Isotope quantum

Tomberli, B., Benmore, C. J., Egelstaff, P. A., Neuefeind, J., and Honkimaki, V., Isotopic quantum effects in water structure measured with high energy photon diffraction. J. Phys. - Cond. Matt. 12, 2597-2612 (2000). 

ArF laser photolyis of H2S seeded in free-jet expansion of Ar used to form Sj. Analysis of LIF spectrum Lifetimes for two vib-rotational levels of Te2(A0 ). Cross-sections for deactivation by Tej Laser emissions from different excited Tcj isotopes Quantum yields for CI2 luminescence at wavelengths 308 nm following VUV excitation in the presence of Ar, Kr, and Xe f Three bound-free transitions observed in LIF from Brj following excitation at 158 nm. Collisional transfer by SF, N2, and He t Near-dissociation behaviour of l2(B n ) tLIF-Fourier transform study of the "near-dissociation behaviour of IjfBO I). Precise value for the well depth of the X state determined... 

For those who are familiar with the statistical mechanical interpretation of entropy, which asserts that at 0 K substances are nonnally restricted to a single quantum state, and hence have zero entropy, it should be pointed out that the conventional thennodynamic zero of entropy is not quite that, since most elements and compounds are mixtures of isotopic species that in principle should separate at 0 K, but of course do not. The thennodynamic entropies reported in tables ignore the entropy of isotopic mixing, and m some cases ignore other complications as well, e.g. ortho- and para-hydrogen. 

Over the next few years, both the mid-infrared and the far-infrared spectra for Ar-HF and Ar-HCl were extended to numerous other bands and to other isotopic species (most importantly those containing deuterium). In 1992, Hutson [18, 39] combined all the available spectroscopic data to produce definitive potential energy surfaces that included both the angle dependence and the dependence on the HF/HCl monomer vibrational quantum number v... 

We further make the following tentative conjecture (probably valid only under restricted circumstances, e.g., minimal coupling between degrees of freedom) In quantum field theories, too, the YM residual fields, A and F, arise because the particle states are truncated (e.g., the proton-neutron multiplet is an isotopic doublet, without consideration of excited states). Then, it is within the truncated set that the residual fields reinstate the neglected part of the interaction. If all states were considered, then eigenstates of the form shown in Eq. (90) would be exact and there would be no need for the residual interaction negotiated by A and F. 

The full quantum mechanical study of nuclear dynamics in molecules has received considerable attention in recent years. An important example of such developments is the work carried out on the prototypical systems H3 [1-5] and its isotopic variant HD2 [5-8], Li3 [9-12], Na3 [13,14], and HO2 [15-18], In particular, for the alkali metal trimers, the possibility of a conical intersection between the two lowest doublet potential energy surfaces introduces a complication that makes their theoretical study fairly challenging. Thus, alkali metal trimers have recently emerged as ideal systems to study molecular vibronic dynamics, especially the so-called geometric phase (GP) effect [13,19,20] (often referred to as the molecular Aharonov-Bohm effect [19] or Berry s phase effect [21]) for further discussion on this topic see [22-25], and references cited therein. The same features also turn out to be present in the case of HO2, and their exact treatment assumes even further complexity [18],... 

Very early in the study of radioactivity it was deterrnined that different isotopes had different X values. Because the laws of gravity and electromagnetism were deterministic, an initial concept was that when each radioactive atom was created, its lifetime was deterrnined, but that different atoms were created having different lifetimes. Furthermore, these different lifetimes were created such that a collection of nuclei decayed in the observed manner. Later, as the probabiUstic properties of quantum mechanics came to be accepted, it was recognised that each nucleus of a given radioactive species had the same probabiUty for decay per unit time and that the randomness of the decays led to the observed decay pattern. 

Here Tq are coordinates in a reference volume Vq and r = potential energy of Ar crystals has been computed [288] as well as lattice constants, thermal expansion coefficients, and isotope effects in other Lennard-Jones solids. In Fig. 4 we show the kinetic and potential energy of an Ar crystal in the canonical ensemble versus temperature for different values of P we note that in the classical hmit (P = 1) the low temperature specific heat does not decrease to zero however, with increasing P values the quantum limit is approached. In Fig. 5 the isotope effect on the lattice constant (at / = 0) in a Lennard-Jones system with parameters suitable for Ne atoms is presented, and a comparison with experimental data is made. Please note that in a classical system no isotope effect can be observed, x "" and the deviations between simulations and experiments are mainly caused by non-optimized potential parameters. 

