Showing papers on "Hot band published in 2016"

Variable-Temperature Tip-Enhanced Raman Spectroscopy of Single-Molecule Fluctuations and Dynamics

Abstract: Structure, dynamics, and coupling involving single-molecules determine function in catalytic, electronic or biological systems. While vibrational spectroscopy provides insight into molecular structure, rapid fluctuations blur the molecular trajectory even in single-molecule spectroscopy, analogous to spatial averaging in measuring large ensembles. To gain insight into intramolecular coupling, substrate coupling, and dynamic processes, we use tip-enhanced Raman spectroscopy (TERS) at variable and cryogenic temperatures, to slow and control the motion of a single molecule. We resolve intrinsic line widths of individual normal modes, allowing detailed and quantitative investigation of the vibrational modes. From temperature dependent line narrowing and splitting, we quantify ultrafast vibrational dephasing, intramolecular coupling, and conformational heterogeneity. Through statistical correlation analysis of fluctuations of individual modes, we observe rotational motion and spectral fluctuations of the molec...

Polarization-Resolved Raman Study of Bulk-like and Davydov-Induced Vibrational Modes of Exfoliated Black Phosphorus

Abstract: Owing to its crystallographic structure, black phosphorus is one of the few 2D materials expressing strongly anisotropic optical, transport, and mechanical properties. We report on the anisotropy of electron–phonon interactions through a polarization-resolved Raman study of the four vibrational modes of atomically thin black phosphorus (2D phosphane): the three bulk-like modes Ag1, B2g, and Ag2 and the Davydov-induced mode labeled Ag(B2u). The complex Raman tensor elements reveal that the relative variation in permittivity of all Ag modes is irrespective of the atomic motion involved lowest along the zigzag direction, the basal anisotropy of these variations is most pronounced for Ag2 and Ag(B2u), and interlayer interactions in multilayer samples lead to reduced anisotropy. The bulk-forbidden Ag(B2u) mode appears for n ≥ 2 and quickly subsides in thicker layers. It is assigned to a Davydov-induced IR to Raman conversion of the bulk IR mode B2u and exhibits characteristics similar to Ag2. Although this mod...

Multi-Layer Multi-Configuration Time-Dependent Hartree (ML-MCTDH) Approach to the Correlated Exciton-Vibrational Dynamics in the FMO Complex

Abstract: The coupled quantum dynamics of excitonic and vibrational degrees of freedom is investigated for high-dimensional models of the Fenna-Matthews-Olson (FMO) complex. This includes a seven and an eight-site model with 518 and 592 harmonic vibrational modes, respectively. The coupling between local electronic transitions and vibrations is described within the Huang-Rhys model using parameters that are obtained by discretization of an experimental spectral density. Different pathways of excitation energy flow are analyzed in terms of the reduced one-exciton density matrix, focussing on the role of vibrational and vibronic excitation. Distinct features due to both competing time scales of vibrational and exciton motion and vibronically-assisted transfer are observed. The question of the effect of initial state preparation is addressed by comparing the case of an instantaneous Franck-Condon excitation at a single site with that of a laser field excitation.

Vibrational averages along thermal lines

Abstract: A method is proposed for the calculation of vibrational quantum and thermal expectation values of physical properties from first principles. Thermal lines are introduced: these are lines in configuration space parametrized by temperature, such that the value of any physical property along them is approximately equal to the vibrational average of that property. The number of sampling points needed to explore the vibrational phase space is reduced by up to an order of magnitude when the full vibrational density is replaced by thermal lines. Calculations of the vibrational averages of several properties and systems are reported, namely, the internal energy and the electronic band gap of diamond and silicon, and the chemical shielding tensor of L-alanine. Thermal lines pave the way for complex calculations of vibrational averages, including large systems and methods beyond semilocal density functional theory.

Visualization of Vibrational Modes in Real Space by Tip-Enhanced Non-Resonant Raman Spectroscopy

Abstract: We present a general theory to model the spatially resolved non-resonant Raman images of molecules. It is predicted that the vibrational motions of different Raman modes can be fully visualized in real space by tip-enhanced non-resonant Raman scattering. As an example, the non-resonant Raman images of water clusters were simulated by combining the new theory and first-principles calculations. Each individual normal mode gives rise its own distinct Raman image, which resembles the expected vibrational motions of the atoms very well. The characteristics of intermolecular vibrations in supermolecules could also be identified. The effects of the spatial distribution of the plasmon as well as nonlinear scattering processes were also addressed. Our study not only suggests a feasible approach to spatially visualize vibrational modes, but also provides new insights in the field of nonlinear plasmonic spectroscopy.

