3P136Ề⣪⤎ྙ⣌ࡡ㉝አྺ཭ࢪ࣋ࢠ ࢹࣜࡡ አ㒂㞹ሔຝᯕ໪ኬ㞹Ꮔ◂ ‫ې‬୯ᯐᏏ࿰࣬ኯ⏛ಘᗽ(e-mail: takan@es.hokudai.ac.jp)࠘ᗆ࠙ ᠻࠍࡢ㞹Ꮔທ㉫≟ឺࡡකᏕ≁ᛮࡡῼᏽ࠽ࡻࡦකທ㉫ࢱ࢕ࢻ࣐ࢠࢪࡡ࣒࢜ࢼࢫ࣑ࡡレ⣵ࢅ᪺ࡼ࠾࡞ࡌࡾࡆ࡛ࢅ┘Ⓩ࡛ࡊ࡙㸡ฦᏄཀྵࡦฦᏄ㞗ᅆࡡ⣰አ࣬ྊっ㡷ᇡ࡞࠽ࡄࡾ㞹Ꮔྺ཭࠽ࡻࡦ⺧කࢪ࣋ࢠࢹࣜࡡአ㒂㞹ሔຝᯕࢅῼᏽࡊ࡙࠷ࡾ 1,2)ࠊᮇ◂✪࡚ࡢ㸡㉝አᇡࡱ࡚㡷ᇡࢅᣉᘿࡊ㸡አ㒂㞹ሔ༰ຊ࡞ఔ࠹㉝አྺ཭ࢪ࣋ࢠࢹࣜࡡን໩(㉝አ㞹ሔྺ཭ࢪ࣋ࢠࢹࣜ)࡞ࡗ࠷࡙᳠
ゞࢅ⾔ࡖࡒ 3)ࠊ㉝አྺ཭ࢪ࣋ࢠࢹࣜࡡአ㒂㞹ሔຝᯕ࡞ࡗ࠷࡙ࡢ㸡ฦᏄᵋ㏸ࢅㄢ࡬ࡾ᩺ࡒ࡝ฦ
කᏕⓏᡥἪ࡛ࡊ࡙Ἰ┘ࢅ㞗ࡴ࡙࠷ࡾ 4–6)ࠊᠻࠍࡢࢰࣤࣂࢠ㈻࡝࡜ࡡ⏍మ⣌࡞ᑊࡊ࡙ᚺ⏕ࢅ⾔࠷㸡⏍మฦᏄ࡝࡜࡞࠽ࡄࡾ᩺ࡒ࡝ᵋ㏸᝗ሒࢅᚋࡾࡆ࡛ࢅ┘Ⓩ࡛ࡊ࡙࠷ࡾࠊ

࠘ᐁ㥺࠙ ㉝አ㞹ሔྺ཭ࢪ࣋ࢠࢹࣜࡡῼᏽ࡞ࡢ SNIFTIRS(Subtractively Normalized Interfacial
FT-IR spectroscopy)ࢅᮇ◂✪࡚ࡢ⏕࠷࡙࠷ࡾ 4,5)ࠊDC 㞹ሔ (0.2–1.5 MV cm–1)࠿ ON ࡡ࡛ࡀࡡ㉝
አྺ཭ࢪ࣋ࢠࢹ࡛ࣜ OFF ࡡ࡛ࡀࡡࢪ࣋ࢠࢹࣜࢅஹப࡞ῼᏽࡊ㸡ࡐࡿࡑࡿ✒⟤ࢅ⾔࠹ࠊON ࡛OFF ࡡ㉝አྺ཭ࢪ࣋ࢠࢹࣜࡡẒࡡᖏ⏕ᑊᩐࢅゝ⟤ࡌࡾࡆ࡛࡞ࡻࡽ㸡㉝አ㞹ሔྺ཭ࢪ࣋ࢠࢹࣜ(ON–OFF)ࢅᚋࡾࡆ࡛࠿࡚ࡀࡾࠊ㧏ฦᏄ⭯モᩩࡢ㸡༖㏩᪺࢓࣐ࣜࢼ࣑ࢗ࠿ⵠ╌ࡈࡿࡒ CaF2 ᇱᯀ୕࡞࢞ࣔࢪࢹἪ࡞ࡻࡖ࡙ࣚࣤࢱ࣑㒼ྡྷ࡛࡝ࡾࡻ࠹࡞షᠺࡊࡒࠊషᠺࡊࡒ㧏ฦᏄ⭯୕࡞ࡈࡼ
࡞༖㏩᪺࢓࣐ࣜࢼ࣑ࢗࢅ┷✭ⵠ╌ࡈࡎ㸡㸧ࡗࡡ࢓࣐ࣜࢼ࣑ࢗ㛣࡞㞹ᅸࢅ༰ຊࡊࡒࠊFIB
㸝Focused Ion Beam㸞ຊᕝ࡛ SEM ふᐳ࡞ࡻࡖ࡙⭯ཉࢅフ౮ࡊࡒ(NSG Techno-Research Co.)ࠊ

