ABSTRACT
We report the results of a (2+1) resonance-enhanced multiphoton ionization (REMPI) study of the E2Sigma+(4ssigma) Rydberg state of NO-Kr. We present an assignment of the two-photon spectrum based on a simulation, and discuss it in the context of previously-reported spectra of NO-Ne and NO-Ar. In addition, we report on spectra in the region of the vNO=1 level of the E, F and H' 4s and 3d Rydberg states of NO-Rg (Rg=Ne-Kr). Since the NO vibrational frequency is affected by electron donation from the rare-gas (Rg) atom to the NO+ core, as well as by the penetration of the Rydberg electron, the fundamental NO-stretch frequency reflects the interactions in the complex. The results indicate that the 4s Rydberg state has a strong interaction between the NO+ core and the Kr atom, as was the case for NO-Ar and NO-Ne. For the 3d Rydberg states, although penetration is not as significant as for the 4s Rydberg states, it does play an important role, with subtle angular effects being notable.
ABSTRACT
We have employed (2 + 1) resonance enhanced multiphoton ionization spectroscopy to investigate the 3d and 4s Rydberg states of the NO molecule when bound to the surface of Rg(x) clusters (Rg = rare gas). We observe that the spectra of the NO-Ar(x) species converge in appearance as x increases, and this is discussed in terms of two Rg atoms interacting with the NO+ core, with other Rg atoms being "outside" the Rydberg orbital. We show that the interaction of each of the Rg atoms with the NO is essentially independent for the NO-Rg2 complexes: both by comparing our spectra for Rydberg states of NO-Rg and NO-Rg2, and from the results of ab initio calculations on NO+ - Rg and NO+ - Rg2. In addition, we discuss the disappearance of some electronic bands upon complexation in terms of Franck-Condon factors that are very sensitive to the angular coordinate. We relate our results to those of the bulk by comparing to the previously reported electronic spectroscopy of NO in both Rg matrices and He nanodroplets.
ABSTRACT
We have collected (2 + 1) Resonance-Enhanced Multiphoton Ionization (REMPI) spectra of van der Waals complexes in which a NO molecule is attached to either CO, N(2), or both N(2) and Ar. The energy region probed corresponds to electronic transitions of uncomplexed NO(X(2)Pi) to the 4s and 3d Rydberg states, and we discuss the observed spectra in light of the expected perturbations to these electronic levels induced by complexation. We employ a model in which the van der Waals partners are assumed to reside within the Rydberg orbital, and discuss the importance of core penetration in the description of the electronic structure. By performing calculations on NO(+) interacting with both N(2) and Ar, we identify the global minimum as being a non-planar structure. Further, the N(2) and Ar are found to interact with the NO(+) largely independently, and we find some evidence for this from the REMPI spectrum of NO-{N(2), Ar}.
Subject(s)
Argon/chemistry , Carbon Monoxide/chemistry , Nitric Oxide/chemistry , Nitrogen/chemistry , Spectrum Analysis/methods , Models, Molecular , Radiation, Ionizing , ThermodynamicsABSTRACT
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 2ppi* orbital to 3dsigma, 3dpi, and 3ddelta Rydberg states. We review the ordering of the 3dlambda 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 H' 2Pi state occurs through the F2Delta 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.
ABSTRACT
The molecular complexes formed between a nitric oxide molecule and the various deuterated isotopomers of the methane molecule have been studied in a supersonic jet expansion. The electronic spectrum arising from the transition corresponding to a 3s<--pi* excitation (approximately A (2)Sigma(+)<-- approximately X (2)Pi) located on the NO chromophore has been recorded employing resonance-enhanced multiphoton ionization spectroscopy, with each of CH(4), CH(3)D, CH(2)D(2), CHD(3), and CD(4) as the complexing partner. Rich spectra are obtained, whose appearance changes in a systematic way as the amount of deuteration increases. Unexpectedly, it was possible to record spectra not only in the parent mass channel, but also in various fragment channels; this also led to the identification of some O atom resonances; and their origin is discussed. Discussion is presented of the structure in the spectra, and its possible sources including hindered internal rotation of the methane and NO moieties, overall rotation of the complex, and tunneling. In addition, some guidance has been gleaned from ab initio calculations, and these are discussed in the light of the experimental results.
ABSTRACT
Small clusters of toluene(n) (n = 1-8) were created in a supersonic expansion of toluene with argon as a carrier gas. Mass-selected resonance enhanced multiphoton ionization spectra of these clusters were recorded for each n. For the dimer, the appearance of the spectrum under warm and very cold conditions was studied. We discuss previous results in the light of the present spectra. For n>2, the spectra resemble very closely that of the dimer.
