7 = 0 rotational state

Infrared Spectroscopy. The infrared spectroscopy of adsorbates has been studied for many years, especially for chemisorbed species (see Section XVIII-2C). In the case of physisorption, where the molecule remains intact, one is interested in how the molecular symmetry is altered on adsorption. Perhaps the conceptually simplest case is that of H2 on NaCl(lOO). Being homo-polar, Ha by itself has no allowed vibrational absorption (except for some weak collision-induced transitions) but when adsorbed, the reduced symmetry allows a vibrational spectrum to be observed. Fig. XVII-16 shows the infrared spectrum at 30 K for various degrees of monolayer coverage [96] (the adsorption is Langmuirian with half-coverage at about 10 atm). The bands labeled sf are for transitions of H2 on a smooth face and are from the 7 = 0 and J = 1 rotational states Q /fR) is assigned as a combination band. The bands labeled... 

The rotational states are characterized by a quantum number J = 0, 1, 2,. .. are degenerate with degeneracy (2J + 1) and have energy t r = ) where 1 is the molecular moment of inertia. Thus... 

Sonnenfroh D M and Leone S R 1989 A laser-induced fluorescence study of product rotational state distributions in the charge transfer reaction Ar <-i. i, ) + Ni Ar + MfXjat 0.28 and 0.40 eV J. them. Phys. 90 1677-85... 

Figure A3.9.5. Population of rotational states versus rotational energy for NO moleeules seattered from an Ag (111) surfaee at two different ineidenee energies and at = 520 K [25] (a) E = 0.85 eV, 0. = 15° and b) E = 0.09 eV, 9. = 15°. Results at = 0.85 eV show a pronoimeed rotational rainbow.

Figure A3.9.9. Dissociation probability versus incident energy for D2 molecules incident on a Cu(l 11) surface for the initial quantum states indicated (u indicates the mitial vibrational state and J the initial rotational state) [100], For clarity, the saturation values have been scaled to the same value irrespective of the initial state, although in reality die saturation value is higher for the u = 1 state.

The strong dependence of the PES on molecular orientation also leads to strong coupling between rotational states, and hence rotational excitation/de-excitation in the scattering. This has been observed experimentally for H2 scattering from Cu surfaces. Recent work has shown that for H2 the changes m rotational state occur almost exclusively when the molecular bond is extended, that is, longer than the gas-phase equilibrium value [ ]. 

RRKM theory assumes a microcanonical ensemble of A vibrational/rotational states within the energy interval E E + dE, so that each of these states is populated statistically with an equal probability [4]. This assumption of a microcanonical distribution means that the unimolecular rate constant for A only depends on energy, and not on the maimer in which A is energized. If N(0) is the number of A molecules excited at / =... 

A situation that arises from the intramolecular dynamics of A and completely distinct from apparent non-RRKM behaviour is intrinsic non-RRKM behaviour [9], By this, it is meant that A has a non-random P(t) even if the internal vibrational states of A are prepared randomly. This situation arises when transitions between individual molecular vibrational/rotational states are slower than transitions leading to products. As a result, the vibrational states do not have equal dissociation probabilities. In tenns of classical phase space dynamics, slow transitions between the states occur when the reactant phase space is metrically decomposable [13,14] on the timescale of the imimolecular reaction and there is at least one bottleneck [9] in the molecular phase space other than the one defining the transition state. An intrinsic non-RRKM molecule decays non-exponentially with a time-dependent unimolecular rate constant or exponentially with a rate constant different from that of RRKM theory. 

Spectral lines are fiirther broadened by collisions. To a first approximation, collisions can be drought of as just reducing the lifetime of the excited state. For example, collisions of molecules will connnonly change the rotational state. That will reduce the lifetime of a given state. Even if die state is not changed, the collision will cause a phase shift in the light wave being absorbed or emitted and that will have a similar effect. The line shapes of collisionally broadened lines are similar to the natural line shape of equation (B1.1.20) with a lifetime related to the mean time between collisions. The details will depend on the nature of the intemrolecular forces. We will not pursue the subject fiirther here. 

A microwave pulse from a tunable oscillator is injected into the cavity by an anteima, and creates a coherent superposition of rotational states. In the absence of collisions, this superposition emits a free-mduction decay signal, which is detected with an anteima-coupled microwave mixer similar to those used in molecular astrophysics. The data are collected in the time domain and Fourier transfomied to yield the spectrum whose bandwidth is detemimed by the quality factor of the cavity. Hence, such instruments are called Fourier transfomi microwave (FTMW) spectrometers (or Flygare-Balle spectrometers, after the inventors). FTMW instruments are extraordinarily sensitive, and can be used to examine a wide range of stable molecules as well as highly transient or reactive species such as hydrogen-bonded or refractory clusters [29, 30]. 

Figure Bl.4.4. (a) An outline of the Harvard University eleetrie diseharge siipersonie nozzle/Foiirier transfonn mierowave speetroineter. (b) The rotational states of HCj N observed with this apparatus [31],...

