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The interaction of a molecule with the quantized electromagnetic field of a nanocavity gives rise to light-induced conical intersections between polaritonic potential energy surfaces. We demonstrate for a realistic model of a polyatomic molecule that the time-resolved ultrafast radiative emission of the cavity enables following both nuclear wavepacket dynamics on, and nonadiabatic population transfer between, polaritonic surfaces without applying a probe pulse. The latter provides an unambiguous (and in principle experimentally accessible) dynamical fingerprint of light-induced conical intersections.

Polaritons - hybrid light-matter states formed in cavity - strongly change the properties of the underlying matter. In optical or plasmonic nanocavities, polaritons decay by radiative emission of the cavity, which is accessible experimentally. Due to the interaction of a molecule with the quantized radiation field, polaritons exhibit light-induced conical intersections (LICIs) which dramatically influence the nuclear dynamics of molecular polaritons. We show that ultrafast radiative emission from the lower polariton is controlled by the geometric phase imposed by the LICI. This finding provides insight into the process of emission and, furthermore, allows one to compute these signals by augmenting the Born-Oppenheimer approximation for polaritons with a geometric phase term.

A discrepancy between theoretical and experimental values of the rotational barrier in benzaldehyde has been observed, which was attributed to inaccurate experimental results in part. Here, we report results on the -CHO torsion of benzaldehyde (C6H5CHO) based on a high resolution spectroscopic investigation in the far-infrared range in an effort to remove the experimental ambiguity. The rotationally-resolved vibrational spectra were measured with an unapodized resolution of 0.00064 cm-1 using synchrotron-based Fourier transform infrared (FTIR) spectroscopy at the Canadian Light Source. The torsional fundamental νt = 109.415429(20) cm-1 was unambiguously assigned via rovibrational analysis, followed by the tentative assignment of the first (2νt-νt) and second (3νt- 2νt) hot bands at 107.58 cm-1 and 105.61 cm-1, respectively, by comparison of the observed Q branch structures at high resolution with simulation based on a previous microwave study. This assignment is different from any previous low resolution infrared studies in which the intensity patterns were misleading. The key result of the assignment of the first three transitions allowed the determination of the barrier to internal rotation of (hc)1533.6 cm-1 (4.38 kcal mol-1). When compared with calculated results from vibrational second-order perturbation theory (VPT2) and the quasiadiabatic channel reaction path Hamiltonian (RPH) approach, the experimental value is still too low and this suggests that the discrepancy between theory and experiment remains despite the best experimental efforts.

A non-linear spectroscopic study of the HDO molecule is performed in the wavelength range of 1.36–1.42 μ m using noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy (NICE-OHMS). More than 100 rovibrational Lamb dips are recorded, with an experimental precision of 2–20 kHz, related to the first overtone of the O–H stretch fundamental of HD16O and HD18O. Significant perturbations, including distortions, shifts, and splittings, have been observed for a number of Lamb dips. These spectral perturbations are traced back to an AC-Stark effect, arising due to the strong laser field applied in all saturation-spectroscopy experiments. The AC-Stark effect mixes parity pairs, that is pairs of rovibrational states whose assignment differs solely in the K c quantum number, where K c is part of the standard J K a , K c asymmetric-top rotational label. Parity-pair mixing seems to be especially large for parity pairs with K a ≥ 3, whereby their energy splittings become as small as a few MHz, resulting in multi-component asymmetric Lamb-dip profiles of gradually increasing complexity. These complex profiles often include crossover resonances. This effect is well known in saturation spectroscopy, but has not been reported in combination with parity-pair mixing. Parity-pair mixing is not seen in H 2 16 O and H 2 18 O, because their parity pairs correspond to ortho and para nuclear-spin isomers, whose interaction is prohibited. Despite the frequency shifts observed for HD16O and HD18O, the absolute accuracy of the detected transitions still exceeds that achievable by Doppler-limited techniques.

Another manifestation of the Aharonov-Bohm effect is introduced to chemistry, in fact to nuclear quantum dynamics and high-resolution molecular spectroscopy. As demonstrated, the overall rotation of a symmetric-top molecule influences the dynamics of an internal vibrational motion in a way that is analogous to the presence of a solenoid carrying magnetic flux. To a good approximation, the low-energy rovibrational energy-level structure of the quasistructural molecular ion H+5can be understood entirely in terms of this effect.

