Vacuum ultraviolet mass-analyzed threshold ionization spectroscopy of hexafluorobenzene: the Jahn-Teller effect and vibrational analysis

One-photon mass-analyzed threshold ionization (MATI) spectrum of hexafluorobenzene was obtained by using vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. The ionization energy of hexafluorobenzene determined from the position of the 0-0 band was 9.9108+/-0.0006 eV. To aid the spectral analysis, the Jahn-Teller coupling parameters for four e(2g) modes of C(6)F(6) (+) in the ground electronic state were calculated from the topographical data of the potential energy surface obtained at the density functional theory (DFT) level. These were used in the initial calculation of the energies of the Jahn-Teller states and upgraded through the multimode fit to the experimental data. Excellent agreement between the experimental and calculated frequencies was achieved. The vibrations which are not linear Jahn-Teller active were observed and could be assigned by referring to the frequencies obtained at the DFT level.     

The orbital interpretation of the photoelectron spectrum of benzene, 1,3,5-trifluorobenzene and hexafluorobenzene

An interpretation of certain features in the vibrational pattern of the 11.5 to 13.0 eV photoelectron spectrum of benzene in terms of a Jahn-Teller effect is presented. This supports Lindholm's orbital assignment of the ionization processes in this region. A change in the assignment of some of the higher systems in the photoelectron spectra of 1,3,5,-trifluorobenzene and hexafluorobenzene is proposed. Some discussion of Rydberg series found in these molecules is also given.     

氯代苯阳离子的密度泛函理论研究

采用B3LYP方法及6-311G(d,p)和6-311+G(d,p)基组,对12种氯代苯阳离子进行了理论研究,优化其电子基态的结构,计算了对应分子的垂直电离势(VIP)和绝热电离势(AIP).依据Jahn-Teller理论,确定了1,3,5-C6H3Cl3+和C6Cl6+离子分别具有C2v(2B1)和D2h(2B2g)结构(对应分子分别为D3h和D6h结构).其余10个离子的构型的对称点群与对应分子相同,但构型参数值有明显差别.用B3LYP方法计算的各氯代苯分子的垂直电离势和绝热电离势与实验值符合得很好.     

The Jahn-Teller effect in the lower electronic states of benzene cation. III. The ground-state vibrations of C6H6+ and C6D6+

New mass analyzed threshold ionization (MATI) spectra of the molecules C(6)H(6) (+) and C(6)D(6) (+) have been collected using tunable vacuum ultraviolet (VUV) single photon excitation from the neutral ground state and also using two-photon excitation through the 6(1) vibration of the (1)B(2u) S(1) state. Emphasis was placed on obtaining accurate relative intensities of the vibrational lines in order to use this information in the vibronic analysis. The MATI spectra collected from VUV (S(0) originating state), triplet (T(1)), and resonant two photon (S(1)) excitation schemes were compared with Jahn-Teller calculations employing the classical model of Longuet-Higgins and Moffitt to obtain the Jahn-Teller coupling parameters of 3 of the 4 linearly active modes (e(2g) modes 6-9 in Wilson's notation). Franck-Condon factors, including the effects of geometry changes, were calculated from the vibronic wave functions and used to identify the lines in the various spectra. It is found that most of the lines with substantial intensity can be understood using only the modes 1, 6, 8, and 9. Weaker peaks are due to various non-e(2g) modes, but these do not derive intensity through Jahn-Teller coupling. When the effects of geometry change were included, simulations of the spectra from the calculated vibrational energies and intensities were close to the experimental spectra. This verifies the applicability of the model to the understanding of the vibrational structure of this type of molecule, but some variations indicate directions for further improvement of the model.     

Structural features of 1,3,5-trifluorobenzene radical anion,as studied by optically detected ESR spectroscopy and quantum chemistry

The ESR spectrum of 1,3,5-trifluorobenzene radical anion was obtained for the first time using optically detected ESR spectroscopy. Experimental data and results of a quantum chemical study of the potential energy surface (density functional theory B3LYP and BHHLYP methods) are indicative of fast interconversions between nonplanar conformations of this radical anion.     