Ab Initio Transient Vibrational Spectral Analysis

Abstract: Pump probe spectroscopy techniques have enabled the direct observation of a variety of transient molecular species in both ground and excited electronic states Time-resolved vibrational spectroscopy is becoming an indispensable tool for investigating photoinduced nuclear dynamics of chemical systems of all kinds On the other hand, a complete picture of the chemical dynamics encoded in these spectra cannot be achieved without a full temporal description of the structural relaxation, including the explicit time-dependence of vibrational coordinates that are substantially displaced from equilibrium by electronic excitation Here we present a transient vibrational analysis protocol combining ab initio direct molecular dynamics and time-integrated normal modes introduced in this work, relying on the recent development of analytic time-dependent density functional theory (TDDFT) second derivatives for excited states Prototypical molecules will be used as test cases, showing the evolution of the vibrational s

Tuning vibrational mode localization with frequency windowing.

Abstract: Local-mode coordinates have previously been shown to be an effective starting point for anharmonic vibrational spectroscopy calculations. This general approach borrows techniques from localized-orbital machinery in electronic structure theory and generates a new set of spatially localized vibrational modes. These modes exhibit a well-behaved spatial decay of anharmonic mode couplings, which, in turn, allows for a systematic, a priori truncation of couplings and increased computational efficiency. Fully localized modes, however, have been found to lead to unintuitive mixtures of characteristic motions, such as stretches and bends, and accordingly large bilinear couplings. In this work, a very simple, tunable localization frequency window is introduced, in order to realize the transition from normal modes to fully localized modes. Partial localization can be achieved by localizing only pairs of modes within this traveling frequency window, which allows for intuitive interpretation of modes. The optimal window size is suggested to be a few hundreds of wave numbers, based on small- to medium-sized test systems, including water clusters and polypeptides. The new sets of partially localized coordinates retain their spatial coupling decay behavior while providing a reduced number of potential energy evaluations for convergence of anharmonic spectra.

Global analysis of the high temperature infrared emission spectrum of 12CH4 in the dyad (ν2/ν4) region

Abstract: We report new assignments of vibration-rotation line positions of methane ((12)CH4) in the so-called dyad (ν2/ν4) region (1100-1500 cm(-1)), and the resulting update of the vibration-rotation effective model of methane, previously reported by Nikitin et al. [Phys. Chem. Chem. Phys. 15, 10071 (2013)], up to and including the tetradecad. High resolution (0.01 cm(-1)) emission spectra of methane have been recorded up to about 1400 K using the high-enthalpy source developed at Institut de Physique de Rennes associated with the Fourier transform spectrometer of the SOLEIL synchrotron facility (AILES beamline). Analysis of these spectra allowed extending rotational assignments in the well-known cold band (dyad-ground state (GS)) and related hot bands in the pentad-dyad system (3000 cm(-1)) up to Jmax = 30 and 29, respectively. In addition, 8512 new transitions belonging to the octad-pentad (up to J = 28) and tetradecad-octad (up to J = 21) hot band systems were successfully identified. As a result, the MeCaSDa database of methane was significantly improved. The line positions assigned in this work, together with the information available in the literature, were fitted using 1096 effective parameters with a dimensionless standard deviation σ = 2.09. The root mean square deviations dRMS are 3.60 × 10(-3) cm(-1) for dyad-GS cold band, 4.47 ×10(-3) cm(-1) for the pentad-dyad, 5.43 × 10(-3) cm(-1) for the octad-pentad, and 4.70 × 10(-3) cm(-1) for the tetradecad-octad hot bands. The resulting new line list will contribute to improve opacity and radiative transfer models for hot atmospheres, such as those of hot-Jupiter type exoplanets.

High temperature Raman investigation of few-layer MoTe2

Abstract: We present a Raman investigation of the temperature effect of single and few layer MoTe2 at an electronic device working temperature range from 300 K to 500 K. We observe linear frequency red-shifts with increasing temperature for the first order Raman active E12g, A1g, Raman inactive B12g mode, and the second order ω2 mode, which can be attributed to the anharmonic effect of the interatomic potential energy. The temperature coefficients of the out-of-plane vibrational B12g modes and inplane vibrational E12g modes are similarly around −0.013 cm−1/K, while lower than that of out-of-plane vibration A1g mode at −0.009 cm−1/K. The temperature coefficient of ω2 mode is −0.00521 cm−1/K, approximately half of those of the first order modes, and the temperature coefficient of transverse acoustic TA (M) mode is indirectly deduced as −0.0102 cm−1/K, which shows the corresponding Mo-Te stretching bonds of TA (M) mode behavior similarly to those of optical Raman vibrations. Our work thus provides temperature dependent lattice vibration information of MoTe2 and could be potentially useful in future optoelectronic devices based on MoTe2 related two dimensional materials.

Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A.

Abstract: We have computationally investigated the role of intramolecular vibrational modes in determining nonradiative relaxation pathways of photoexcited electronic states in isolated chlorophyll A (ChlA) molecules. To simulate the excited state relaxation from the initially excited Soret state to the lowest excited state Qy, the approach of nonadiabatic excited state molecular dynamics has been adopted. The intramolecular vibrational energy relaxation and redistribution that accompany the electronic internal conversion process is followed by analyzing the excited state trajectories in terms of the ground state equilibrium normal modes. The time dependence of the normal mode velocities is determined by projecting instantaneous Cartesian velocities onto the normal mode vectors. Our analysis of the time evolution of the average mode energies uncovers that only a small subset of the medium-to-high frequency normal modes actively participate in the electronic relaxation processes. These active modes are characterized...

Coupling of Carbon Dioxide Stretch and Bend Vibrations Reveals Thermal Population Dynamics in an Ionic Liquid

Abstract: The population relaxation of carbon dioxide dissolved in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf2) was investigated using polarization-selective ultrafast infrared pump-probe spectroscopy and two-dimensional infrared (2D IR) spectroscopy. Due to the coupling of the bend with the asymmetric stretch, excitation of the asymmetric stretch of a molecule with a thermally populated bend leads to an additional peak, a hot band, which is red-shifted from the main asymmetric absorption band by the combination band shift. This hot band peak exchanges population with the main peak through the gain and loss of bend excitation quanta. The isotropic pump-probe signal originating from the unexcited bend state displays a fast, relatively small amplitude, initial growth followed by a longer time scale exponential decay. The signal is analyzed over its full time range using a kinetic model to determine both the vibrational lifetime (the final decay) and rate constant for the loss of the bend energy. This bend relaxation manifests as the fast initial growth of the stretch/no bend signal because the hot band (stretch with bend) is "over pumped" relative to the ground state equilibrium. The nonequilibrium pumping occurs because the hot band has a larger transition dipole moment than the stretch/no bend peak. The system is then prepared, utilizing an acousto-optic mid-infrared pulse shaper to cut a hole in the excitation pulse spectrum, such that the hot band is not pumped. The isotropic pump-probe signal from the stretch/no bend state is altered because the initial excited state population ratio has changed. Instead of a growth due to relaxation of bend quanta, a fast initial decay is observed because of thermal excitation of the bend. Fitting this curve gives the rate constant for thermal excitation of the bend and the lifetime, which agree with those determined in the pump-probe experiments without frequency-selective pumping.

Couplings Across the Vibrational Spectrum Caused by Strong Hydrogen Bonds: A Continuum 2D IR Study of the 7-Azaindole-Acetic Acid Heterodimer

Abstract: Strongly hydrogen-bonded motifs provide structural stability and can act as proton transfer relays to drive chemical processes in biological and chemical systems. However, structures with medium and strong hydrogen bonds are difficult to study due to their characteristically broad vibrational bands and large anharmonicity. This is further complicated by strong interactions between the high-frequency hydrogen-bonded vibrational modes, fingerprint modes, and low-frequency intradimer modes that modulate the hydrogen-bonding. Understanding these structures and their associated dynamics requires studying much of the vibrational spectrum. Here, mid-IR continuum spectroscopy of the cyclic 7-azaindole–acetic acid (7AI–AcOH) heterodimer reveals the vibrational relaxation dynamics and couplings of this complex hydrogen-bonded system. Within this dimer, the NH bond of 7AI exhibits a band at 3250 cm–1 caused by a medium strength hydrogen bond, while the strongly hydrogen-bonded OH modes of acetic acid exhibit a broad...

