Geometry optimization and force constant calculations with two-component spinor formalism and relativistic effective core potentials이성분 스피너와 상대론적 유효중심포텐셜을 이용한 구조 최적화 방법과 힘상수 계산

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A geometry optimization and force constant calculation code using analytic gradient has been implemented to a two-component Kramers`` restricted Hartree-Fock(KRHF) method for the polyatomic molecules with closed-shell configurations. The KRHF method utilizes the relativistic effective core potentials(RECPs) with effective one-electron spin-orbit operators at the Hartree-Fock level in a variational manner and produces molecular spinors obeying the double group symmetry. Electron correlations are treated at the coupled-cluster level of theory with and without spin-orbit interactions. Spin-orbit effects on many molecules containing sixth-row p-block elements(Tl-Rn), transactinide d-block elements(Rf, Db, and Sg), and p-block elements(Element 113, 117, and 118) are evaluated and discussed. In the present work, the spin-orbit effect is defined by the difference between the results of one- and two-component RECPs. Particular attention is paid to molecular geometries, harmonic vibrational frequencies, and dissociation energies for the ground states of the molecules. Comparisons with available all-electron Dirac-Fock results indicate that the two-component approaches are very promising tools in the calculations for the heavy atom systems. In particular, the straightforward two-component coupled-cluster calculations are useful when the size-extensive property is necessary to determine accurate molecular properties as in the case like $Rn_2$ and when the spin-orbit effects become very large as in the cases like (113)H and (117)H. In the calculations for the molecules containing sixth-row p-block and transactinide d-block elements, spin-orbit effects on the geometries and harmonic vibrational frequencies are very small. Only the dissociation energies are significantly changed by incorporating spin-orbit interactions. However, for the molecules containing transactinide p-block elements, considering spin-orbit interactions in the calculations is necessary to obtain reliable...
Advisors
Lee, Yoon-Supresearcher이윤섭researcher
Description
한국과학기술원 : 화학과,
Publisher
한국과학기술원
Issue Date
1999
Identifier
156120/325007 / 000965421
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 1999.8, [ v, 100 p. ]

Keywords

Effective core potential; Geometry optimization; Spin-orbit effect; Superheavy element; Relativistic effect; 상대론적 효과; 유효중심포텐셜; 구조 최적화; 스핀-궤도 효과; 초중량원소

URI
http://hdl.handle.net/10203/31517
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=156120&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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