion behaves like that of a free rotor.

Theoretical calculations and vibrational potential energy surface of 4-silaspiro(3,3)heptane.

Theoretical computations have been carried out on 4-silaspiro(3,3)heptane (SSH) in order to calculate its molecular structure and conformational energies. The molecule has two puckered four-membered rings with dihedral angles of 34.2° and a tilt angle of 9.4° between the two rings. Energy calculations were carried out for different conformations of SSH. These results allowed the generation of a two-dimensional ring-puckering potential energy surface (PES) of the form V = a(x1 (4) + x2 (4)) - b(x1 (2) + x2 (2)) + cx1 (2)x2 (2), where x1 and x2 are the ring-puckering coordinates for the two rings. The presence of sufficiently high potential energy barriers prevents the molecule from undergoing pseudorotation. The quantum states, wave functions, and predicted spectra resulting from the PESs were calculated.

Fluorescence excitation and ultraviolet absorption spectra and theoretical calculations for benzocyclobutane: vibrations and structure of its excited S(1)(π,π(*)) electronic state.

The fluorescence excitation spectra of jet-cooled benzocyclobutane have been recorded and together with its ultraviolet absorption spectra have been used to assign the vibrational frequencies for this molecule in its S1(π,π(*)) electronic excited state. Theoretical calculations at the CASSCF(6,6)/aug-cc-pVTZ level of theory were carried out to compute the structure of the molecule in its excited state. The calculated structure was compared to that of the molecule in its electronic ground state as well as to the structures of related molecules in their S0 and S1(π,π(*)) electronic states. In each case the decreased π bonding in the electronic excited states results in longer carbon-carbon bonds in the benzene ring. The skeletal vibrational frequencies in the electronic excited state were readily assigned and these were compared to the ground state and to the frequencies of five similar molecules. The vibrational levels in both S0 and S1(π,π(*)) states were remarkably harmonic in contrast to the other bicyclic molecules. The decreases in the frequencies of the out-of-plane skeletal modes reflect the increased floppiness of these bicyclic molecules in their S1(π,π(*)) excited state.

Trans effect in halobismuthates and haloantimonates revisited. Molecular structures and vibrations from theoretical calculations.

Ab initio and density functional theory computations have been carried out to calculate the structures and vibrational spectra of halobismuthates and haloantimonates of formulas MX6(3-), M2X10(4-), and M2X9(3-) for M = Bi or Sb and X = I, Br, or Cl. The results have been compared to experimental crystal structures and the infrared and Raman spectra of these species as well as the (MX5(2-))n and (MX4(1-))n anions. Even though the calculations neglect the effect of which cation is present, they do a good job in verifying the observed trends in bond distances and bond stretching vibrational frequencies. External bonds across from bridging bonds are the shortest and have the highest stretching frequencies for all of the ions investigated. This supports the previously postulated "trans effect". Since the calculations were carried out for individual noninteracting anions, the computed results can be expected to best represent the idealized species unperturbed by the effect of the cations present. The trans effect results in shortening of the M-X bonds by 0.08-0.13 Å. It also leads to frequency increases of about 20% for the M-X stretching vibrations.

Infrared, Raman, and ultraviolet absorption spectra and theoretical calculations and structure of 2,6-difluoropyridine in its ground and excited electronic states.

The infrared and Raman spectra of 2,6-difluoropyridine (26DFPy) along with ab initio and DFT computations have been used to assign the vibrations of the molecule in its S0 electronic ground state and to calculate its structure. The ultraviolet absorption spectrum showed the electronic transition to the S1(π,π*) state to be at 37,820.2 cm(-1). With the aid of ab initio computations the vibrational frequencies for this excited state were also determined. TD-B3LYP and CASSCF computations for the excited states were carried out to calculate the structures for the S1(π,π*) and S2(n,π*) excited states. The CASSCF results predict that the S1(π,π*) state is planar and that the S2(n,π*) state has a barrier to planarity of 256 cm(-1). The TD-B3LYP computations predict a barrier of 124 cm(-1) for the S1(π,π*) state, but the experimental results support the planar structure. Hypothetical models for the ring-puckering potential energy function were calculated for both electronic excited states to show the predicted quantum states. The changes in the vibrational frequencies in the two excited states reflect the weaker π bonding within the pyridine ring.