We report the first measurement of the spectrum of the NO-N(2) complex in the region of the first vibrational NO overtone transition. The origin band of the complex is blueshifted by 0.30 cm(-1) from the corresponding NO monomer frequency. The observed spectrum consists of three bands assigned to the origin band, the excitation of one quantum of z-axis rotation and one associated hot band. The spacing of the bands and the rotational structure indicate a T-shaped vibrationally averaged structure with the NO molecule forming the top of the T. These findings are confirmed by high level ab initio calculations of the potential energy surfaces in planar symmetry. The deepest minimum is found for a T-shaped geometry on the A(")-surface. As a result the sum potential also has the global minimum for this structure. The different potential surfaces show several additional local minima at slightly higher energies indicating that the complex most likely will perform large amplitude motion even in its ground vibrational state. Nevertheless, as suggested by the measured spectra, the complex must, on average, spend a substantial amount of time near the T-shaped configuration.
We have employed (2+1) resonance-enhanced multiphoton ionization spectroscopy to record electronic absorption spectra of NO–Rg (Rg=Ne,Ar,Kr) van der Waals complexes. The nitric oxide molecule is the chromophore, and the excitation corresponds to an electron being promoted from the 2pπ* orbital to 3dσ, 3dπ, and 3dδ Rydberg states. We review the ordering of the 3dλ states of NO and use this as a basis for discussing the 3d components in the NO–Rg complexes, in terms of the interactions between the Rydberg electron, the core, and the Rg atom. Predissociation of the H̃′Π2 state occurs through the F̃Δ2 state for NO–Ar and NO–Kr, and this will be considered. We shall also outline problems encountered when trying to record similar spectra for NO–Xe, related to the presence of atomic Xe resonances.
We describe the first measurement of the near IR spectrum of the NO-Kr van der Waals complex. A variant of IR-REMPI double-resonance spectroscopy is employed in which the IR and UV lasers are scanned simultaneously in such a way that throughout the scan the sum of the two photon energies is kept constant, matching a UV resonance of the system. In the region of the first overtone vibration of the NO monomer, we observe several rotationally resolved bands for the NO-Kr complex. In addition to the origin band located at 3723.046 cm(-1), we observe excited as well as hot bands involving the excitation of one or two quanta of z-axis rotation. Another band is assigned to the excitation of one quantum of bending vibration. The experimental spectra are compared with results of bound-state calculations for a new set of potential energy surfaces calculated at the spin-restricted coupled cluster level. For the average vibration-rotation energies, there is excellent agreement between the theoretical results based on the coupled states (CS) approximation and the full close-coupling (CC) treatment. Finer details like the electrostatic splitting and the P-type doubling of the rotational levels are accounted for only within the CC formalism. The comparison of the CC results with the measured spectra confirms the high quality of the PESs. However, the high resolution of the experiments is sufficient to identify some inaccuracies in the difference between the potential energy surfaces of A' and A'' reflection symmetry.
We describe a new approach to IR-UV double resonance spectroscopy of NO-containing van der Waals complexes. The basic idea combines REMPI detection through a hot band transition with a simultaneous frequency scan of the IR and UV lasers in such a way that the combined photon energy is kept constant throughout the scan, matching a UV resonance transition in the system. As a result, the two-dimensional frequency problem is reduced to a fixed number of one-dimensional frequency scans, each defined by a particular photon energy sum. The method is applied to the near-IR spectrum of NO-Ar using hot band detection via the electronic A state of the complex. In the frequency range from 3718 to 3765 cm(-1), we recorded the previously known vibrational bands with improved frequency resolution. The increased sensitivity of the present experiment allowed us to measure for the first time their overtone, combination, and hot bands. Through the comparison with results of a close-coupling (CC) calculation, we were able to assign most of the rovibrational structures of the spectrum. Except for the first intermolecular stretch level, the band positions and rotational structures of the observed bands are in good agreement with the predictions of the CC calculations.
We report the first measurement of the near IR spectrum of the NO-CH(4) complex in the region of the first vibrational NO overtone transition in an IR-resonance enhanced multiphoton ionization double resonance experiment. The origin band is located at 3723.26 cm(-1), i.e., redshifted by 0.59 cm(-1) from the corresponding NO monomer frequency. The observed spectrum consists of two bands assigned to the origin band and the excitation of hindered rotation of the NO monomer in the complex similar to z-axis rotation. The spacing and the relative intensity of the bands are consistent with a structure in which NO resides preferentially in a position perpendicular to the intermolecular axis. The deviation from the linear configuration with C(3v) symmetry can be regarded as a Jahn-Teller (JT) distortion. Each band is dominated by two broad peaks with a few resolved rotational structures. The large spacing between the two peaks is indicative of significant angular momentum quenching, possibly another manifestation of the JT effect. The delay dependence between the IR and UV laser pulses reveals a lifetime of about 10 ns for the vibrationally excited complex due to vibrational predissociation. On the other hand, the linewidth of the narrowest spectral features indicates a much shorter excited state lifetime of about 100 ps, most likely due to intramolecular vibrational redistribution.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.