Normalized correlation function, quantum

In Equation (5), we can first notice (i) the factor 1/r6 which makes the spectral density very sensitive to the interatomic distance, and (ii) the dynamical part which is the Fourier transform of a correlation function involving the Legendre polynomial. We shall denote this Fourier transform by (co) (we shall dub this quantity "normalized spectral density"). For calculating the relevant longitudinal relaxation rate, one has to take into account the transition probabilities in the energy diagram of a two-spin system. In the expression below, the first term corresponds to the double quantum (DQ) transition, the second term to single quantum (IQ) transitions and the third term to the zero quantum (ZQ) transition. 

The calculated ln(j2(f)<2(0)) for the first three quantum levels for the CH3I case is shown in Fig. 12. The overtone normal coordinate time correlation function, Q(t)Q(0)), is obtained from the frequency-modulation time corre-... 

These normal modes evolve independently of each other. Their classical equations of motion are Uk = —co Uk, whose general solution is given by Eqs (6.81). This bath is assumed to remain in thermal equilibrimn at all times, implying the phase space probability distribution (6.77), the thermal averages (6.78), and equilibrium time correlation functions such as (6.82). The quantum analogs of these relationships were discussed in Section 6.5.3. 

In the case of the quantum description of the field, the first- and second-order correlation functions are defined in terms of the normally ordered field operators E(+) and E as... 

We concentrate on the role of quantum interference in the correlation of photons emitted from a coherently driven V-type atom, recently analyzed by Swain et al. [58]. We calculate the normalized second-order two-time correlation function g (R, t R, t + x) for the fluorescent field emitted from a three-level V-type atom driven by a coherent laser field coupled to both atomic transitions. The fluorescence field is observed by a single detector located at a point R = RR, where R is the unit vector in the direction of the observation. 

It should be noted that the imaginary time correlation function in Eq. (2.4) provides a measure of the localization of quantum particles in condensed media [17-19,52]. From this point on, the notation denotes an averaging by integrating some centroid-dependent function over the centroid position q weighted by the normalized centroid density p q ) Z. An alternative method for defining the correlation function... 

In the CMD correlation function [Eq. (3.10)], the notation )p means that the exact (normalized) phase-space centroid density is used to average the initial conditions of the centroid trajectories in the usual classical sense. Once the centroid correlation function C (f) in Eq. (3.10) is calculated, the exact quantum position correlation function C(t) can be estimated through a Fourier transform relationship similar to Eq. (3.8),... 

MaxweU-Boltzmaim particles are distinguishable, and a partition function, or distribution, of these particles can be derived from classical considerations. Real systems exist in which individual particles ate indistinguishable. Eor example, individual electrons in a soHd metal do not maintain positional proximity to specific atoms. These electrons obey Eermi-Ditac statistics (133). In contrast, the quantum effects observed for most normal gases can be correlated with Bose-Einstein statistics (117). The approach to statistical thermodynamics described thus far is referred to as wave mechanics. An equivalent quantum theory is referred to as matrix mechanics (134—136). 

In standard quantum-mechanical molecular structure calculations, we normally work with a set of nuclear-centred atomic orbitals Xi< Xi CTOs are a good choice for the if only because of the ease of integral evaluation. Procedures such as HF-LCAO then express the molecular electronic wavefunction in terms of these basis functions and at first sight the resulting HF-LCAO orbitals are delocalized over regions of molecules. It is often thought desirable to have a simple ab initio method that can correlate with chemical concepts such as bonds, lone pairs and inner shells. A theorem due to Fock (1930) enables one to transform the HF-LCAOs into localized orbitals that often have the desired spatial properties. 

It is not possible to use normal AO basis sets in relativistic calculations The relativistic contraction of the inner shells makes it necessary to design new basis sets to account for this effect. Specially designed basis sets have therefore been constructed using the DKH Flamiltonian. These basis sets are of the atomic natural orbital (ANO) type and are constructed such that semi-core electrons can also be correlated. They have been given the name ANO-RCC (relativistic with core correlation) and cover all atoms of the Periodic Table.36-38 They have been used in most applications presented in this review. ANO-RCC are all-electron basis sets. Deep core orbitals are described by a minimal basis set and are kept frozen in the wave function calculations. The extra cost compared with using effective core potentials (ECPs) is therefore limited. ECPs, however, have been used in some studies, and more details will be given in connection with the specific application. The ANO-RCC basis sets can be downloaded from the home page of the MOLCAS quantum chemistry software (http //www.teokem.lu.se/molcas). 

Odelius and co-workers reported some time ago an important study involving a combined quantum chemistry and molecular dynamics (MD) simulation of the ZFS fluctuations in aqueous Ni(II) (128). The ab initio calculations for hexa-aquo Ni(II) complex were used to generate an expression for the ZFS as a function of the distortions of the idealized 7), symmetry of the complex along the normal modes of Eg and T2s symmetries. An MD simulation provided a 200 ps trajectory of motion of a system consisting of a Ni(II) ion and 255 water molecules, which was analyzed in terms of the structure and dynamics of the first solvation shell of the ion. The fluctuations of the structure could be converted in the time variation of the ZFS. The distribution of eigenvalues of ZFS tensor was found to be consistent with the rhombic, rather than axial, symmetry of the tensor, which prompted the development of the analytical theory mentioned above (89). The time-correlation... 

Wave functions (13) apply to any pair of coupled centrosymmetric protons, irrespective of the distance and of the magnitude of the coupling term. Quantum correlation arises exclusively from normal coordinates representing dynamics of indistinguishable particles. It has been proposed [Keen 2003] that quantum entanglement could be due to the overlap integral of the one-particle wave functions >Pi, (a o , ) for protons ... 

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