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Nuclear Quantum Effects in the Phase Transitions of Hydrogen-Bonded Systems
Nuclear Quantum Effects in the Phase Transitions of Hydrogen-Bonded Systems
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20250211152019
- ISBN
- 9798384463405
- DDC
- 542
- 저자명
- Yang, Bingjia.
- 서명/저자
- Nuclear Quantum Effects in the Phase Transitions of Hydrogen-Bonded Systems
- 발행사항
- [Sl] : Princeton University, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 94 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-04, Section: B.
- 주기사항
- Advisor: Car, Roberto.
- 학위논문주기
- Thesis (Ph.D.)--Princeton University, 2024.
- 초록/해제
- 요약The nuclear quantum effects (NQEs) in several hydrogen-bonded materials, including potassium dihydrogen phosphate (KDP), high-pressure phases of ice, ice Ih, and liquid water, are studied using all-atom path integral molecular dynamics (PIMD) simulations. As a systematic approximation to the quantum statistical mechanics, PIMD allows modeling isotope effects, a manifestation of NQEs that experiments can directly probe. Our PIMD simulations are based on neural network atomistic models trained on data provided by approximated density functional theory. In our studies, the atomistic models inherit errors in the adopted functional approximation, which overestimates the strength of hydrogen bonds.For KDP, the error from functional approximation excessively destabilizes the ferroelectric state. We circumvent this difficulty by empirically adjusting the spring constant used in PIMD simulations to match the average off-center bond displacements observed in neutron diffraction. Then, our simulations predict deuteration effects on the lattice structure, the magnitude of polarization, and the transition temperature, all in good agreement with experiments. We further show that these effects derive from quantum dipolar defects, with unbalanced donor and acceptor hydrogen bonds, that are removed by deuteration. For high-pressure phases of ice, without an empirical fix, our PIMD simulations recover the deuteration effects that shift the pressure required for the ice VIIIVII phase transition by roughly 10GPa.For both KDP and high-pressure ices, our simulations reveal the critical role of hydrogen-bond disordering and the accompanying local violations of the long-range order. Protons favor such violations more than deuterons, leading to pronounced isotope effects. In the case of the liquid water to ice Ih phase transition, we calculated the quantum correction to free energy differences using quantum thermodynamic integration. The predicted NQEs stabilize the solid phase instead of the liquid phase. The contradiction to experiments originates from the error in the adopted functional approximation. The finding underscores the possibility that the error in hydrogen-bond strength can lead to incorrect qualitative descriptions of weak NQEs.The methodology and physical insights presented in this study can be applied to investigating other hydrogen-bonded materials, preferably those known to exhibit strong isotope effects in experiments.
- 일반주제명
- Computational chemistry
- 일반주제명
- Computational physics
- 일반주제명
- Quantum physics
- 일반주제명
- Physical chemistry
- 일반주제명
- Nuclear chemistry
- 키워드
- Deep learning
- 키워드
- Ferroelectrics
- 키워드
- Phase transition
- 기타저자
- Princeton University Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-04B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
008250123s2024 us c eng d■001000017162499
■00520250211152019
■006m o d
■007cr#unu||||||||
■020 ▼a9798384463405
■035 ▼a(MiAaPQ)AAI31332115
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a542
■1001 ▼aYang, Bingjia.
■24510▼aNuclear Quantum Effects in the Phase Transitions of Hydrogen-Bonded Systems
■260 ▼a[Sl]▼bPrinceton University▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a94 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-04, Section: B.
■500 ▼aAdvisor: Car, Roberto.
■5021 ▼aThesis (Ph.D.)--Princeton University, 2024.
■520 ▼aThe nuclear quantum effects (NQEs) in several hydrogen-bonded materials, including potassium dihydrogen phosphate (KDP), high-pressure phases of ice, ice Ih, and liquid water, are studied using all-atom path integral molecular dynamics (PIMD) simulations. As a systematic approximation to the quantum statistical mechanics, PIMD allows modeling isotope effects, a manifestation of NQEs that experiments can directly probe. Our PIMD simulations are based on neural network atomistic models trained on data provided by approximated density functional theory. In our studies, the atomistic models inherit errors in the adopted functional approximation, which overestimates the strength of hydrogen bonds.For KDP, the error from functional approximation excessively destabilizes the ferroelectric state. We circumvent this difficulty by empirically adjusting the spring constant used in PIMD simulations to match the average off-center bond displacements observed in neutron diffraction. Then, our simulations predict deuteration effects on the lattice structure, the magnitude of polarization, and the transition temperature, all in good agreement with experiments. We further show that these effects derive from quantum dipolar defects, with unbalanced donor and acceptor hydrogen bonds, that are removed by deuteration. For high-pressure phases of ice, without an empirical fix, our PIMD simulations recover the deuteration effects that shift the pressure required for the ice VIIIVII phase transition by roughly 10GPa.For both KDP and high-pressure ices, our simulations reveal the critical role of hydrogen-bond disordering and the accompanying local violations of the long-range order. Protons favor such violations more than deuterons, leading to pronounced isotope effects. In the case of the liquid water to ice Ih phase transition, we calculated the quantum correction to free energy differences using quantum thermodynamic integration. The predicted NQEs stabilize the solid phase instead of the liquid phase. The contradiction to experiments originates from the error in the adopted functional approximation. The finding underscores the possibility that the error in hydrogen-bond strength can lead to incorrect qualitative descriptions of weak NQEs.The methodology and physical insights presented in this study can be applied to investigating other hydrogen-bonded materials, preferably those known to exhibit strong isotope effects in experiments.
■590 ▼aSchool code: 0181.
■650 4▼aComputational chemistry
■650 4▼aComputational physics
■650 4▼aQuantum physics
■650 4▼aPhysical chemistry
■650 4▼aNuclear chemistry
■653 ▼aDeep learning
■653 ▼aFerroelectrics
■653 ▼aNuclear quantum effects
■653 ▼aPhase transition
■653 ▼aPotassium dihydrogen phosphate
■690 ▼a0219
■690 ▼a0216
■690 ▼a0599
■690 ▼a0494
■690 ▼a0738
■71020▼aPrinceton University▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-04B.
■790 ▼a0181
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17162499▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