The nuclei of many isotopes possess an angular momentum, called spin, whose magnitude is described by the spin quantum number / (also called the nuclear spin). This quantity, which is characteristic of the nucleus, may have integral or halfvalues thus / = 0, 5, 1, f,. . . The isotopes C and 0 both have / = 0 hence, they have no magnetic properties. H, C, F, and P are important nuclei having / = 5, whereas and N have / = 1. 

Consider a reactant molecule in which one atom is replaced by its isotope, for example, protium (H) by deuterium (D) or tritium (T), C by C, etc. The only change that has been made is in the mass of the nucleus, so that to a very good approximation the electronic structures of the two molecules are the same. This means that reaction will take place on the same potential energy surface for both molecules. Nevertheless, isotopic substitution can result in a rate change as a consequence of quantum effects. A rate change resulting from an isotopic substitution is called a kinetic isotope effect. Such effects can provide valuable insights into reaction mechanism. 

Phosphorus has only one stable isotope, J P, and accordingly (p. 17) its atomic weight is known with extreme accuracy, 30.973 762(4). Sixteen radioactive isotopes are known, of which P is by far the most important il is made on the multikilogram scale by the neutron irradiation of S(n,p) or P(n,y) in a nuclear reactor, and is a pure -emitter of half life 14.26 days, 1.7()9MeV, rntan 0.69MeV. It finds extensive use in tracer and mechanistic studies. The stable isotope has a nuclear spin quantum number of and this is much used in nmr spectroscopy. Chemical shifts and coupling constants can both be used diagnostically to determine structural information. 

The isotope has a nuclear spin quantum number I and so is potentially useful in nmr experiments (receptivity to nmr detection 17 X 10 that of the proton). The resonance was first observed in 1951 but the low natural abundance i>i S(0.75%) and the quadrupolar broadening of many of the signals has so far restricted the amount of chemically significant work appearing on this rcsonance, However, more results are expected now that pulsed fourier-transform techniques have become generally available. 

Isotope Nuclear spin quantum no. I NMR frequency rel to H(SiMe4) = 100.000 Relative receptivity D ( Nuclear quadmpole moment Q (e 10-2 ... 

Receptivity D is proportional to y NKJ + 1) where y is the magnetogyric ratio, N the natural abundance of the isotope, and / the nuclear spin quantum number Dp is the receptivity relative to that of the proton taken as 1.000. 

All have zero nuclear spin except (33.8% abundance) which has a nuclear spin quantum number this isotope finds much use in nmr spectroscopy both via direct observation of the Pt resonance and even more by the observation of Pt satellites . Thus, a given nucleus coupled to Pt will be split into a doublet symmetrically placed about the central unsplit resonance arising from those species containing any of the other 5 isotopes of Pt. The relative intensity of the three resonances will be (i X 33.8) 66.2 ( x 33.8), i.e. 1 4 1. 

We often say that an electron is a spin-1/2 particle. Many nuclei also have a corresponding internal angular momentum which we refer to as nuclear spin, and we use the symbol I to represent the vector. The nuclear spin quantum number I is not restricted to the value of 1/2 it can have both integral and halfintegral values depending on the particular isotope of a particular element. All nuclei for which 7 1 also posses a nuclear quadrupole moment. It is usually given the symbol Qn and it is related to the nuclear charge density Pn(t) in much the same way as the electric quadrupole discussed earlier ... 

This morc-philosophicai view of Ihc elements has come to the rescue of chemistry as its own field, rather than simply a pari of physics, on more than one occasion. It suggests that chemistry possesses an essential philoscphlcal foundation even though It Is popularly presumed lo reduce to quantum physics and thus to be devoid of a philosophical character. In the early years of the 20th century, when Isotopes of many elements were discovered, it suddenly seemed as if the number of "elements," in the sense of simplest substances, that can be Isolated had multiplied. Some chemists believed that this proliferation would signal the demise of the periodic table, which would give way to a table of Ihe isotopes. 

The number of energy levels found to date, with the aid of the Zeeman effect and the isotope shift data, is 605 even and 586 odd levels for Pu I and 252 even and 746 odd for Pu II. The quantum number J has been determined for all these levels, the Lande g-factor for most of them, and the isotope shift for almost all of the Pu I levels and for half of those of Pu II. Over 31000 lines have been observed of which 52% have been classified as transitions between pairs of the above levels. These represent 23 distinct electron configurations. 

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