Quantum states spectroscopy

Molecular rotors are useful as reporters of their microenvironment, because their fluorescence emission allows to probe TICT formation and solvent interaction. Measurements are possible through steady-state spectroscopy and time-resolved spectroscopy. Three primary effects were identified in Sect. 2, namely, the solvent-dependent reorientation rate, the solvent-dependent quantum yield (which directly links to the reorientation rate), and the solvatochromic shift. Most commonly, molecular rotors exhibit a change in quantum yield as a consequence of nonradia-tive relaxation. Therefore, the fluorophore s quantum yield needs to be determined as accurately as possible. In steady-state spectroscopy, emission intensity can be calibrated with quantum yield standards. Alternatively, relative changes in emission intensity can be used, because the ratio of two intensities is identical to the ratio of the corresponding quantum yields if the fluid optical properties remain constant. For molecular rotors with nonradiative relaxation, the calibrated measurement of the quantum yield allows to approximately compute the rotational relaxation rate kor from the measured quantum yield [Pg.284]

Infrared Excitation between vibrational quantum states Infrared spectroscopy... 

Microwaves Excitation between rotational quantum states Rotational spectroscopy... 

In general, though, Raman spectroscopy is concerned with vibrational transitions (in a manner akin to infrared spectroscopy), since shifts of these Raman bands can be related to molecular structure and geometry. Because the energies of Raman frequency shifts are associated with transitions between different rotational and vibrational quantum states, Raman frequencies are equivalent to infrared frequencies within the molecule causing the scattering. 

Tunable laser spectroscopic techniques such as laser-induced fluorescence (LIF) or resonantly enhanced multi-photon ionization (REMPI) are well-established mature fields in gas-phase spectroscopy and dynamics, and their application to gas-surface dynamics parallels their use elsewhere. The advantage of these techniques is that they can provide exceedingly sensitive detection, perhaps more so than mass spectrometers. In addition, they are detectors of individual quantum states and hence can measure nascent internal state population distributions produced via the gas-surface dynamics. The disadvantage of these techniques is that they are not completely general. Only some interesting molecules have spectroscopy amenable to be detected sensitively in this fashion, e.g., H2, N2, NO, CO, etc. Other interesting molecules, e.g. 02, CH4, etc., do not have suitable spectroscopy. However, when applicable, the laser spectroscopic techniques are very powerful. 

Thermal emission spectroscopy can be used in middle- and far-infrared spectral regions to make stratospheric measurements, and it has been applied to a number of important molecules with balloon-borne and satellite-based detection systems. In this approach, the molecules of interest are promoted to excited states through collisions with other molecules. The return to the ground state is accompanied by the release of a photon with energy equal to the difference between the quantum states of the molecule. Therefore, the emission spectrum is characteristic of a given molecule. Calculation of the concentration can be complicated because the emission may have originated from a number of stratospheric altitudes, and this situation may necessitate the use of computer-based inversion techniques (24-27) to retrieve a concentration profile. 

When the fine structure frequencies fall below 100 MHz they can also be measured by quantum beat spectroscopy. The basic principle of quantum beat spectroscopy is straightforward. Using a polarized pulsed laser, a coherent superposition of the two fine structure states is excited in a time short compared to the inverse of the fine structure interval. After excitation, the wavefunctions of the two fine structure levels evolve at different rates due to their different energies. For example if the nd3/2 and nd5/2 mf = 3/2 states are coherently excited from the 3p3/2 state at time t = 0, the nd wavefunction at a later time t can be written as40... 

Molecular systems exist in discrete quantum states, the study of which lies in the realm of molecular structure and wave mechanics. Transitions between quantum states occur either by absorption or emission of radiation (spectroscopy) or by collisional processes. There are two main types of collisional transitions which are important in chemical physics these are first, reactive processes in which chemical rearrangement takes place (reaction kinetics), and secondly collisions in which the energy distribution is changed without overall chemical reaction. It may therefore be concluded that the energy transfer processes discussed here are of fundamental importance in all molecular systems, and that the subject, like molecular structure, is enormously varied and complex. 