First-principles lattice dynamics and Raman scattering in ionic conductor β-Ag2S

Abstract: The phonon structure of the silver sulfide Ag2S was investigated, experimentally using Raman spectroscopy, and theoretically using the density-functional perturbation theory for the first time. Seven Raman-active modes were observed and identified at 23, 39, 42, 44, 62, 65, and 243 cm−1. Symmetry assignments of all the vibrational modes were derived from considerations of point group symmetry. The phonon band structure and the relative Raman intensities were also investigated by ab initio calculations and compared with the experimental data. The temperature, laser power, and illumination time dependencies of frequency, linewidth, and intensity of the Raman-active modes are discussed. In the Raman spectra at higher frequencies 1300–1700 cm−1, additional broad Raman modes observed in all samples at higher laser powers 8–10 mW were ascribed to luminescence from β-Ag2S. The phonon and Raman spectra of the β-Ag2S provide a useful insight into the β-Ag2S → α-Ag2S phase transition. Finally, calculated infrared vibrational mode frequencies were compared with measured infrared mode frequencies.

High resolution FTIR study of 34S16O2: The bands 2ν1, ν1+ν3, ν1+ν2+ν3−ν2 and ν1+ν2+ν3

Abstract: The high resolution infrared spectra of the 34S16O2 molecule were recorded in the region of location of the 2ν1 and ν 1 + ν 3 bands. The hot band ν 1 + ν 2 + ν 3 − ν 2 , which is located in the same spectral region, and the very weak band ν 1 + ν 2 + ν 3 were also recorded and theoretically analyzed. Considerably more transitions, compared to the preceding studies, were assigned to the ν 1 + ν 3 and ν 1 + ν 2 + ν 3 − ν 2 bands. For the 2ν1 band more than 3280 transitions were assigned in the recorded spectra (only 16 transitions belonging to the 2ν1 band have been mentioned in the earlier literature). Ro-vibrational energies of the states (200), (101) and (111) were determined on the basis of the assigned transitions and then were used in the weighted fit procedure with the Hamiltonian model which takes into account the presence of resonance interactions. The obtained sets of parameters reproduce the initial experimental data with the accuracies close to experimental uncertainties.

Raman spectral probe on increased local vibrational modes and phonon lifetimes in Ho3+‐doped Bi2O3 micro‐rods

Abstract: We report the appearance and enhancement in intensity of impurity related local vibrational modes in Bi2O3 : Ho micro-rods along with normal modes. Pure and Ho-doped Bi2O3 micro-rods were synthesized by conventional co-precipitation method at 60 °C. The structural and morphological studies were carried out using powder X-ray diffraction technique and scanning electron microscopy, respectively. Raman spectroscopic studies reveal the existence of local phonon vibrational modes (LVM) due to the incorporation of Ho3+. Harmonic approximation method was employed to find the dopant-related peak in the Raman spectra. Variation in full width at half maximum for LVM with increase in Ho3+ was also investigated. This increase in FWHM indicates the decrease in crystallinity of the doped samples. The phonon lifetime calculation carried out for each samples and the decrease in phonon lifetime with doping concentration make this material a potential candidate for optical and electronic applications. Copyright © 2016 John Wiley & Sons, Ltd.

Vibrational Quantum Decoherence in Liquid Water

Abstract: Traditional descriptions of vibrational energy transfer consider a quantum oscillator interacting with a classical environment. However, a major limitation of this simplified description is the neglect of quantum decoherence induced by the different interactions between two distinct quantum states and their environment, which can strongly affect the predicted energy-transfer rate and vibrational spectra. Here, we use quantum–classical molecular dynamics simulations to determine the vibrational quantum decoherence time for an OH stretch vibration in liquid heavy water. We show that coherence is lost on a sub-100 fs time scale due to the different responses of the first shell neighbors to the ground and excited OH vibrational states. This ultrafast decoherence induces a strong homogeneous contribution to the linear infrared spectrum and suggests that resonant vibrational energy transfer in H2O may be more incoherent than previously thought.

Structure-dependent vibrational dynamics of Mg(BH4)2 polymorphs probed with neutron vibrational spectroscopy and first-principles calculations

Abstract: The structure-dependent vibrational properties of different Mg(BH4)2 polymorphs (α, β, γ, and δ phases) were investigated with a combination of neutron vibrational spectroscopy (NVS) measurements and density functional theory (DFT) calculations, with emphasis placed on the effects of the local structure and orientation of the BH4− anions. DFT simulations closely match the neutron vibrational spectra. The main bands in the low-energy region (20–80 meV) are associated with the BH4− librational modes. The features in the intermediate energy region (80–120 meV) are attributed to overtones and combination bands arising from the lower-energy modes. The features in the high-energy region (120–200 meV) correspond to the BH4− symmetric and asymmetric bending vibrations, of which four peaks located at 140, 142, 160, and 172 meV are especially intense. There are noticeable intensity distribution variations in the vibrational bands for different polymorphs. This is explained by the differences in the spatial distribution of BH4− anions within various structures. An example of the possible identification of products after the hydrogenation of MgB2, using NVS measurements, is presented. These results provide fundamental insights of benefit to researchers currently studying these promising hydrogen-storage materials.