The coupling of a molecule and a cavity induces nonadiabaticity in the molecule which makes the description of its dynamics complicated. For polyatomic molecules, reduced-dimensional models and the use of the Born–Oppenheimer approximation (BOA) may remedy the situation. It is demonstrated that contrary to expectation, BOA may even fail in a one-dimensional model and is generally expected to fail in two- or more-dimensional models due to the appearance of conical intersections induced by the cavity., The coupling of a molecule and a cavity induces nonadiabaticity in the molecule which makes the description of its dynamics complicated.

A new one-dimensional model is proposed for the low-energy vibrational quantum dynamics of CH 5 +based on the motion of an effective particle confined to a 60-vertex graphΓ 60with a single edge length parameter. Within this model, the quantum states of CH 5 +are obtained in analytic form and are related to combinatorial properties ofΓ 60. The bipartite structure ofΓ 60gives a simple explanation for curious symmetries observed in numerically exact variational calculations on CH 5 +

The fourth age of quantum chemistry offers fully flexible, black-box-type protocols for the accurate and detailed study of nuclear motions, applicable equally well to semirigid, floppy, flexible, polytopic, fluxional, and quasistructural polyatomic molecular systems, including complexes and clusters. Several codes, based on advanced fourth-age protocols, have been developed for the variational (or variational-like) solution of the time-independent nuclear-motion (rotational-vibrational) Schrodinger equation. These codes yield accurate rovibrational energy levels, wavefunctions, and to some extent quantum-number assignments for bound, resonance, and scattering states, revealing important spectroscopic and dynamical characteristics about the systems studied. When no approximations are introduced to the kinetic energy part of the rovibrational Hamiltonian, the accuracy of the computed results, assuming the validity of the Born–Oppenheimer approximation, depends solely on the accuracy of the representation of the potential energy surface utilized during these computations. From the point of view of potential applications it is important to emphasize that the most general codes can be employed both in full and any number of reduced dimensions. Several a posteriori analysis tools are available to improve the understanding of the extreme amount of numerical results produced by the stationary-state nuclear-motion computations. As shown through a few examples, these stationary-state solutions can straightforwardly be utilized for detailed quantum-dynamics studies. The applications briefly detailed at the end of this chapter help appreciate the power of the fourth-age quantum-chemical techniques developed and available to the spectroscopic and dynamics communities.

International audience; Nonadiabaticity, i.e., the effect of mixing electronic states by nuclear motion, is a central phenomenon in molecular science. The strongest nonadiabatic effects arise due to the presence of conical intersections of electronic energy surfaces. These intersections are abundant in polyatomic molecules. Laser light can induce in a controlled manner new conical intersections, called light-induced conical intersections, which lead to strong nonadiabatic effects similar to those of the natural conical intersections. These effects are, however, controllable and may even compete with those of the natural intersections. In this work we show that the standard low-energy vibrational spectrum of the electronic ground state can change dramatically by inducing nonadiabaticity via a light-induced conical intersection. This generic effect is demonstrated for an explicit example by full-dimensional high-level quantum calculations using a pump-probe scheme with a moderate-intensity pump laser and a weak probe laser.

The first application of quantum graphs to the vibrational quantum dynamics of molecules is reported. The quantum-graph model is applied to the quasistructural molecular ion CH5+, whose nuclear dynamics challenges the traditional understanding of chemical structures and molecular spectra. The vertices of the quantum graph represent versions of the equilibrium structure with distinct atom numbering, while the edges refer to collective nuclear motions transforming the versions of the equilibrium structure into one another. These definitions allow the mapping of the complex vibrational quantum dynamics of CH5+ onto the motion of a particle confined in a quantum graph. The quantum-graph model provides a simple understanding of the low-energy vibrational quantum dynamics of CH5+ and is able to reproduce the low-lying vibrational energy levels of CH5+ (and CD5+) with remarkable accuracy.