Indirect photodissociation involves two more or less separate steps the absorption of the photon and the fragmentation of the excited complex. Resonances, which mirror the quasi-bound states of the intermediate complex in the upper electronic state, are the main features. They have an inherently quantum mechanical origin. If we consider — in very general terms — the inner region, before the fragments have obtained their identities, as the transition state, then the resolution of resonance structures in the absorption spectrum manifests transition state spectroscopy in the original sense of the word (Foth, Polanyi, and Telle 1982 Brooks 1988). 

The Buck method is most useful for medium sized clusters, and in experiments that do not attempt detailed photochemical studies of the size selected clusters. High resolution spectroscopy of the selected clusters is impractical because the number per quantum state is small, due to the many occupied ro-vibrational... 

Walther, Th., Bitto, H. and Huber, J.R. (1993). High-resolution quantum beat spectroscopy in the electronic ground state of a polyatomic molecule by IR-UV pump-probe method, Chem. Phys. 

Nuclear magnetic resonance (NMR) spectroscopy is routinely applied to small carbohydrate molecules. NMR spectroscopy is based on the principle that radiofrequencies are absorbed by hydrogen and carbon atoms ( H and 13C) spinning in one of two directions (spin quantum number +1 /2) in a magnetic field. In liquids, absorption is recorded as sharp peaks. The frequency displacement (chemical shift) is a function of the H and 1SC surroundings. +A is proportional to the number of photons absorbed between these two quantum states, correlating well with anomeric and... 

The classical concept of object dissolves in so far the configuration space for the internal degrees of freedom is concerned. The material elements such as electrons and nuclei must be present to sustain quantum states, but locali-zability is not a requirement it may be a result of specific operators. The configuration space is an abstract mathematical space. Of course, one can force a representation as position vectors for particles. Consequently, one has to interpret the wavefunction. But again, Eqs. (3 and 4) demand amplitudes, energy gaps, and quantum numbers. This is spectroscopy of one type or another. The introduction of I-frames allows classical frameworks to be naturally incorporated. 

Any quantum system can be associated to an I-frame thereby, internal and "external" (I-frame) quantum states can be determined or at least observed as done in astronomy. Probing (measuring) a quantum system breaks Hilbert space-time evolution thereby preparing a new quantum state. This latter can be used to detect the result due to probing. See Ref. [29] for an illustration. Gravitation is a prototype of classical effects. From neutron interference spectroscopy gravitation effects on quantum states are well documented. 

In impulsive multidimensional (1VD) Raman spectroscopy a sample is excited by a train of N pairs of optical pulses, which prepare a wavepacket of quantum states. This wavepacket is probed by the scattering of the probe pulse. The electronically off-resonant pulses interact with the electronic polarizability, which depends parametrically on the vibrational coordinates (19), and the signal is related to the 2N + I order nonlinear response (18). Seventh-order three-dimensional (3D) coherent Raman scattering, technique has been proposed by Loring and Mukamel (20) and reported in Refs. 12 and 21. Fifth-order two-dimensional (2D) Raman spectroscopy, proposed later by Tanimura and Mukamel (22), had triggered extensive experimental (23-28) and theoretical (13,25,29-38) activity. Raman techniques have been reviewed recently (12,13) and will not be discussed here. 

UV absorption spectroscopy is usually not sensitive enough to monitor ions direetly in the jet. Even if the original ion pair is somehow dissociated in to two separate ions having a eharacteristie absorption, their detection by high-resolution absorption speetroscopy is often impraetieal. The nascent product ions are formed in a large number of quantum states, and the small population of a single state eannot be detected with reasonable signal-to-noise ratio. 

One of the most important motivations for the study of gaseous systems, as repeatedly hinted at, is the hope of obtaining a better connection with theory and theoretical modeling. The structure of solvated adducts and charge-transfer pairs in solution cannot be deduced directly from experimental data. In the gas phase, rota-tionally resolved spectroscopy provides information on the structure. The method also allows a much better vibrational resolution than liquid-phase spectroscopy, allowing in principle the elucidation of subtle effects such as the role of torsional motion. All of these advantages are enhanced in supersonic jets, where only a small number of quantum states are initially populated. 

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