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The Analytic Gradient with a Reduced Molecular Orbital Space for the Equation-of-Motion Coupled-Cluster Theory: Systematic Study of the Magnitudes and Trends in Simple Molecules
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  • The Analytic Gradient with a Reduced Molecular Orbital Space for the Equation-of-Motion Coupled-Cluster Theory: Systematic Study of the Magnitudes and Trends in Simple Molecules
  • The Analytic Gradient with a Reduced Molecular Orbital Space for the Equation-of-Motion Coupled-Cluster Theory: Systematic Study of the Magnitudes and Trends in Simple Molecules
저자명
백경기,전상일,Baek. Gyeong Gi,Jeon. Sang Il
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2000년|21권 7호|pp.720-726 (7 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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기타
이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
서지반출

기타언어초록

The analytic gradient method for the equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) energy has been extended to employ a reduced molecular orbital (MO) space. Not only the innermost core MOs but also some of the outermost virtua l MOs can be dropped in the reduced MO space, and a substantial amount of computation time can be reduced without deteriorating the results. In order to study the magnitudes and trends of the effects of the dropped MOs, the geometries and vibrational properties of the ground and excited states of BF, CO, CN, N2, AlCl, SiS, P2, BCl, AIF, CS, SiO, PN and GeSe are calculated with different sizes of molecular orbital space. The 6-31 G* and the aug-cc-pVTZ basis sets are employed for all molecules except GeSc for which the 6-311 G* and the TZV+f basis sets are used. It is shown that the magnitudes of the drop-MO effects are about $0.005AA$ in bond lengths and about 1% on harmonic frequencies and IR intensities provided that the dropped MOs correspond to (1s), (1s,2s,2p), an (1s,2s,2p,3s,3p) atomic orbitals of the first, the second, and the third row atoms, respectively. The geometries and vibrational properties of the first and the second excited states of HCN and HNC are calculated by using a drastically reduced virtual MO space as well as with the well defined frozen core MO space. The results suggest the possibility of using a very smalI MO space for qualitative study of valence excited states.