We report the first successful high-resolution analyses of the Fourier transform infrared (FTIR) spectrum of trisulfane. A band centered at 861.0292 cm−1 can be assigned unambiguously to the chiral trans conformer by means of ground state combination differences in comparison with known rotational spectra. A second band near 864.698 cm−1 is tentatively assigned to the cis conformer by comparison with theory. The results are discussed in relation to their importance for experimental attempts to measure the parity violating energy difference ΔpvE between the ground states of enantiomers of chiral molecules.

We report high resolution spectroscopic results of 1,2-dithiine-(1,2-dithia-3,5-cyclohexadiene, C4H4S2) in the gigahertz and terahertz spectroscopic ranges and exploratory theoretical calculations of parity violation and tunneling processes in view of a possible experimental determination of the parity violating energy difference ΔpvE in this chiral molecule. Theory predicts that the parity violating energy difference between the enantiomers in their ground state (ΔpvE ≃ 1.1 × 10−11(hc) cm−1) is in principle measurable as it is much larger than the calculated tunneling splitting for the symmetrical potential ΔE± < 10−24 (hc) cm−1. With a planar transition state for stereomutation at about 2500 cm−1 tunneling splitting becomes appreciable above 2300 cm−1. This makes levels of well-defined parity accessible to parity selection by the available powerful infrared lasers and thus useful for one of the existing experimental approaches towards molecular parity violation. The new GHz spectroscopy leads to greatly improved ground state rotational parameters for 1,2-dithiine. These are used as starting points for the first successful analyses of high resolution interferometric Fourier transform infrared (FTIR, THz) spectra of the fundamentals ν17 (1308.873 cm−1 or 39.23903 THz), ν22 (623.094 cm−1 or 18.67989 THz) and ν3 (1544.900 cm−1 or 46.314937 THz) for which highly accurate spectroscopic parameters are reported. The results are discussed in relation to current efforts to measure ΔpvE., Physical Chemistry Chemical Physics, 18 (31), ISSN:1463-9084, ISSN:1463-9076

The fourth-age quantum chemical code GENIUSH is used for the variational determination of rotational-vibrational energy levels corresponding to reduced- and full-dimensional models of H(+)(5), a molecular ion exhibiting several strongly coupled large-amplitude motions. The computations are supplemented with one- and two-dimensional analytic results which help to understand the peculiar rovibrational energy-level structure computed correctly for the first time. An unusual aspect of the results is that the canonical Eckart-embedding of molecule-fixed axes, a cornerstone of the computational spectroscopy of semirigid molecules, is found to be inadequate. Furthermore, it is shown that while the 1D "active torsion" model provides proper results when compared to the full, 9D treatment, models excluding the torsion have limited physical significance. The structure of the rovibrational energy levels of H(+)(5) proves that this is a prototypical astructural molecule: the rotational and vibrational level spacings are of the same order of magnitude and the level structure drastically deviates from that computed via perturbed rigid-rotor and harmonic-oscillator models.

International audience; This is the third of a series of articles reporting critically evaluated rotational-vibrational line positions, transition intensities, and energy levels, with associated critically reviewed labels and uncertainties, for all the main isotopologues of water. This paper presents experimental line positions, experimental-quality energy levels, and validated labels for rotational-vibrational transitions of the most abundant isotopologue of water, H216O. The latest version of the MARVEL (Measured Active Rotational-Vibrational Energy Levels) line-inversion procedure is used to determine the rovibrational energy levels of the electronic ground state of H216O from experimentally measured lines, together with their self-consistent uncertainties, for the spectral region up to the first dissociation limit. The spectroscopic network of H216O containstwo components, an ortho (o) and a para (p) one. For o-H216O and p-H216O, experimentally measured, assigned, and labeled transitions were analyzed from more than 100 sources. The measured lines come from one-photon spectra recorded at room temperature in absorption, from hot samples with temperatures up to 3000 K recorded in emission, and from multiresonance excitation spectra which sample levels up to dissociation. The total number of transitions considered is 184 667 of which 182 156 are validated: 68 027 between para states and 114 129 ortho ones. These transitions give rise to 18 486 validated energy levels, of which 10 446 and 8040 belong to o-H216O and p-H216O, respectively. The energy levels, including their labeling with approximate normal-mode and rigid-rotor quantum numbers, have been checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators as well as against previous compilations of energy levels. The extensive list of MARVEL lines and levels obtained are deposited in the supplementary data of this paper, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved.