Microstructural analysis of poly(vinylidene fluoride) using benzene derivative pyrolysis products

Poly(vinylidene fluoride) (PVDF) was pyrolyzed, and the pyrolysis products were analyzed using gas chromatography/mass spectrometry (GC/MS) to develop a method for identification of the microstructures of head-to-tail (H-T), tail-to-tail (T-T), and head-to-head-to-tail-to-tail (H-H-T-T) sequences. Key pyrolysis products to determine the relative degrees of the microstructures were benzene derivatives. 1,4-Difluorobenzene, 1,2,4-trifluorobenzene, and 1,3,5-trifluorobenzene were major pyrolysis products as benzene derivatives. 1,3,5-Trifluorobenzene and 1,2,4-trifluorobenzene were formed from two HF-eliminated PVDF by 1,6-HF elimination and 1,6-rearrangement, while 1,4-difluorobenzene was generated from two HF-eliminated PVDF by 1,6-H₂ elimination and 1,6-rearrangement. 1,3,5-Trifluorobenzene was generated from the H-T sequence, whereas 1,4-difluorobenzene was formed from the T-T one. 1,2,4-Trifluorobenzene can be formed from the H-H-T-T sequence. Relative component ratios of the H-T, T-T, and H-H-T-T sequences of PVDFs can be estimated by comparing relative abundances of the benzene derivative pyrolysis products.     

Fluorobenzene-nucleobase interactions: hydrogen bonding or pi-stacking?

Studies on modified DNA oligomers and polymerase reactions have previously demonstrated that canonical nucleobases can exhibit stable and even selective pairing with shape-complementary fluorobenzene nucleotides. Because of the fluorination of the pairing edges, hydrogen bonds are believed to be absent, and the local DNA stability has been attributed to pi-stacking and shape complementarity. Using two-color resonant two-photon ionization and fluorescence emission spectroscopies, we show here that supersonically cooled complexes of the nucleobase analogue 2-pyridone with seven substituted fluorobenzenes (1-fluorobenzene, 1,2- and 1,4-difluorobenzene, 1,3,5- and 1,2,3-trifluorobenzene, 1,2,4,5- and 1,2,3,4-tetrafluorobenzene) are hydrogen-bonded and not pi-stacked. The S1 <--> S0 vibronic spectra show intermolecular vibrational frequencies that are characteristic for doubly hydrogen bonded complexes. The bands shift to the blue with increasing hydrogen-bond strength; the measured spectral blue shifts deltanu are in excellent agreement with the ab initio calculated shifts. The spectral shifts are also linearly correlated with the calculated hydrogen-bond dissociation energies D0, published in a companion paper (Frey, J. A.; Leist, R.; Leutwyler, S. J. Phys. Chem. A 2006, 110, 4188). This correlation allows us to reliably estimate the ground-state dissociation energies as D0 approximately 6 kcal/mol of the 2-pyridone.fluorobenzene complexes from the observed spectral shifts.     

Mass spectral fragmentation pathways in RDX and HMX. A mass analyzed ion kinetic energy spectrometric/collisional induced dissociation study

A collisional induced dissociation study of 1,3,5-trinitro-1,3,5 triazacyclohexane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX) was carried out using mass analyzed kinetic energy spectrometry. High resolution mass spectra and mass analyzed ion kinetic energy/collisional induced dissociation spectra of RDX and HMX were recorded in the electron impact, chemical ionization and negative ion chemical ionization modes. Fragmentation pathways of the compounds investigated were determined in all three modes of ionization. It was found that a major part of the fragment ions in RDX and HMX originate from formation of the aduct ions [M+NO]⁺ and [M+NO₂]⁺ in electron impact and chemical ionization, and from [M+NO]^? and [M+NO₂]^? in negative chemical ionization, followed by dissociation.     

The Jahn-Teller effect in CH3Cl+(X̃2E): a combined high-resolution experimental measurement and ab initio theoretical study

The energy levels of CH(3)Cl(+)X?(2)E showing strong spin-vibronic coupling effect (Jahn-Teller effect) have been measured up to 3500 cm(-1) above the ground vibrational state using one-photon zero-kinetic energy photoelectron and mass-analyzed threshold ionization spectroscopic method. Theoretical calculations have been also performed to calculate the spin-vibronic energy levels using a diabatic model and ab initio adiabatic potential energy surfaces (PESs). In the theoretical calculations the diabatic potential energy surfaces are expanded by the Taylor expansions up to the fourth-order including the multimode vibronic interactions. The calculated spin-orbit energy splitting (224.6 cm(-1)) for the ground vibrational state is in good agreement with the experimental data (219 ± 3 cm(-1)), which indicates that the Jahn-Teller and the spin-orbit coupling have been properly described in the theoretical model near the zero-point energy level. Based on the assignments predicted by the theoretical calculations, the experimentally measured energy levels were fitted to those from the diabatic model by optimizing the main spectroscopic parameters. The PESs from the ab initio calculations at the level of CASPT2/vq(t)z were thus compared with those calculated from the experimentally determined spectroscopic parameters. The theoretical diagonal elements in the diabatic potential matrix are in good agreement with those determined using the experimental data, however, the theoretical off-diagonal elements appreciably deviate from those determined using the experimental data for geometric points far away from the conical intersections. It is also concluded that the JT effect in CH(3)Cl(+) mainly arises from the linear coupling and the mode coupling between the CH(3) deform (υ(5)) and CH(3) rock (υ(6)) vibrations. The mode couplings between the symmetric C-Cl stretching vibration υ(3) with υ(5) and υ(6) are also important to understand the spin-vibronic structure of the molecule.     

