Hamiltonian Density

In order to interpret the above results, consider the expectation value of the total energy density in the vacuum state, i.e., of the hamiltonian density, Eq. (10-12). There is a contribution J u(x)Al(x) from the external field and a contribution m<0 j (a ) 0)ln 4 (a ) from the induced current, hence to lowest order... 

Similar considerations lead to the transformation properties of the one-photon states and of the photon in -operators which create photons of definite momentum and helicity. We shall, however, omit them here. Suffice it to remark that the above transformation properties imply that the interaction hamiltonian density Jf mAz) = transforms like a scalar under restricted inhomogeneous Lorentz transformation... 

The interaction hamiltonian density jin A x) transforms like a scalar ... 

We now turn to the potential (4) for nonequilibrium phase transition. We separate the Hamiltonian density H into a quadratic part Ho and a perturbation part Hp ... 

Numerical solutions of the Schrodinger equation can be obtained within several degrees of approximation, for almost any system, using its exact Hamiltonian. Density functional theory has proven to be one of the most effective techniques, because it provides significantly greater accuracy than Hartree-Fock theory with just a modest increase in computational cost.io> 3-45 The accuracy of DFT method is comparable, and even greater than other much more expensive theoretical methods that also include electron correlation such as second and higher order perturbation theory. 

Alternatively, the Hamiltonian for fhe radiation field in multipolar formalism may be written explicitly in terms of fhe Maxwell field operators. From the second term of Eq. (2), fhe Hamiltonian density for the electromagnetic field is... 

For the following it is furthermore crucial that normal order in (8, 9) refers to the creation and annihilation operators of the (renormalized) asymptotic fields of the homogeneous system, i.e. with zero external four-potential A, so that this intrinsic Hamiltonian density is independent of the external four-potential. 

Thus we have provided justification elsewhere for the view that the dynamical law of Schrodinger s mechanics is the equality of the mean values of the Hamiltonian density and the energy density ... 

Similarly to the Lagrangian formulation the Hamiltonian for continuous systems described by fields is given as the spatial integral over the Hamiltonian density H,... 

Since the Hamiltonian is the space integral of the Hamiltonian density... 

A differential equation for the time evolution of the density operator may be derived by taking the time derivative of equation (Al.6.49) and using the TDSE to replace the time derivative of the wavefiinction with the Hamiltonian operating on the wavefiinction. The result is called the Liouville equation, that is. 

A stationary ensemble density distribution is constrained to be a functional of the constants of motion (globally conserved quantities). In particular, a simple choice is pip, q) = p (W (p, q)), where p (W) is some fiinctional (fiinction of a fiinction) of W. Any such fiinctional has a vanishing Poisson bracket (or a connnutator) with Wand is thus a stationary distribution. Its dependence on (p, q) through Hip, q) = E is expected to be reasonably smooth. Quanttun mechanically, p (W) is die density operator which has some fiinctional dependence on the Hamiltonian Wdepending on the ensemble. It is also nonnalized Trp = 1. The density matrix is the matrix representation of the density operator in some chosen representation of a complete orthononnal set of states. If the complete orthononnal set of eigenstates of die Hamiltonian is known ... 

The above derivation leads to the identification of the canonical ensemble density distribution. More generally, consider a system with volume V andA particles of type A, particles of type B, etc., such that N = Nj + Ag +. . ., and let the system be in themial equilibrium with a much larger heat reservoir at temperature T. Then if fis tlie system Hamiltonian, the canonical distribution is (quantum mechanically)... 

The usual context for linear response theory is that the system is prepared in the infinite past, —> -x, to be in equilibrium witii Hamiltonian H and then is turned on. This means that pit ) is given by the canonical density matrix... 

The hypersurface fomied from variations in the system s coordinates and momenta at//(p, q) = /Tis the microcanonical system s phase space, which, for a Hamiltonian with 3n coordinates, has a dimension of 6n -1. The assumption that the system s states are populated statistically means that the population density over the whole surface of the phase space is unifomi. Thus, the ratio of molecules at the dividing surface to the total molecules [dA(qi, p )/A]... 

The basic equation [8] is tlie equation of motion for the density matrix, p, given in equation (B2.4.25), in which H is the Hamiltonian. 

It is more convenient to re-express this equation in Liouville space [8, 9 and 10], in which the density matrix becomes a vector, and the commutator with the Hamiltonian becomes the Liouville superoperator. In tliis fomuilation, the lines in the spectrum are some of the elements of the density matrix vector, and what happens to them is described by the superoperator matrix, equation (B2.4.25) becomes (B2.4.26). 

A simple, non-selective pulse starts the experiment. This rotates the equilibrium z magnetization onto the v axis. Note that neither the equilibrium state nor the effect of the pulse depend on the dynamics or the details of the spin Hamiltonian (chemical shifts and coupling constants). The equilibrium density matrix is proportional to F. After the pulse the density matrix is therefore given by and it will evolve as in equation (B2.4.27). If (B2.4.28) is substituted into (B2.4.30), the NMR signal as a fimction of time t, is given by (B2.4.32). In this equation there is a distinction between the sum of the operators weighted by the equilibrium populations, F, from the unweighted sum, 7. The detector sees each spin (but not each coherence ) equally well. 

In the usual preparatioii-evohition-detection paradigm, neither the preparation nor the detection depend on the details of the Hamiltonian, except hi special cases. Starthig from equilibrium, a hard pulse gives a density matrix that is just proportional to F. The detector picks up only the unweighted sum of the spin operators,... 

The current iteration s density is used in the KS equations to detennine tlie Hamiltonian -1/2V + V(r)... 

Continuum models go one step frirtlier and drop the notion of particles altogether. Two classes of models shall be discussed field theoretical models that describe the equilibrium properties in temis of spatially varying fields of mesoscopic quantities (e.g., density or composition of a mixture) and effective interface models that describe the state of the system only in temis of the position of mterfaces. Sometimes these models can be derived from a mesoscopic model (e.g., the Edwards Hamiltonian for polymeric systems) but often the Hamiltonians are based on general symmetry considerations (e.g., Landau-Ginzburg models). These models are well suited to examine the generic universal features of mesoscopic behaviour. 

A particularly convenient notation for trajectory bundle system can be introduced by using the classical Liouville equation which describes an ensemble of Hamiltonian trajectories by a phase space density / = f q, q, t). In textbooks of classical mechanics, e.g. [12], it is shown that Liouville s equation... 

The so-ealled Hohenberg-Kohn theorem states that the ground-state eleetron density p(r) deseribing an N-eleetron system uniquely determines the potential V(r) in the Hamiltonian... 

The most common way of including relativistic effects in a calculation is by using relativisticly parameterized effective core potentials (RECP). These core potentials are included in the calculation as an additional term in the Hamiltonian. Core potentials must be used with the valence basis set that was created for use with that particular core potential. Core potentials are created by htting a potential function to the electron density distribution from an accurate relativistic calculation for the atom. A calculation using core potentials does not have any relativistic terms, but the effect of relativity on the core electrons is included. 

A number of types of calculations can be performed. These include optimization of geometry, transition structure optimization, frequency calculation, and IRC calculation. It is also possible to compute electronic excited states using the TDDFT method. Solvation effects can be included using the COSMO method. Electric fields and point charges may be included in the calculation. Relativistic density functional calculations can be run using the ZORA method or the Pauli Hamiltonian. The program authors recommend using the ZORA method. 

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