Korean Journal of Mineralogy and Petrology (광물과 암석)

The Petrological Society of Korea & The Mineralogical Society of Korea (한국암석학회 & 한국광물학회)
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First-principles Calculations of K-edge Absorption Spectra of Ca-bearing Minerals

Ca-함유 광물에 대한 제1원리 K-edge 흡수 스펙트럼 계산

  • Sanggeon Kim (Department of Geology, Kangwon National University) ;
  • Sangbo Son (Department of Geology, Kangwon National University) ;
  • Kideok D. Kwon (Department of Geology, Kangwon National University)
  • 김상건 (강원대학교 자연과학대학 지질학과) ;
  • 손상보 (강원대학교 자연과학대학 지질학과) ;
  • 권기덕 (강원대학교 자연과학대학 지질학과)
  • Received : 2024.05.07
  • Accepted : 2024.06.30
  • Published : 2024.06.30
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Abstract

X-ray absorption near-edge structure (XANES) spectroscopy can provide qualitative insights into the coordination chemistry of calcium (Ca) across a variety of geological materials. However, systematic studies on Ca K-edge XANES spectral features and the Ca coordination parameters are rare. This study investigated potential correlations between the spectral features of Ca K-edge XANES and the coordination parameters of Ca for selected Ca-bearing minerals (anorthite, aragonite, calcite, diopside, dolomite, grossular, monohydrocalcite, perovskite, and wollastonite), employing density functional theory (DFT) calculations. DFT calculations accurately reproduced the main features of their experimental Ca K-edge XANES spectra for representative silicates, carbonates, and titanates. No strong correlation was observed between XANES peak positions vs. Ca-O distances (or Ca coordination numbers). However, a significant correlation was noted between the peak intensity of post-edge peaks vs. the effective coordination number of Ca in minerals of similar chemical compositions. These results show the potential, yet limited, applicability of XANES spectra for molecular-level research of Ca-bearing geomaterials, and highlight the critical role of DFT computations in interpretating XANES spectra.

X-선 absorption near-edge structure (XANES) 분광분석은 다양한 지구물질의 칼슘(Ca)화학결합에 대한 정성적인 정보를 제공할 수 있으나, XANES 스펙트럼과 Ca 배위환경 간의 상관관계는 아직 체계적으로 규명되어 있지 않다. 이번 연구에서는 밀도범함수이론(density functional theory; DFT) 계산을 통해 대표적인 규산염(회장석, 투휘석, 그로슐라, 규회석), 탄산염(아라고나이트, 방해석, 백운석, 모노하이드로캘사이트), 티탄산염(페로브스카이트) 광물에 대한 Ca K-edge 흡수 스펙트럼과 Ca의 배위환경 사이의 상관관계를 조사하였다. DFT로 계산된 Ca K-edge 흡수 스펙트럼은 실험 XANES 스펙트럼의 주요 형태를 재현할 수 있었다. 광물의 평균 Ca-O 결합거리(또는 Ca의 배위수)와 흡수-끝(absorption edge) 피크 위치 사이에 뚜렷한 상관관계는 관찰되지 않았다. 반면에 Ca의 유효배위수(effective coordination number)가 증가할수록 post-edge 피크의 세기가 감소하는 경향이 관찰되었다. Ca의 유효배위수와 post-edge 피크의 세기 사이의 상관관계는 화학조성이 비슷한 광물에서 더 뚜렷하게 나타났다. 이번 연구결과는 Ca K-edge XANES 스펙트럼을 통해 Ca의 배위 화학의 이해가 제한적으로 가능함을 제시하며, 분광분석 스펙트럼 해석에 DFT 계산 연구의 유용성을 강조한다.

Keywords

Acknowledgement

이연구는 한국연구재단의지원(2019R1A2C2084299)을 받아 수행되었으며, KISTI 슈퍼컴퓨터 자원(KSC-2023-CRE-0070)을 일부 사용하였다.

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