Fragment-molecule adduct ion formation in the mass spectra of cyclic N-acetylamines and related nitramines

Mass spectra of seven related N-heterocyclics, introduced by direct exposure probe, were determined in electron impact (EI) and positive- and negative-ion chemical ionization (PCI and NCI) modes. Proton adducts were the predominant molecular ion species in the EI and PCI modes. In addition, a variety of fragment–molecule adduct ions were observed for each compound in one or more of the modes. The propensity of 1,3,5-trinitrohexahydro-1,3,5-triazine for fragment–molecule adduct formation was high in all three ionization modes. Fragmentation processes were documented by collision-induced dissociation experiments.     

One-photon mass-analyzed threshold ionization spectroscopy of 2-chloropropene (2-C3H5Cl) and its vibrational assignment based on the density-functional theory calculations

A high-quality mass-analyzed threshold ionization (MATI) spectrum of 2-chloropropene, 2-C3H5Cl, is reported. Its ionization energy determined for the first time from the 0-0 band position was 9.5395+/-0.0006 eV. Almost all the peaks in the MATI spectrum could be vibrationally assigned utilizing the frequencies calculated at the B3LYP6-311++G(3df,3pd) level and the Franck-Condon factors calculated with the molecular parameters obtained at the same level. In particular, the observed methyl torsional progression could be reproduced very well through quantum-mechanical calculations using the molecular parameters obtained at this level. Dramatic lowering of the torsional barrier inferred from the experimental data was entirely compatible with the B3LYP6-311++G(3df,3pd) results. The torsional barrier and the internal rotational constant determined by fits to six torsional peaks were 53.6 and 5.20 cm(-1), respectively. A brief discussion at the level of molecular orbital is presented to account for the dramatic lowering of the torsional barrier upon ionization.     

Ab initio study of the spectroscopy of (CH3)(3)CN and (CH3)(2)CHN

Using the complete active space self-consistent field (CASSCF) method with 6-311++g(3df,3pd) basis sets, a few electronic states of nitrenes (CH3)3CN and (CH3)2CHN and their positive ions are calculated. All calculated states are valence states, and their characteristics are discussed in detail. In order to investigate the Jahn-Teller effect on (CH3)3CN radical, Cs symmetry was used for (CH3)3CN and (CH3)2CHN in the calculations. The results of our calculations (CASPT2 adiabatic excitation energies and RASSI oscillator strengths) suggest that the calculated transitions of (CH3)3CN at 27,710 cm(-1) and (CH3)2CHN at 28,110 cm(-1) are attributed to 23A' --> 13A', while those of (CH3)3CN at 28,916 cm(-1) and (CH3)2CHN at 29,316 cm(-1) are attributed to 13A' --> 13A'. The vertical and adiabatic ionization energies were obtained to compare with the photoelectron spectroscopic data. These results are in agreement with previous experimental data. Also, we present a comprehensive review on the CAS calculation results for (CH3)nCH(3-n)N (n = 0-3) presented in our previous and present papers.     

DFT-based studies on the Jahn-Teller effect in 3d hexacyanometalates with orbitally degenerate ground states

