The UV absorption spectrum of C60 (buckminsterfullerene): A narrow band at 3860 Å

The absorption spectrum of the special C60 cluster buckminsterfullerene has been studied in a supersonic beam by laser depletion of the cold van der Waals complexes of C60 with benzene and methylene chloride. Both complexes were found to display a single, isolated absorption band in the near ultraviolet superimposed on a structureless absorption continuum. For the methylene chloride complex this feature is centered at 3860 Å, and is roughly 50 cm−1 wide. In the benzene van der Waals cluster, the corresponding feature is located at 3863 Å, and has a similar width. This spectrum is tentatively assigned to the 0–0 band of the lowest 1T1u<--1Ag (LUMO+1<--HOMO) transition of a truncated icosahedral carbon shell structure, broadened by coupling to the underlying quasicontinuum of ground state vibrational levels

Photophysics of buckminsterfullerene and other carbon cluster ions

The laser-induced fragmentation behavior of positive carbon cluster ions has been investigated by tandem time-of-flight techniques for the jet-cooled clusters up to 80 atoms in size. Two distinct photophysical regimes were found. The first applies to clusters with 34 atoms or more, all of which dissociate to produce even numbered fragments. Large even clusters fragment by the loss of the high energy species C2, odd ones lose a C atom. The second regime applies to clusters composed of 31 or less atoms, all of which fragment by the loss of C3. These two regimes are sharply separated by C + 32 which fragments to produce small cluster ions in the 10–19 atom size range. Fragmentation of the large clusters occurs on a microsecond or faster time scale only at very high levels of excitation (>12.8 eV). These photophysical results are interpreted as consequences of the large even clusters having edgeless, spheroidal cage structures while the small ones have linear chain or ring structures

Semiconductor cluster beams: One and two color ionization studies of Six and Gex

Supersonic beams of clusters of Si and Ge atoms have been produced by laser vaporization followed by supersonic expansion in a helium carrier. The cluster beams were characterized by F2(7.9 eV) and ArF(6.4 eV) excimer laser ionization accompanied by time-of-flight mass analysis. In addition, the feasibility of a resonant two-photon ionization (R2PI) spectroscopic study was explored by two-color experiments involving initial excitation with the second (2.36 eV) and third (3.54 eV) harmonics of the Nd:YAG followed by excimer laser ionization. All two-photon ionization processes were found to produce extensive fragmentation of the larger clusters. The observed fragmentation pattern for the silicon and germanium clusters were remarkably similar to each other, but drastically different from that seen for metal clusters in the same apparatus. Unlike metal clusters, which tend to lose one atom at a time, these semiconductor clusters appear to fragment by a fission process, the daughter ions falling almost exclusively in the size range from 6 to 11 atoms. Time delay studies in the two-color experiments established that clusters of both Si and Ge have excited electronic states with lifetimes of approximately 100 ns. This again is dramatically different from the behavior found with metal clusters, and indicates the feasibility of R2PI spectroscopy on these cold semiconductor particles. The existence of such long-lived excited states indicates that there is probably an energy gap between the band of electronic states being excited and the ground electronic state

Magnetic Properties of Undoped C60C_{60}

The Heisenberg antiferromagnet, which arises from the large $U$ Hubbard model, is investigated on the $C_{60}$ molecule and other fullerenes. The connectivity of $C_{60}$ leads to an exotic classical ground state with nontrivial topology. We argue that there is no phase transition in the Hubbard model as a function of $U/t$, and thus the large $U$ solution is relevant for the physical case of intermediate coupling. The system undergoes a first order metamagnetic phase transition. We also consider the S=1/2 case using perturbation theory. Experimental tests are suggested.Comment: 12 pages, 3 figures (included

Coherent control of enrichment and conversion of molecular spin isomers

A theoretical model of nuclear spin conversion in molecules controlled by an external electromagnetic radiation resonant to rotational transition has been developed. It has been shown that one can produce an enrichment of spin isomers and influence their conversion rates in two ways, through coherences and through level population change induced by radiation. Influence of conversion is ranged from significant speed up to almost complete inhibition of the process by proper choice of frequency and intensity of the external field.Comment: REVTEX, 13 pages + 6 eps figure

Magic Numbers of Silicon Clusters

A structural model for intermediate sized silicon clusters is proposed that is able to generate unique structures without any dangling bonds. This structural model consists of bulk-like core of five atoms surrounded by fullerene-like surface. Reconstruction of the ideal fullerene geometry results in the formation of crown atoms surrounded by $\pi$-bonded dimer pairs. This model yields unique structures for \Si{33}, \Si{39}, and \Si{45} clusters without any dangling bonds and hence explains why these clusters are least reactive towards chemisorption of ammonia, methanol, ethylene, and water. This model is also consistent with the experimental finding that silicon clusters undergo a transition from prolate to spherical shapes at \Si{27}. Finally, reagent specific chemisorption reactivities observed experimentally is explained based on the electronic structures of the reagents.Comment: 4 pages + 3 figures (postscript files after \end{document}

Small-Size Resonant Photoacoustic Cell of Inclined Geometry for Gas Detection

A photoacoustic cell intended for laser detection of trace gases is represented. The cell is adapted so as to enhance the gas-detection performance and, simultaneously, to reduce the cell size. The cell design provides an efficient cancellation of the window background (a parasite response due to absorption of laser beam in the cell windows) and acoustic isolation from the environment for an acoustic resonance of the cell. The useful photoacoustic response from a detected gas, window background and noise are analyzed in demonstration experiments as functions of the modulation frequency for a prototype cell with the internal volume ~ 0.5 cm^3. The minimal detectable absorption for the prototype is estimated to be ~ 1.2 10^{-8} cm^{-1} W Hz^{-1/2}.Comment: 11 pages, 5 figure

Raman scattering in C_{60} and C_{48}N_{12} aza-fullerene: First-principles study

We carry out large scale {\sl ab initio} calculations of Raman scattering activities and Raman-active frequencies (RAFs) in ${\rm C}_{48}{\rm N}_{12}$ aza-fullerene. The results are compared with those of ${\rm C}_{60}$. Twenty-nine non-degenerate polarized and 29 doubly-degenerate unpolarized RAFs are predicted for ${\rm C}_{48}{\rm N}_{12}$. The RAF of the strongest Raman signal in the low- and high-frequency regions and the lowest and highest RAFs for ${\rm C}_{48}{\rm N}_{12}$ are almost the same as those of ${\rm C}_{60}$. The study of ${\rm C}_{60}$ reveals the importance of electron correlations and the choice of basis sets in the {\sl ab initio} calculations. Our best calculated results for ${\rm C}_{60}$ with the B3LYP hybrid density functional theory are in excellent agreement with experiment and demonstrate the desirable efficiency and accuracy of this theory for obtaining quantitative information on the vibrational properties of these molecules.Comment: submitted to Phys.Rev.