Relativistic mass-velocity operator

Perhaps the simplest and most cost-effective way of treating relativistic contributions in an all-electron framework is the first-order perturbation theory of the one-electron Darwin and mass-velocity operators [46, 47]. For variational wavefunctions, these contributions can be evaluated very efficiently as expectation values of one-electron operators. 

It comprises the non-relativistic Hamiltonian of the form pf/2me + V and the relativistic correction terms, such as the mass-velocity operator —pf/8m c2, the Darwin term proportional to Pi E and the spin-orbit coupling term proportional... 

Another method, devised by Cohen et al. to determine oxygen-rate gas collision parameters is to define an effective spin-orbit operator that includes r dependence, Zeff/r3, where the value of Zeff is adjusted to match experimental data (76). Langhoff has compared this technique with all-electron calculations using the full microscopic spin-orbit Hamiltonian for the rare-gas-oxide potential curves and found very good agreement (77). This operator has also been employed in REP calculations on Si (73), UF6 (78), U02+ and Th02 (79), and UF5 (80). The REPs employed in these calculations are based on Cowen-Griffin atomic orbitals, which include the relativistic mass-velocity and Darwin effects but do not include spin-orbit effects. Wadt (73), has made comparisons with calculations on Si by Stevens and Krauss (81), who employed the ab initio REP-based spin-orbit operator of Ermler et al. (35). 

Here we see a relativistic correction to the kinetic energy, which is commonly called the mass-velocity operator, and a relativistic correction to the potential. The latter term reduces using the equivalent of (4.14) to... 

It is clear that this approach of successive transformations in the expansion parameter 1/c yields operators that involve higher and higher powers of p the commutator series is in fact a series in p/mc. Powers of the momentum operator higher than 2 are not bounded, and when operating on the potential V produce highly singular operators. This makes it problematic to use any but the lowest-order terms in a calculation, and since the mass-velocity operator is unbounded from below, this form of the relativistic corrections must be used in perturbation theory only. 

The first of the relativistic correction terms is called the mass-velocity operator. If we expand the square root operator in the classical relativistic Hamiltonian for a free particle, we find... 

In M0ller-Plesset theory, first-order perturbation theory does not improve on the HF energy because the zeroth-order Hamiltonian is not itself the HF Hamiltonian. However, first-order perturbation theory can be useful for estimating energetic effects associated with operators that extend the HF Hamiltonian. Typical examples of such terms include the mass-velocity and one-electron Darwin corrections that arise in relativistic quantum mechanics. It is fairly difficult to self-consistently optimize wavefunctions for systems where these tenns are explicitly included in the Hamiltonian, but an estimate of their energetic contributions may be had from simple first-order perturbation theory, since that energy is computed simply by taking the expectation values of the operators over the much more easily obtained HF wave functions. 

The first two terms, the mass-velocity and the Darwin operators, are called scalar relativistic terms since they do not involve the electron spin. They are given by... 

The so-called mass-velocity term Hmv /which represents the first order (in a ) relativistic correction to the non-relativistic kinetic energy operator... 

Spin-orbit (SO) coupling corrections were calculated for the Pt atom since the relativistic effects are essential for species containing heavy elements. Other scalar relativistic corrections like the Darwin and mass-velocity terms are supposed to be implicitly included in (quasi)relativistic pseudopotentials because they mostly affect the core region of the considered heavy element. Their secondary influence can be seen in the contraction of the outer s-orbitals and the expansion of the d-orbitals. This is considered in the construction of the pseudoorbitals. The effective SO operator can be written within pseudopotential (PS) treatment in the form71 75... 

The non-relativistic PolMe (9) and quasirelativistic NpPolMe (10) basis sets were used in calculations reported in this paper. The size of the [uncontractd/contracted] sets for B, Cu, Ag, and Au is [10.6.4./5.3.2], [16.12.6.4/9.7.3.2], [19.15.9.4/11.9.5.2], and [21.17.11.9/13.11.7.4], respectively. The PolMe basis sets were systematically generated for use in non-relativistic SCF and correlated calculations of electric properties (10, 21). They also proved to be successful in calculations of IP s and EA s (8, 22). Nonrelativistic PolMe basis sets can be used in quasirelativistic calculations in which the Mass-Velocity and Darwin (MVD) terms are considered (23). This follows from the fact that in the MVD approximation one uses the approximate relativistic hamiltonian as an external perturbation with the nonrelativistic wave function as a reference. At the SCF and CASSCF levels one can obtain the MVD quasi-relativistic correction as an expectation value of the MVD operator. In perturbative CASPT2 and CC methods one needs to use the MVD operator as an external perturbation either within the finite field approach or by the analytical derivative schems. The first approach leads to certain numerical accuracy problems. 

The method works as follows. The mass velocity, Darwin and spin-orbit coupling operators are applied as a perturbation on the non-relativistic molecular wave-functions. The redistribution of charge is then used to compute revised Coulomb and exchange potentials. The corrections to the non-relativistic potentials are then included as part of the relativistic perturbation. This correction is split into a core correction, and a valence electron correction. The former is taken from atomic calculations, and a frozen core approximation is applied, while the latter is determined self-consistently. In this way the valence electrons are subject to the direct influence of the relativistic Hamiltonian and the indirect effects arising from the potential correction terms, which of course mainly arise from the core contraction. 

The velocity operator is usually defined as the time-derivative of the position operator. In nonrelativistic quantum mechanics, the velocity is equal to (mass times) momentum and hence a constant of motion - in agreement with Newton s second law which characterizes the free motion by a constant velocity. In relativistic quantum mechanics, however, we find... 

This method was then applied to the hydrogen halides in order to estimate relativistic contributions to the EFG. The mass-velocity and Darwin terms were hereby employed as relativistic operators in combination with a many-body correlation treatment. From the results in... 

Other relativistic corrections, such as the mass-velocity and Darwin terms, affect the wave function but do not lead to operators associated with molecular... 

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