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Because of their central importance in chemistry and biology, water molecules have been the subject of decades of intense spectroscopic investigations. Rotational spectroscopy of water vapor has yielded detailed information about the structure and dynamics of isolated water molecules, as well as water dimers and clusters. Nonlinear rotational spectroscopy in the terahertz regime has been developed recently to investigate the rotational dynamics of linear and symmetric-top molecules whose rotational energy levels are regularly spaced. However, it has not been applied to water or other lower-symmetry molecules with irregularly spaced levels. We report the use of recently developed two-dimensional (2D) terahertz rotational spectroscopy to observe high-order rotational coherences and correlations between rotational transitions that were previously unobservable. The results include two-quantum (2Q) peaks at frequencies that are shifted slightly from the sums of distinct rotational transitions on two different molecules. These results directly reveal the presence of previously unseen metastable water complexes with lifetimes of 100 ps or longer. Several such peaks observed at distinct 2Q frequencies indicate that the complexes have multiple preferred bimolecular geometries. Our results demonstrate the sensitivity of rotational correlations measured in 2D terahertz spectroscopy to molecular interactions and complexation in the gas phase.

 

Ammonia is special. It is nonplanar, yet in v = 1 of the umbrella mode (ν 2 ) its inversion motion is faster than J = 0↔1 rotation. Does the simplicity of the Chemist's concept of an electric dipole moment survive the competition between rotation, inversion, and a strong external electric field? NH 3 is a favorite pedagogical example of tunneling in a symmetric double-minimum potential. Tunneling is a dynamical concept, yet the quantitative characteristics of tunneling are expressed in a static, eigenstate-resolved spectrum. The inverting-umbrella tunneling motion in ammonia is both large amplitude and profoundly affected by an external electric field. We report how a uniquely strong (up to 10 8 V/m) direct current (DC) electric field causes a richly detailed sequence of reversible changes in the frequency-domain infrared spectrum (the v = 0→1 transition in the ν 2 umbrella mode) of ammonia, freely rotating in a 10 K Ar matrix. Although the spectrum is static, encoded in it is the complete inter- and intramolecular picture of tunneling dynamics. 

The 193-nm photolysis of CH₂CHCN illustrates the capability of chirped-pulse Fourier transform millimeter-wave spectroscopy to characterize transition states. We investigate the HCN, HNC photofragments in highly excited vibrational states using both frequency and intensity information. Measured relative intensities ofJ= 1–0 rotational transition lines yield vibrational-level population distributions (VPD). These VPDs encode the properties of the parent molecule transition state at which the fragment molecule was born. A Poisson distribution formalism, based on the generalized Franck–Condon principle, is proposed as a framework for extracting information about the transition-state structure from the observed VPD. We employ the isotopologue CH₂CDCN to disentangle the unimolecular 3-center DCN elimination mechanism from other pathways to HCN. Our experimental results reveal a previously unknown transition state that we tentatively associate with the HCN eliminated via a secondary, bimolecular reaction.

 

STIRAP (stimulated Raman adiabatic passage) is a powerful laser-based method, usually involving two photons, for efficient and selective transfer of populations between quantum states. A particularly interesting feature is the fact that the coupling between the initial and the final quantum states is via an intermediate state, even though the lifetime of the latter can be much shorter than the interaction time with the laser radiation. Nevertheless, spontaneous emission from the intermediate state is prevented by quantum interference. Maintaining the coherence between the initial and final state throughout the transfer process is crucial. STIRAP was initially developed with applications in chemical dynamics in mind. That is why the original paper of 1990 was published inThe Journal of Chemical Physics. However, from about the year 2000, the unique capabilities of STIRAP and its robustness with respect to small variations in some experimental parameters stimulated many researchers to apply the scheme to a variety of other fields of physics. The successes of these efforts are documented in this collection of articles. In Part A the experimental success of STIRAP in manipulating or controlling molecules, photons, ions or even quantum systems in a solid-state environment is documented. After a brief introduction to the basic physics of STIRAP, the central role of the method in the formation of ultracold molecules is discussed, followed by a presentation of how precision experiments (measurement of the upper limit of the electric dipole moment of the electron or detecting the consequences of parity violation in chiral molecules) or chemical dynamics studies at ultralow temperatures benefit from STIRAP. Next comes the STIRAP-based control of photons in cavities followed by a group of three contributions which highlight the potential of the STIRAP concept in classical physics by presenting data on the transfer of waves (photonic, magnonic and phononic) between respective waveguides. The works on ions or ion strings discuss options for applications, e.g. in quantum information. Finally, the success of STIRAP in the controlled manipulation of quantum states in solid-state systems, which are usually hostile towards coherent processes, is presented, dealing with data storage in rare-earth ion doped crystals and in nitrogen vacancy (NV) centers or even in superconducting quantum circuits. The works on ions and those involving solid-state systems emphasize the relevance of the results for quantum information protocols. Part B deals with theoretical work, including further concepts relevant to quantum information or invoking STIRAP for the manipulation of matter waves. The subsequent articles discuss the experiments underway to demonstrate the potential of STIRAP for populating otherwise inaccessible high-lying Rydberg states of molecules, or controlling and cooling the translational motion of particles in a molecular beam or the polarization of angular-momentum states. The series of articles concludes with a more speculative application of STIRAP in nuclear physics, which, if suitable radiation fields become available, could lead to spectacular results.