Keil and co-workers (Dhamiasena et al [16]) have combined the crossed-beam teclmique with a state-selective detection teclmique to measure the angular distribution of HF products, in specific vibration-rotation states, from the F + Fl2 reaction. Individual states are detected by vibrational excitation with an infrared laser and detection of the deposited energy with a bolometer [30]. 

NO prodnet from tire H + NO2 reaetion [43]. Individnal lines in the various rotational branehes are denoted by the total angidar momentum J of the lower state, (b) Simnlated speetnim with the NO rotational state populations adjusted to reprodnee the speetnim in (a). (By permission from AIP.)... 

The anisotropy of the product rotational state distribution, or the polarization of the rotational angular momentum, is most conveniently parametrized tluough multipole moments of the distribution [45]. Odd multipoles, such as the dipole, describe the orientation of the angidar momentum /, i.e. which way the tips of the / vectors preferentially point. Even multipoles, such as the quadnipole, describe the aligmnent of /, i.e. the spatial distribution of the / vectors, regarded as a collection of double-headed arrows. Orr-Ewing and Zare [47] have discussed in detail the measurement of orientation and aligmnent in products of chemical reactions and what can be learned about the reaction dynamics from these measurements. 

Recently, the state-selective detection of reaction products tluough infrared absorption on vibrational transitions has been achieved and applied to the study of HF products from the F + H2 reaction by Nesbitt and co-workers (Chapman et al [7]). The relatively low sensitivity for direct absorption has been circumvented by the use of a multi-pass absorption arrangement with a narrow-band tunable infrared laser and dual beam differential detection of the incident and transmission beams on matched detectors. A particular advantage of probing the products tluough absorption is that the absolute concentration of the product molecules in a given vibration-rotation state can be detenuined. 

This book presents a detailed exposition of angular momentum theory in quantum mechanics, with numerous applications and problems in chemical physics. Of particular relevance to the present section is an elegant and clear discussion of molecular wavefiinctions and the detennination of populations and moments of the rotational state distributions from polarized laser fluorescence excitation experiments. 

A MBER spectrometer is shown schematically in figure C1.3.1. The teclmique relies on using two inhomogeneous electric fields, the A and B fields, to focus the beam. Since the Stark effect is different for different rotational states, the A and B fields can be set up so that a particular rotational state (with a positive Stark effect) is focused onto the detector. In MBER spectroscopy, the molecular beam is irradiated with microwave or radiofrequency radiation in the... 

C3.3.4 DEDUCING ENERGY TRANSFER MECHANISMS FROM POPULATION AND VELOCITY DISTRIBUTIONS OF THE SCATTERED BATH MOLECULES ROTATIONAL STATE POPULATION DISTRIBUTIONS FOR VIBRATIONAL EXCITATION OF THE BATH... 

For heavy molecules with very small rotational state spacing, this limit on AJ puts severe upper limits on the amount of energy that can be taken up in the rotations of a heavy molecule during a collision. Despite these limitations, P(E, E ) distributions have been obtained by inverting data of the type described here for values of AE in the range -1500 cm > AE > -8000 cnD for the two donor molecules pyrazine and hexafluorobenzene with carbon dioxide as a bath acceptor molecule [15,16]. Figure C3.3.11 shows these experimentally derived... 

It is beyond the scope of these introductory notes to treat individual problems in fine detail, but it is interesting to close the discussion by considering certain, geometric phase related, symmetry effects associated with systems of identical particles. The following account summarizes results from Mead and Truhlar [10] for three such particles. We know, for example, that the fermion statistics for H atoms require that the vibrational-rotational states on the ground electronic energy surface of NH3 must be antisymmetric with respect to binary exchange... 

In Figure 1, we see that there are relative shifts of the peak of the rotational distribution toward the left from f = 12 to / = 8 in the presence of the geometiic phase. Thus, for the D + Ha (v = 1, DH (v, f) - - H reaction with the same total energy 1.8 eV, we find qualitatively the same effect as found quantum mechanically. Kuppermann and Wu [46] showed that the peak of the rotational state distribution moves toward the left in the presence of a geometric phase for the process D + H2 (v = 1, J = 1) DH (v = 1,/)- -H. It is important to note the effect of the position of the conical intersection (0o) on the rotational distribution for the D + H2 reaction. Although the absolute position of the peak (from / = 10 to / = 8) obtained from the quantum mechanical calculation is different from our results, it is worthwhile to see that the peak... 

The calculations showed [54,55] significant effect of the GP on scattering angle resolved cross-sections for a particular final rotational state. It is interesting to see the change of these distributions due to the geometric phase... 

Differential cross-sections for particular final rotational states (f) of a particular vibrational state (v ) are usually smoothened by the moment expansion (M) in cosine functions mentioned in Eq, (38). Rotational state distributions for the final vibrational state v = 0 and 1 are presented in [88]. In each case, with or without GP results are shown. The peak position of the rotational state distribution for v = 0 is slightly left shifted due to the GP effect, on the contrary for v = 1, these peaks are at the same position. But both these figures clearly indicate that the absolute numbers in each case (with or without GP) are different. 

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