Variational rotational-vibrational quantum chemical computations are performed for the F(-)-CH4 and F(-)-CH2D2 anion complexes using several reduced-dimensional models in a curvilinear polyspherical coordinate system and utilizing an accurate ab initio potential energy surface (PES). The implementation of the models is made practical by using the general rovibrational code GENIUSH, which constructs the complicated form of the exact rovibrational kinetic energy operator in reduced and full dimensions in any user-specified coordinates and body-fixed frames. A one-dimensional CF stretch, 1D(RCF), a two-dimensional intermolecular bend, 2D(θ,φ), and a three-dimensional intermolecular, 3D(RCF,θ,φ), rigid methane model provide vibrational energies for the low-frequency, large-amplitude modes in good agreement with full-dimensional MCTDH results for F(-)-CH4. The 2D(θ,φ) and 3D(RCF,θ,φ) four-well computations, describing equally the four possible CH-F(-) bonds, show that the ground-state tunneling splitting is less than 0.01 cm(-1). For the hydrogen-bonded CH stretching fundamental a local-mode model is found to have almost spectroscopic accuracy, whereas a harmonic frequency analysis performs poorly. The 2D(θ,φ) and 3D(RCF,θ,φ) rotational-vibrational computations on the Td-symmetric four-well PES reveal that in most cases F(-)-CH4 behaves as a semirigid C3v symmetric top. For the degenerate intermolecular bending vibrational states substantial splittings of the rigid rotor levels are observed. For F(-)-CH2D2 the rotational levels guide the assignment of the vibrational states to either F(-)-H or F(-)-D connectivity.

Measurements result in effective, usually temperature-dependent structural parameters of molecules, and never directly in equilibrium structures, which are theoretical constructs. A recent high-accuracy semiglobal potential energy surface of the electronic ground state of the ammonia molecule, called NH3-Y2010 (J. Mol. Spectrosc. 2011, 268, 123), which exhibits mass-independent equilibrium NH bond length and a HNH bond angle of 1.0109 Å and 106.75°, respectively, is employed together with the variational nuclear motion code GENIUSH (J. Chem. Phys. 2009, 130, 134112; 2011, 134, 074105) to determine directly measurable, effective structural parameters of the (14)NH(3) and (14)ND(3) molecules. The effective r(g)- and r(a)-type NH(ND) distances determined at 300 K are 1.0307(1.0254) and 1.0256(1.0217) Å, respectively, with an estimated accuracy of 2 × 10(-4) Å. The effective θ(g) HNH and DND bond angles at 300 K are 106.91° and 106.85°, respectively. The root-mean-square amplitudes of vibration, l(g), for the NH(ND) distances at 300 K are 0.073(0.062) Å. These structural parameters confirm the less accurate results of a room-temperature gas-electron-diffraction study (J. Chem. Phys. 1968, 49, 2488, all data in Å): r(g)(NH) = 1.030(2), l(g)(NH) = 0.073(2), r(g)(ND) = 1.027(3), and l(g)(ND) = 0.061(2). The computed difference in the r(g,T)(NH) bond lengths of the two spin isomers (ortho and para forms) of (14)NH(3) is 3 × 10(-5) Å at 0 K, the difference diminishes at temperatures of about 30-50 K.

Scaling factors for Pulay’s scaled quantum mechanical (SQM) scheme have been determined for four different widely used DFT functionals (PBE, B3LYP, B3PW91, and M06-2X) and for two basis sets (6-31++G** and aug-cc-pVTZ) by fitting computed results to 347 fundamental experimental vibrational frequencies of 33 molecules. Measurements in the gas phase and in solid argon matrices were used independently in the fitting procedure in order to provide a simple method of estimating matrix shifts. The accuracy of the new scaling factors is demonstrated on test molecules including hydrogen-bonded systems and molecules containing chlorine and sulfur atoms.