PMID- 32321268
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20200423
IS  - 1089-7690 (Electronic)
IS  - 0021-9606 (Linking)
VI  - 152
IP  - 15
DP  - 2020 Apr 21
TI  - Phonon-assisted proton tunneling in the hydrogen-bonded dimeric selenates of 
      Cs(3)H(SeO(4))(2).
PG  - 154502
LID - 10.1063/1.5145108 [doi]
AB  - In phases III and IV of Cs(3)H(SeO(4))(2), the vibrational state and intrabond 
      transfer of the proton in the dimeric selenates are systematically studied with a 
      wide range of absorbance spectra, a spin-lattice relaxation rate of (1)H-NMR 
      (T(1) (-1)), and DFT calculations. The OH stretching vibrations have extremely 
      broad absorption at around 2350 (B band) and 3050 cm(-1) (A band), which 
      originate from the 0-1 and 0-2 transitions in the asymmetric double minimum 
      potential, respectively. The anharmonic-coupling calculation makes clear that the 
      A band couples not only to the libration but also to the OH bending band. The 
      vibrational state (nano-second order) is observed as the response of the proton 
      basically localized in either of the two equivalent sites. The intrabond transfer 
      between those sites (pico-second order) yields the protonic fluctuation reflected 
      in T(1) (-1). Together with the anomalous absorption [nu(p2) phonon, libration, 
      tetrahedral deformation (delta(440)), and 610-cm(-1) band], we have demonstrated that 
      the intrabond transfer above 70 K is dominated by the thermal hopping that is 
      collectively excited at 610 cm(-1) and the phonon-assisted proton tunneling 
      (PAPT) relevant to the tetrahedral deformation [PAPT(def)]. Below 70 K, T(1) (-1) 
      is largely enhanced toward the antiferroelectric ordering and the distinct 
      splitting emerges in the libration, which dynamically modulates the O(2)-O'(2) 
      distance of the dimer. The PAPT(lib) associated with the libration is confirmed 
      to be a driving force of the AF ordering.
FAU - Matsui, Hiroshi
AU  - Matsui H
AUID- ORCID: 0000000274020755
AD  - Department of Physics, Graduate School of Science, Tohoku University, Sendai 
      980-8578, Japan.
FAU - Shimatani, Kazuki
AU  - Shimatani K
AD  - Department of Physics, Graduate School of Science, Tohoku University, Sendai 
      980-8578, Japan.
FAU - Ikemoto, Yuka
AU  - Ikemoto Y
AUID- ORCID: 0000000162660977
AD  - SPring-8, Japan Synchrotron Radiation Research Institute, Sayo, Hyogo 679-5198, 
      Japan.
FAU - Sasaki, Takahiko
AU  - Sasaki T
AUID- ORCID: 0000000207675428
AD  - Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan.
FAU - Matsuo, Yasumitsu
AU  - Matsuo Y
AUID- ORCID: 0000000349719326
AD  - Department of Life Science, Faculty of Science & Engineering, Setsunan 
      University, Neyagawa 572-8508, Japan.
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Chem Phys
JT  - The Journal of chemical physics
JID - 0375360
SB  - IM
EDAT- 2020/04/24 06:00
MHDA- 2020/04/24 06:01
CRDT- 2020/04/24 06:00
PHST- 2020/04/24 06:00 [entrez]
PHST- 2020/04/24 06:00 [pubmed]
PHST- 2020/04/24 06:01 [medline]
AID - 10.1063/1.5145108 [doi]
PST - ppublish
SO  - J Chem Phys. 2020 Apr 21;152(15):154502. doi: 10.1063/1.5145108.