Auxeticity from nonlinear vibrational modes

Abstract: authoren It is demonstrated that the large-amplitude, short-wavelength vibrational modes excited in the lattice can change its elastic properties due to physical and/or geometric nonlinearity of the lattice bonds. Depending on the symmetry of the vibrational mode the symmetry of the elastic properties of the lattice can also change. Using as an example the two-dimensional honeycomb structure with -FPU pairwise interparticle interactions, we demonstrate that the excitation of a large-amplitude vibrational mode in combination with equiaxial tensile strain can change the sign of the Poisson's ratio from positive to negative, thus leading to the auxetic property of the lattice. It is shown that the considered lattice supports discrete breathers, i.e., spatially localized nonlinear vibrational modes. The excitation of the discrete breathers as a result of the modulational instability of the extended short-wavelength modes is analyzed. Our results contribute to the understanding of the relation between the elastic properties and nonlinear dynamics of the lattices of interacting particles. Extended vibrational modes in the 2D honeycomb lattice presented by the stroboscopic pictures of the particle motion. Excitation of such modes with sufficiently large amplitude in combination with equiaxial tension changes the sign of the Poisson's ratio of the lattice from positive to negative.

Vibrational memory in quantum localized states

Abstract: The rovibrational eigenenergy set of molecular systems is a key feature needed to understand and model elementary chemical reactions. A unique class of molecular systems, represented by an ${}^{4}{A}^{\ensuremath{'}\ensuremath{'}}$ excited electronic state of the ${[\mathrm{H},\mathrm{S},\mathrm{N}]}^{\ensuremath{-}}$ system comprising several distinct dipole-bound isomers, is found to contain both bent and linear minima separated by relatively small barriers. Full-dimensional nuclear-motion computations performed in Jacobi coordinates using three-dimensional potential energy surfaces describing the stable isomers and the related transition states yield rovibrational eigenstates located both below and above the barriers. The rovibrational wave functions are well localized, regardless of whether the state's energy is below or above the barriers. We also show that the states preserve the memory of the isomeric forms they ``originate from,'' which is signature of a strong vibrational memory effect above isomerization barriers.

The rotation-vibration structure of the SO2 C̃1B2 state explained by a new internal coordinate force field

Abstract: A new quartic force field for the SO2 C(1)B2 state has been derived, based on high resolution data from S(16)O2 and S(18)O2. Included are eight b2 symmetry vibrational levels of S(16)O2 reported in the first paper of this series [G. B. Park et al., J. Chem. Phys. 144, 144311 (2016)]. Many of the experimental observables not included in the fit, such as the Franck-Condon intensities and the Coriolis-perturbed effective C rotational constants of highly anharmonic C state vibrational levels, are well reproduced using our force field. Because the two stretching modes of the C state are strongly coupled via Fermi-133 interaction, the vibrational structure of the C state is analyzed in a Fermi-system basis set, constructed explicitly in this work via partial diagonalization of the vibrational Hamiltonian. The physical significance of the Fermi-system basis is discussed in terms of semiclassical dynamics, based on study of Fermi-resonance systems by Kellman and Xiao [J. Chem. Phys. 93, 5821 (1990)]. By diagonalizing the vibrational Hamiltonian in the Fermi-system basis, the vibrational characters of all vibrational levels can be determined unambiguously. It is shown that the bending mode cannot be treated separately from the coupled stretching modes, particularly at vibrational energies of more than 2000 cm(-1). Based on our force field, the structure of the Coriolis interactions in the C state of SO2 is also discussed. We identify the origin of the alternating patterns in the effective C rotational constants of levels in the vibrational progressions of the symmetry-breaking mode, νβ (which correlates with the antisymmetric stretching mode in our assignment scheme).

