• Bulletin of the Korean Chemical Society
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• 제6권5호
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• pp.309-311
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• 1985

When a molecule is perturbed by an external field, the perturbed moecue can be described as a doubly perturbed system. Hartree-Fock operator in the absence of the field is the zeroth order Hamiltonian, and a correlation operator and the external field operator are perturbations. The effective Hamiltonian, which is a projection of the total Hamiltonian onto a small finite subspace (usually a valence space), has been formally derived. The influence of the external field to the molecular Hamiltonian itself has been examined within an effective Hamiltonian framework. The first order effective expectation values, for instance electromagnetic transition amplitudes, between valence states are found to be easily calculated - by simply taking matrix elements of the effective external field operator. Implications of the terms in perturbation expansion are discussed.

• Bulletin of the Korean Chemical Society
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• 제6권3호
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• pp.168-170
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• 1985

The pairing properties of electronic structure are investigated from ab initioists' point of view. Numerical results of exact ab initio effective valence shell Hamiltonian are compared with simple semiempirical Hamiltonian calculations. In the oxygen atom case it was found that effective three-electron interaction terms break the similarity between electron-states and hole-states. With the trans-butadiene as an example the pairing theorem was studied. Even for alternant hydrocarbons, the deviation from the pairing was found to be enormous. The pairing theorem, which is usually stated for semiempirical Hamiltonians, is not valid when the exact effective Hamiltonian is considered. The present study indicates that comparisons between the pairing theorem of semiempirical methods and ab initio effective Hamiltonian give important information on the accuracy of semiempirical methods.

• Bulletin of the Korean Chemical Society
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• 제11권1호
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• pp.34-41
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• 1990

The second order ab initio effective valence shell Hamiltonian is calculated for the valence state potential energy curves of NH and $NH^+$. From the potential energy curves various spectroscopic constants of valence states are determined. The results are in good agreement with experiments and configuration interaction calculations. They show the composite picture of potential energy curves and also indicate that the second order effective Hamiltonian theory is adequate for describing various valence states of a molecule and its ions simultaneously.

• Bulletin of the Korean Chemical Society
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• 제24권6호
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• pp.723-727
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• 2003

Recently the ab initio effective valence shell Hamiltonian method $H^v$ has been extended to treat spin-orbit coupling in atoms or molecules. The quasidegenerate many-body perturbation theory based $H^v$ method has an advantage of determining the spin-orbit coupling energies of all valence states for both the neutral species and its ions with a similar accuracy from a single computation of the effective spin-orbit coupling operator. The new spin-orbit $H^v$ method is applied to calculating the fine structure splittings of the valence states of SiH, $SiH^+$, and $SiH^{2+}$ not only to assess the accuracy of the method but also to investigate the spin-orbit interaction of highly excited states of SiH species. The computed spin-orbit splittings for ground states are in good agreement with experiment and the few available ab initio computations. The ordering of fine structure levels of the bound and quasi-bound spin-orbit coupled valence states of SiH and its ions, for which neither experiment nor theory is available, is predicted.

• Bulletin of the Korean Chemical Society
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• 제9권2호
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• pp.101-105
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• 1988

The ab initio effective valence shell Hamiltonian method, based on quasidegenerate many-body perturbation theory, is generalized to calculate molecular properties as well as the valence state energies which have previously been determined for atoms and small molecules. The procedure requires the evaluation of effective operator for each molecular property. Effective operators are perturbatively expanded in powers of correlation and contain contributions from excitations outside of the multireference valence space. To demonstrate the validity of this method, calculations for dipole moments of several low lying valence states of OH, $OH^+$, and $OH^-$ to first order in the correlations have been performed and compared with configuration interaction calculations.

• Nuclear Engineering and Technology
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• 제1권2호
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• pp.103-106
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• 1969

gauge독립한 새로운 unitary변환을 도입함으로서 진동하고 있는 전장안에서의 spin 1/2 가전입자의 운동을 기술하는데 적합한 Dirac 방정식의 표시가 도출되고 있다. 이 새로운 표시에 있어서 potentials를 포함하지 않은 유효 Hamiltonian은 그 비상대론적 근거에서 새로운 특성을 나타내는 사실을 보여주고 있다.

• Bulletin of the Korean Chemical Society
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• 제15권8호
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• pp.694-697
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• 1994

• Bulletin of the Korean Chemical Society
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• 제13권6호
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• pp.699-701
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• 1992

• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.985-993
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• 1998

The second order effective valence shell Hamiltonian ($H^v$), which is based on quasidegencrate many-body perturbation theory, is applied to determining the potential energy surfaces and the dipole moment functions of the various valence states of $NH_2$. The $H^v$ calculated values are found to be in good agreement with those of other ab initio calculations or experiments. It signifies the fact that the $H^v$ is a good ab initio method to describe the energies and properties of various valence states with a same chemical accuracy. Furthermore, it is shown that the lowest (second order for energy and the first order for property) order $H^v$ method is very accurate for small molecules like $NH_2$ and the matrix elements of Hv which are computed only once are all we need to accurately describe all the valence states simultaneously.

• Bulletin of the Korean Chemical Society
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• 제13권4호
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• pp.429-440
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• 1992

The second order ab initio effective valence shall Hamiltonian ($H^v$) which is based on quasidegenerate many-body perturbation theory is applied to the SiH, PH, and their positive ions. A singie Hv computation for the neutral molecule is used for a whole set of valence states of a molecule and its ion simultaneously. The low-lying valence state potential energy curves of SiH, PH and their positive ions are computed. And various spectroscopic constants of the low-lying bound valence states are determined from the potential energy curves. The $H^v$ results are found to be in good agreement with other theoretical and experimental data.