The topology of the ground-state potential energy surface of M(CN)(6) with orbitally degenerate (2)T(2g) (M = Ti(III) (t(2g)(1)), Fe(III) and Mn(II) (both low-spin t(2g)(5))) and (3)T(1g) ground states (M = V(III) (t(2g)(2)), Mn(III) and Cr(II) (both low-spin t(2g)(4))) has been studied with linear and quadratic Jahn-Teller coupling models in the five-dimensional space of the epsilon(g) and tau(2g) octahedral vibrations (Tg[symbol: see text](epsilon(g)+tau(2g)) Jahn-Teller coupling problem (T(g) = (2)T(2g), (3)T(1g))). A procedure is proposed to give access to all vibronic coupling parameters from geometry optimization with density functional theory (DFT) and the energies of a restricted number of Slater determinants, derived from electron replacements within the t(2g)(1,5) or t(2g)(2,4) ground-state electronic configurations. The results show that coupling to the tau(2g) bending mode is dominant and leads to a stabilization of D(3d) structures (absolute minima on the ground-state potential energy surface) for all complexes considered, except for [Ti(CN)(6)](3-), where the minimum is of D(4h) symmetry. The Jahn-Teller stabilization energies for the D3d minima are found to increase in the order of increasing CN-M pi back-donation (Ti(III) < V(III) < Mn(III) < Fe(III) < Mn(II) < Cr(II)). With the angular overlap model and bonding parameters derived from angular distortions, which correspond to the stable D(3d) minima, the effect of configuration interaction and spin-orbit coupling on the ground-state potential energy surface is explored. This approach is used to correlate Jahn-Teller distortion parameters with structures from X-ray diffraction data. Jahn-Teller coupling to trigonal modes is also used to reinterpret the anisotropy of magnetic susceptibilities and g tensors of [Fe(CN)(6)](3-), and the (3)T(1g) ground-state splitting of [Mn(CN)(6)](3-), deduced from near-IR spectra. The implications of the pseudo Jahn-Teller coupling due to t(2g)-e(g) orbital mixing via the trigonal modes (tau(2g)) and the effect of the dynamic Jahn-Teller coupling on the magnetic susceptibilities and g tensors of [Fe(CN)(6)](3-) are also addressed.     

Zero kinetic energy spectroscopy of hydroquinone-water (1:1) complex: a probe for conformer assignment

Zero kinetic energy (ZEKE) photoelectron spectroscopy of the hydroquinone-water (HQW) complex was carried out to characterize its S(1)-S(0) resonantly enhanced multiphoton ionization (REMPI) spectrum in terms of the cis and trans conformers. The ZEKE spectra of the hydroquinone isomers show differences in the Franck-Condon (FC) activity of a few ring modes, viz., modes 15, 9b, and 6b, due to the different symmetries of the two isomers. These modes were used as a "diagnostic tool" to carry out the categorical assignment of the REMPI spectrum of the HQW complex. It was found that the FC activity of these diagnostic modes in the cationic ground state (D(0)) of the water complex is similar as that of the monomer. The two lowest energy transitions in the REMPI spectrum of the water complex, 33,175 and 33,209 cm(-1), were reassigned as the band origins of the cis and trans hydroquinone-water complexes, which is opposite of the previous assignment. The intermolecular stretching mode (sigma) of the complex shows a long progression, up to v(')=4, in the cationic ground state and is strongly coupled to other observed ring modes. The Franck-Condon factors for different members in the progression were calculated using the potential energy surfaces computed ab initio. These agree well with the observed intensity patterns in the progression. The ionization potential of the trans and cis complexes was determined to be 60,071+/-4 and 60,024+/-4 cm(-1), respectively.     

Temperature-dependent optical Kerr effect spectroscopy of aromatic liquids

Ultrafast optical Kerr effect (OKE) spectroscopy has been used to study the temperature-dependent dynamics of five aromatic liquids: benzene, benzene-d(6), hexafluorobenzene, mesitylene, and 1,3,5-trifluorobenzene. The intermediate response time of all of the liquids was found to scale with the collective orientational correlation time, as has been observed for other simple liquids. The spectra of hexafluorobenzene, 1,3,5-trifluorobenzene, and mesitylene are qualitatively different from those of the other liquids and exhibit different behavior with temperature. These spectra allow us to assess the influence of different molecular parameters on the shape of the OKE spectrum. On the basis of these data, we propose a model that links the differences in the OKE spectra to corresponding differences in the local ordering of the liquids.     

Experimental investigation of the Jahn-Teller effect in the ground and excited electronic states of the tropyl radical. Part II. Vibrational analysis of the A 2E"3-X 2E"2 electronic transition

Laser-induced fluorescence (LIF) and laser-excited dispersed fluorescence (LEDF) spectra of the cycloheptatrienyl (tropyl) radical C7H7 have been observed under supersonic jet-cooling conditions. Assignment of the LIF excitation spectrum yields detailed information about the A-state vibronic structure. The LEDF emission was collected by pumping different vibronic bands of the A 2E"3<--X 2E"2 electronic spectrum. Analysis of the LEDF spectra yields valuable information about the vibronic levels of the X 2E"2 state. The X- and A-state vibronic structures characterize the Jahn-Teller distortion of the respective potential energy surfaces. A thorough analysis reveals observable Jahn-Teller activity in three of the four e'3 modes for the X 2E"2 state and two of the three e'1 modes for the A 2E"3 state and provides values for their deperturbed vibrational frequencies as well as linear Jahn-Teller coupling constants. The molecular parameters characterizing the Jahn-Teller interaction in the X and A states of C7H7 are compared to theoretical results and to those previously obtained for C5H5 and C6H6+.     

