Quantum nature

C3.2.4.3 INTERPRETING THE QUANTUM NATURE OF PROTEINS REDUCED HAMILTONIANS AND CURRENT LOOPS... 

Classical descriptions of molecular phenomena can be remarkably successful, but we have to keep our eye on the intrinsic quantum nature of microscopic systems. 

Abstract The statistical properties of the electromagnetic field find their origin in its quantum nature. While most experiments can be interpreted relying on classical electrodynamics, in the past thirty years, many experiments need a quantum description of the electromagnetic field. This gives rises to distinct statistical properties. 

In future improvements in technology may mean that that read noise no longer is the dominant noise source, and Poisson noise arising from the quantum nature of light is in fact the limiting factor. In this case the variance of the centroid noise is equal to. 

The new delightful book by Greenstein and Zajonc(9) contains several examples where the outcome of experiments was not what physicists expected. Careful analysis of the Schrddinger equation revealed what the intuitive argument had overlooked and showed that QM is correct. In Chapter 2, Photons , they tell the story that Einstein got the Nobel Prize in 1922 for the explaining the photoelectric effect with the concept of particle-like photons. In 1969 Crisp and Jaynes(IO) and Lamb and Scullyfl I) showed that the quantum nature of the photoelectric effect can be explained with a classical radiation field and a quantum description for the atom. Photons do exist, but they only show up when the EM field is in a state that is an eigenstate of the number operator, and they do not reveal themselves in the photoelectric effect. 

Transition state theory, as embodied in Eq. 10.3, or implicitly in Arrhenius theory, is inherently semiclassical. Quantum mechanics plays a role only in consideration of the quantized nature of molecular vibrations, etc., in a statistical fashion. But, a critical assumption is that only those molecules with energies exceeding that of the transition state barrier may undergo reaction. In reality, however, the quantum nature of the nuclei themselves permits reaction by some fraction of molecules possessing less than the energy required to surmount the barrier. This phenomenon forms the basis for QMT. ... 

If the wavelengths of the reacting nuclei become comparable to barrier widths, that is, the distance nuclei must move to go from reactant well to product well, then there is some probability that the nuclear wave functions extend to the other side of the barrier. Thus, the quantum nature of the nuclei allows the possibility that molecules tunnel through, rather than pass over, a barrier. 

The AIMS method treats both the electrons and the nuclei quantum mechanically. The previous section dealt with the quantum nature of the electrons, and here we... 

Spin-orbit coupling problems are of a genuine quantum nature since a priori spin is a quantity that only occurs in quantum mechanics. However, already Thomas (Thomas, 1927) had introduced a classical model for spin precession. Later, Rubinow and Keller (Rubinow and Keller, 1963) derived the Thomas precession from a WKB-like approach to the Dirac equation. They found that although the spin motion only occurs in the first semiclassical correction to the relativistic classical electron motion, it can be expressed in merely classical terms. 

Electromagnetic radiation has its origins in atomic and molecular processes. Experiments demonstrating reflection, refraction, diffraction and interference phenomena show that the radiation has wave-like characteristics, while its emission and absorption are better explained in terms of a particulate or quantum nature. Although its properties and behaviour can be expressed mathematically, the exact nature of the radiation remains unknown. 

The theory of electron-transfer reactions presented in Chapter 6 was mainly based on classical statistical mechanics. While this treatment is reasonable for the reorganization of the outer sphere, the inner-sphere modes must strictly be treated by quantum mechanics. It is well known from infrared spectroscopy that molecular vibrational modes possess a discrete energy spectrum, and that at room temperature the spacing of these levels is usually larger than the thermal energy kT. Therefore we will reconsider electron-transfer reactions from a quantum-mechanical viewpoint that was first advanced by Levich and Dogonadze [1]. In this course we will rederive several of, the results of Chapter 6, show under which conditions they are valid, and obtain generalizations that account for the quantum nature of the inner-sphere modes. By necessity this chapter contains more mathematics than the others, but the calculations axe not particularly difficult. Readers who are not interested in the mathematical details can turn to the summary presented in Section 6. 

In spite of the frequency-shifted excitation, the quantized PIP inevitably excites multiple sidebands located at n/At ( = 1, 2,...) from the centre band. An attempt was made16 to calculate the excitation profile of multiple bands created by a PIP of a constant RF field strength, using an approximate method based on the Fourier analysis. The accuracy of the method relies partly on the linear response of the spin system, which is, unfortunately, not true in most cases except for a small angle excitation. In addition, the spins inside a magnet consitute a quantum system, which is sensitive not only to the strengths but also to the phases of the RF fields. Any classical description is doomed to failure if the quantum nature of the spin system emerges. 

In 1967, Dogonadze, Kuznetsov, and Levich began the development of a theoretical model that would account for the full quantum nature of the transferring proton [10, 18, 52, 53]. In contrast to the model based on transition state theory where the quantum properties of the proton are an ad hoc addition to the model,... 

Does T differ significantly from unity in typical electron transfer reactions It is difficult to get direct evidence for nuclear tunnelling from rate measurements except at very low temperatures in certain systems. Nuclear tunnelling is a consequence of the quantum nature of oscillators involved in the process. For the corresponding optical transfer, it is easy to see this property when one measures the temperature dependence of the intervalence band profile in a dynamically-trapped mixed-valence system. The second moment of the band,... 

While most derivations focus on the equation of motion, an equally important aspect of the MFT method is the correct representation of the quantum-mechanical initial state. It is well known that the classical limit of quantum dynamics in general is represented by an ensemble of classical orbits [23, 24, 26, 204]. Hence it is not appropriate to use a single classical trajectory, but it is necessary to average over many trajectories, the initial conditions of which are chosen to mimic the quantum nature of the initial state of the classically treated subsystem. Interestingly, it turns out that several misconceptions concerning the theory and performance of the MFT method are rooted in the assumption of a single classical trajectory. 

The applications of NN to solvent extraction, reported in section 16.4.6.2., suffer from an essential limitation in that they do not apply to processes of quantum nature therefore they are not able to describe metal complexes in extraction systems on the microscopic level. In fact, the networks can describe only the pure state of simplest quantum systems, without superposition of states. Neural networks that indirectly take into account quantum effects have already been applied to chemical problems. For example, the combination of quantum mechanical molecular electrostatic potential surfaces with neural networks makes it possible to predict the bonding energy for bioactive molecules with enzyme targets. Computational NN were employed to identify the quantum mechanical features of the... 

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