2D-IR spectroscopy of hydrogen-bond-mediated vibrational excitation transfer

Abstract: Vibrational excitation transfer along the hydrogen-bond-mediated pathways in the complex of methyl acetate (MA) and 4-cyanophenol (4CP) was studied by dual-frequency femtosecond two-dimensional infrared spectroscopy. We excited the energy-donating ester carbonyl stretching vibrational mode and followed the transfer to the energy-accepting benzene ring and cyano stretching vibrations. The complexes with no, one, and two hydrogen-bonded 4CP molecules were studied. Vibrational relaxation of the carbonyl mode is more efficient in both hydrogen-bonded complexes as compared with free MA molecules. The inter-molecular transport in a hydrogen-bonded complex involving a single 4CP molecule is slower than that in a complex with two 4CP molecules. In the former, vibrational relaxation leads to local heating, as shown by the spectroscopy of the carbonyl mode, whereas the local heating is suppressed in the latter because the excitation redistribution is more efficient. At early times, the transfer to the benzene ring is governed by its direct coupling with the energy-donating carbonyl mode, whereas at later times intermediate states are involved. The transfer to a more distant site of the cyano group in 4CP involves intermediate states at all times, since no direct coupling between the energy-donating and accepting modes was observed. We anticipate that our findings will be of importance for spectroscopic studies of bio-molecular structures and dynamics, and inter- and intra-molecular signaling pathways, and for developing molecular networking applications.

The effective degeneracy of protein normal modes.

Abstract: Normal modes are frequently computed and used to portray protein dynamics and interpret protein conformational changes. In this work, we investigate the nature of normal modes and find that the normal modes of proteins, especially those at the low frequency range (0-600 cm(-1)), are highly susceptible to degeneracy. Two or more modes are degenerate if they have the same frequency and consequently any orthogonal transformation of them also is a valid representation of the mode subspace. Thus, degenerate modes can no longer characterize unique directions of motions as regular modes do. Though the normal modes of proteins are usually of different frequencies, the difference in frequency between neighboring modes is so small that, under even slight structural uncertainty that unavoidably exists in structure determination, it can easily vanish and as a result, a mode becomes effectively degenerate with its neighboring modes. This can be easily observed in that some modes seem to disappear and their matching modes cannot be found when the structure used to compute the modes is modified only slightly. We term this degeneracy the effective degeneracy of normal modes. This work is built upon our recent discovery that the vibrational spectrum of globular proteins is universal. The high density of modes observed in the vibrational frequency spectra of proteins renders their normal modes highly susceptible to degeneracy, under even the smallest structural uncertainty. Indeed, we find the degree of degeneracy of modes is proportional to the density of modes in the vibrational spectrum. This means that for modes at the same frequency, degeneracy is more severe for larger proteins. Degeneracy exists also in the modes of coarse-grained models, but to a much lesser extent than those of all-atom models. In closing, we discuss the implications of the effective degeneracy of normal modes: how it may significantly affect the ways in which normal modes are used in various normal modes-based applications.

Double resonant absorption measurement of acetylene symmetric vibrational states probed with cavity ring down spectroscopy

Abstract: A novel mid-infrared/near-infrared double resonant absorption setup for studying infrared-inactive vibrational states is presented. A strong vibrational transition in the mid-infrared region is excited using an idler beam from a singly resonant continuous-wave optical parametric oscillator, to populate an intermediate vibrational state. High output power of the optical parametric oscillator and the strength of the mid-infrared transition result in efficient population transfer to the intermediate state, which allows measuring secondary transitions from this state with a high signal-to-noise ratio. A secondary, near-infrared transition from the intermediate state is probed using cavity ring-down spectroscopy, which provides high sensitivity in this wavelength region. Due to the narrow linewidths of the excitation sources, the rovibrational lines of the secondary transition are measured with sub-Doppler resolution. The setup is used to access a previously unreported symmetric vibrational state of acetylene,...

A combined Gigahertz and Terahertz (FTIR) spectroscopic investigation of meta-D-phenol: observation of tunnelling switching

Abstract: We report results on the dynamics of tunnelling switching based on a high-resolution spectroscopic investigation of meta-D-phenol in GHz and THz ranges. The pure rotational spectra were recorded in the range of 72–117 GHz and assigned to the localized syn- and anti-structures in the ground and the first excited torsional states. Specific torsional states were unambiguously assigned by comparison of the experimental rotational constants with theoretical results from quasiadiabatic channel reaction path Hamiltonian (RPH) calculations. The torsional fundamental νT at ≈ 309 cm−1 and the first hot band (2νT – νT) at ≈ 277 cm−1 were subsequently assigned in synchrotron based high-resolution Fourier transform infrared (FTIR, THz) spectra. The analyses provided accurate spectroscopic constants of all six states involved. It was found that the 2νT states are interacting through anharmonic resonances, indicating tunnelling switching as predicted by theory. Furthermore, tunnelling–rotation–vibration transiti...