Ab initio study of the spectroscopy of CH3N and CH3CH2N

Complete active space (CAS) calculations with 6-311++g(3df,3pd) basis sets were performed for a large number of electronic states of the nitrate free radical (CH3N/CH3CH2N) and their positive and negative ions. All calculated states are valence states, and their characters are discussed in detail. To investigate the Jahn-Teller effect on the CH3N radical, Cs symmetry was used for both CH3N and CH3CH2N in calculations. The results (CASPT2 adiabatic excitation energies and CASSI oscillator strengths) suggest that the calculated transitions of CH3N at 32172 and 32139 cm(-1) are attributed to the 2(3)A' ' --> 1(3)A' ' and 1(3)A' --> 1(3)A' ', respectively, which is in accordance with the A3E --> X3A2 emission spectrum at T0 = 31 817 cm(-1). The calculated transitions of CH3CH2N at 334 nm are attributed to the 1(3)A' ' --> 2(3)A' ' and 1(3)A' ' --> 1(3)A', respectively, which is in accordance with the UV absorption spectrum of a series of 11 bands beginning at 335 nm. The vertical and adiabatic ionization energies were obtained to compare with the PES data. These results are in agreement with previous experimental data, which is discussed in detail.     

Two-color resonance-enhanced multiphoton ionization study of the lowest Rydberg p state of bis(eta6-benzene)chromium and its deuterated derivatives

Two-color resonance-enhanced multiphoton ionization (REMPI) spectra of jet-cooled (eta(6)-C(6)H(6))(2)Cr(1), (eta(6)-C(6)D(6))(2)Cr(2), and (eta(6)-C(6)D(6))(eta(6)-C(6)D(5)H)Cr(3) have been measured with use of the 3d(z)2-->R4p(x,y) Rydberg transition as the first step of the electronic excitation. The 0(0) (0) Rydberg component shifts by 59 and 54 cm(-1) to red when one goes from 1 to 2 and 3, respectively. Surprisingly, the REMPI spectra of 1-3 show very rich vibronic structures revealing both totally symmetric vibrations and degenerate vibrational modes. Presence of intense peaks corresponding to the e(2g) modes in the spectra of 1 and 2 is indicative of Jahn-Teller coupling in the R4p(x,y) Rydberg state. Additional REMPI resonances appear on going from 1 and 2 to 3 as a result of the symmetry reduction. The vibronic components in the spectra of 1-3 were assigned on the basis of the selection rules and comparison with the vibrational frequencies of the 1 and 2 ground-state molecules. The frequencies of over 10 normal vibrations have been determined for the gas-phase 1-3 Rydberg-state molecules from the REMPI experiment. The wavenumber corresponding to the lowest-energy mode (the ring torsion vibration) appears to be 40 cm(-1) in 1 and 35 cm(-1) in the deuterated complexes. The REMPI peaks are homogeneously broadened. The lower lifetime limits for the upper-state components increase on going from the vibrationless level to higher-lying vibronic states and on going from 1 to the deuterated derivatives.     

Magnitude of the CH/pi interaction in the gas phase: experimental and theoretical determination of the accurate interaction energy in benzene-methane

The accurate CH/pi interaction energy of the benzene-methane model system was experimentally and theoretically determined. In the experiment, mass analyzed threshold ionization spectroscopy was applied to the benzene-methane cluster in the gas phase, prepared in a supersonic molecular beam. The binding energy in the neutral ground state of the cluster, which is regarded as the CH/pi interaction energy for this model system, was evaluated from the dissociation threshold measurements of the cluster cation. The experimentally determined binding energy (D(0)) was 1.03-1.13 kcal/mol. The interaction energy of the model system was calculated by ab initio molecular orbital methods. The estimated CCSD(T) interaction energy at the basis set limit (D(e)) was -1.43 kcal/mol. The calculated binding energy (D(0)) after the vibrational zero-point energy correction (1.13 kcal/mol) agrees well with the experimental value. The effects of basis set and electron correlation correction procedure on the calculated CH/pi interaction energy were evaluated. Accuracy of the calculated interaction energies by DFT methods using BLYP, B3LYP, PW91 and PBE functionals was also discussed.