Hamiltonian operators quantum mechanics

No distinction in notation will be made betivecm the classical Hamiltonian the quantum-mechanical Hamiltonian operator H, or, later, the... 

Up until now, little has been said about time. In classical mechanics, complete knowledge about the system at any time t suffices to predict with absolute certainty the properties of the system at any other time t. The situation is quite different in quantum mechanics, however, as it is not possible to know everything about the system at any time t. Nevertheless, the temporal behavior of a quantum-mechanical system evolves in a well defined way drat depends on the Hamiltonian operator and the wavefiinction T" according to the last postulate... 

Applications of quantum mechanics to chemistry invariably deal with systems (atoms and molecules) that contain more than one particle. Apart from the hydrogen atom, the stationary-state energies caimot be calculated exactly, and compromises must be made in order to estimate them. Perhaps the most useful and widely used approximation in chemistry is the independent-particle approximation, which can take several fomis. Conuiion to all of these is the assumption that the Hamiltonian operator for a system consisting of n particles is approximated by tlie sum... 

At this point the reader may feel that we have done little in the way of explaining molecular synnnetry. All we have done is to state basic results, nonnally treated in introductory courses on quantum mechanics, connected with the fact that it is possible to find a complete set of simultaneous eigenfiinctions for two or more commuting operators. However, as we shall see in section Al.4.3.2. the fact that the molecular Hamiltonian //coimmites with and F is intimately coimected to the fact that //commutes with (or, equivalently, is invariant to) any rotation of the molecule about a space-fixed axis passing tlirough the centre of mass of the molecule. As stated above, an operation that leaves the Hamiltonian invariant is a symmetry operation of the Hamiltonian. The infinite set of all possible rotations of the... 

Traditionally, for molecular systems, one proceeds by considering the electronic Hamiltonian which consists of the quantum mechanical operators for the kinetic energy of the electrons, their mutual Coulombic repulsions, and... 

Hamiltonian quantum mechanical operator for energy, hard sphere assumption that atoms are like hard billiard balls, which is implemented by having an infinite potential inside the sphere radius and zero potential outside the radius Hartree atomic unit of energy... 

The path-integral quantum mechanics relies on the basic relation for the evolution operator of the particle with the time-independent Hamiltonian H x, p) = -i- V(x) [Feynman and... 

The Hamiltonian operator is the quantum-mechanical analogue of the energy, and we say that the allowed values of the energy, the , above, are the eigenvalues... 

Where // is the complete Hamiltonian operator for the unperturbed system and the usual quantum-mechanical integrals over all space are indicated. 

As we know the quantum mechanical Hamiltonian operator determines the properties of a spin system as follows,... 

The treatment developed here is based on the density matrix of quantum mechanics and extends previous work using wavefunctions.(42 5) The density matrix approach treats all energetically accessible electronic states in the same fashion, and naturally leads to average effective potentials which have been shown to give accurate results for electronically diabatic collisions. 19) The approach is taken here for systems where the dynamics can be described by a Hamiltonian operator, as it is possible for isolated molecules or in models where environmental effects can be represented by terms in an effective Hamiltonian. 

The variational theorem which has been initially proved in 1907 (24), before the birthday of the Quantum Mechanics, has given rise to a method widely employed in Qnantnm calculations. The finite-field method, developed by Cohen andRoothan (25), is coimected to this method. The Stark Hamiltonian —fi.S explicitly appears in the Fock monoelectronic operator. The polarizability is derived from the second derivative of the energy with respect to the electric field. The finite-field method has been developed at the SCF and Cl levels but the difficulty of such a method is the well known loss in the numerical precision in the limit of small or strong fields. The latter case poses several interconnected problems in the calculation of polarizability at a given order, n ... 

The appearance of the Hamiltonian operator in equation (3.55) as stipulated by postulate 5 gives that operator a special status in quantum mechanics. Knowledge of the eigenfunctions and eigenvalues of the Hamiltonian operator for a given system is sufficient to determine the stationary states of the system and the expectation values of any other dynamical variables. 

Accordingly, the quantum-mechanical Hamiltonian operator H for this system is proportional to the square of the angular momentum operator U-... 

In order to apply quantum-mechanical theory to the hydrogen atom, we first need to find the appropriate Hamiltonian operator and Schrodinger equation. As preparation for establishing the Hamiltonian operator, we consider a classical system of two interacting point particles with masses mi and m2 and instantaneous positions ri and V2 as shown in Figure 6.1. In terms of their cartesian components, these position vectors are... 

The quantum-mechanical Hamiltonian operator H is obtained by replacing and p p in equation (6.8) by the operators and respec-... 

If we replace the z-component of the classical angular momentum in equation (6.87) by its quantum-mechanical operator, then the Hamiltonian operator Hb for the hydrogen-like atom in a magnetic field B becomes... 

A theory for nonequilibrium quantum statistical mechanics can be developed using a time-dependent, Hermitian, Hamiltonian operator Hit). In the quantum case it is the wave functions [/ that are the microstates analogous to a point in phase space. The complex conjugate / plays the role of the conjugate point in phase space, since, according to Schrodinger, it has equal and opposite time derivative to v /. 

In the quantum mechanical applications of the two-body problem, the classical energy of the system becomes the Hamiltonian operator The conversion... 

The Hamiltonian models are broadly variable. Even for an isolated molecule, it is necessary to make models for the Hamiltonian - the Hamiltonian is the operator whose solutions give both the static energy and the dynamical behavior of quantum mechanical systems. In the simplest form of quantum mechanics, the Hamiltonian is the sum of kinetic and potential energies, and, in the Cartesian coordinates that are used, the Hamiltonian form is written as... 

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