Spectroscopic investigation of pressure-induced phase transitions in TCNQ complex salts |
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| Affiliation: | 1. Graduate School of Science and Technology, Kumamoto University, Kurokami 2-39-1, Kumamoto 860-8555, Japan;2. Department of Manufacturing System, Kumamoto Prefectural College of Technology, Haramizu 4455-1, Kikuyou-town, Kikuchi-gun, Kumamoto 869-1102, Japan;3. Department of Chemistry, Faculty of Science, Kumamoto University, Kurokami 2-39-1, Kumamoto 860-8555, Japan;1. Department of Pediatric Surgery, McGovern Medical School at the University of Texas Health Science Center at Houston and Children''s Memorial Hermann Hospital, Houston, TX;2. Center for Surgical Trials and Evidence-based Practice (CSTEP), University of Texas Medical School at Houston, Houston, TX;3. Department of Pediatric Surgery, Vanderbilt University School of Medicine, Nashville, TN;4. Department of Pediatric Surgery, University of Tennessee Health Science Center, Memphis, TN;1. Institute of Photogrammetry and GeoInformation, Leibniz University Hannover, 30167 Hannover, Germany;2. GFZ German Research Centre for Geosciences (GFZ), Department of Geodesy, Section of Remote Sensing and Geoinformatics, 14473 Potsdam, Germany;1. Shanxi Province Key Laboratory of Higee-Oriented Chemical Engineering, North University of China, Taiyuan, Shanxi 030051, China;2. State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, Ningxia University, Yinchuan 750021, China;1. Sir Peter Mansfield Imaging Centre, School of Physics and Astronomy, University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom;2. Centre for Translational Neuroimaging in Mental Health, Institute of Mental Health, School of Medicine, University of Nottingham, Jubilee Campus, Triumph Road, Nottingham, UK;3. Diagnostic Imaging, Hospital for Sick Children, 555 University Avenue, Toronto, Ontario M5G 1X8, Canada;4. Neurosciences and Mental Health Program, The Hospital for Sick Children Research Institute, Toronto M5G0A4, Canada;5. Department of Medical Imaging, University of toronto, Toronto M5T1W7, Canada;6. Oxford Centre for Human Brain Activity, Wellcome Centre for Integrative Neuroimaging, Department of Psychiatry, University of Oxford, United Kingdom;1. Center for Chronic Disease Outcomes Research, Minneapolis VA Health Care System, Minneapolis, USA;2. Division of General Internal Medicine, University of Minnesota, Minneapolis, USA;3. Division of Pulmonology, Minneapolis VA Health Care System, Minneapolis, USA;4. Division of Pulmonary, Allergy, Critical Care and Sleep Medicine, University of Minnesota, Minneapolis, USA;5. Pulmonary and Critical Care, Wayne State University, Detroit, USA |
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| Abstract: | In most of the TCNQ complex salts, conduction electrons are localized on specific TCNQ sites, so that these salts show nonmetalic behavior. The caesium salt, Cs2(TCNQ)3, is one of the 2:3 complex salts. In the crystal, TCNQ molecules form trimeric units, which consist of two TCNQ radical anion sandwiching a neutral TCNQ along the column. The rubidium salt, Rb2(TCNQ)3, also has a similar crystal structure to Cs2(TCNQ)3. We measured infrared absorption (IR) and Raman spectra for these salts under high pressure by using a diamond anvil cell. In the case of IR spectra, Cs2(TCNQ)3 showed a spectral change probably due to a pressure-induced phase transition. Similar feature was not clearly observed in the Rb2(TCNQ)3. On the other hand, the Raman spectra, Cs2(TCNQ)3 showed two phase transition at 2.5 and 4.1 GPa in the compression stage. The change from localization phase to delocalization phase occurred at latter transition with large hysteresis. Similar phase transition occurred at 3.2 GPa in the Rb2(TCNQ)3. The reason for the difference in transition pressure is that the ion radius of Rb+ is smaller than that of Cs+, because a small ion radius of the counter ion probably favors the charge localization-delocalization transition of the TCNQ column. |
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