࠘⤎ᯕ࡛⩻ᐳ࠙ Fig. 1 ࡞࣎ࣛ-γ-࣊ࣤࢩࣜ-L-ࢡࣜࢰ࣒࣭ࢹ(PBLG)ࡡ㉝አ㞹ሔྺ཭ࢪ࣋ࢠࢹࣜࢅ♟ࡌࠊPBLG ࡢࢰࣤࣂࢠ㈻࡛ྜྷࡋࡂ࣋ࣈࢲࢺᇱࢅ㦭᰹࡞ᣚࡗྙᠺ㧏ฦᏄ࡚࠵ࡽ㸡ᖲᆍฦᏄ㔖ࡷ⭯ࡡషᠺ᪁Ἢ࡞ᚉ࠷ᵕࠍ࡝❟మᵋ㏸ࢅᙟᠺࡌࡾࡆ࡛࠿▩ࡼࡿ࡙࠷ࡾࠊ࢓࣐ࢺࣁࣤࢺࡡἴᩐన⨠࠾ࡼ㸡ᮇ◂✪࡞⏕࠷ࡒ㧏ฦᏄ⭯ࡢ α-ࣉࣛࢴࢠࢪࡡ❟మᵋ㏸ࢅᙟᠺࡊ࡙࠷ࡾ࡛⩻࠻ࡼࡿࡾ 7)ࠊふῼࡈࡿࡒ㉝አ㞹ሔྺ཭ࢪ࣋ࢠࢹࣜࡢ㏳ᖏࡡ㉝አྺ཭ࢪ࣋ࢠࢹ࡛ࣜࡢᙟ≟࠿ኬࡀࡂ␏࡝ࡽ㸡྘ᣲິࣁࣤࢺ࠿≁᭯ࡡ㞹ሔຝᯕࢅ♟ࡊ࡙࠷ࡾࡆ࡛࠿ࢂ࠾ࡾࠊ
 Liptay ࡼࡡᏽᘟ໩࡞ࡻࡿࡣ㸡ࣚࣤࢱ࣑㒼ྡྷ⣌࡞࠽ࡄࡾྺ཭ࢪ࣋ࢠࢹࣜࡡ㞹ሔຝᯕ(A(ν))ࡢ㸡ྺ཭ࢪ࣋ࢠࢹࣜࡡ 0 ḗ᚜ฦ㸡1 ḗ᚜ฦ㸡2 ḗ᚜ฦࡡ⥲ᙟ⤎ྙ࡚⾪ࡌࡆ࡛࠿࡚ࡀࡾ 8)ࠊ
ΔA( ν) = (fF)2[A'A( ν)+B'ν{d(A( ν)/ν)/d ν}+C'ν{d2(A( ν)/ν)/d ν2}]

(1)F ࡢአ㒂㞹ሔ㸡f ࡢහ㒂㞹ሔ⿭ḿᅄᏄ࡚࠵ࡾࠊ౿ᩐ A'ࡢฦᏄࡡ㐼⛛ฦᴗ⋙࠽ࡻࡦฦᏄࡡ㒼ྡྷ࡞౪Ꮛࡊ㸡B'ࡢකທ㉫࡞ఔ࠹ฦᏄฦ
ᴗ⋙ࡡን໩(Δα )࡞୹࡞౪ᏋࡌࡾࠊC'ࡢකທ㉫࡞ఔ࠹ཫᴗᏄ࣓࣭࣒ࣤࢹࡡን໩(Δµ )࡞
౪Ꮛࡊ㸡ḗᘟ࡚⾪ࡌࡆ࡛࠿࡚ࡀࡾࠊ
C' = |Δµ |2[5+(3cos2ξ-1)(3cos2χ-1)]/(30h2c2) (2)ᘟ(2)࡞࠽࠷࡙㸡χࡢΔµ ࡛አ㒂㞹ሔ࡛ࡡ㛣ࡡ

Fig. 1. (a) IR absorption spectrum and (b) IR E-A spectrum ofPBLG. Applied field strength was 0.6 MV cm–1.

みᗐ㸡ξࡢΔµ ࡛㐼⛛࣓࣭࣒ࣤࢹ࡛ࡡ㛣ࡡみᗐ࡚࠵ࡾࠊ Fig. 2 ࡞♟ࡌࡻ࠹࡞㸡྘ᣲິࣁࣤࢺࡡ㉝አ㞹ሔྺ཭ࡡᙁᗐࡢ༰ຊ㞹ሔ࡞ᑊࡊ࡙ 2 ஋ࡡን໩ࢅ
♟ࡊ࡙࠷ࡾࠊᘟ(1)ࢅ⏕࠷࡙㸡㉝አ㞹ሔྺ཭ࢪ࣋ࢠࢹࣜࢅ්⌟ࡊࡒ⤎ᯕࢅ Fig. 3 ࡞♟ࡌࠊ྘ᣲິࣁࣤࢺࡢ㸡0 ḗ᚜ฦ㸡1 ḗ᚜ฦ㸡2 ḗ᚜ฦࡡ⥲ᙟ⤎ྙ࡚⾪ࡌࡆ࡛࠿࡚ࡀ㸡ᘟ(1)࠿࣎ࣛ࣋ࣈࢲ
ࢺࡡ㉝አ㞹ሔྺ཭࡞ࡵ㐲⏕࡚ࡀࡾࡆ࡛࠿ࢂ࠾ࡾࠊ୹㙈ࡡᣲິࡡ㉝አ㞹ሔྺ཭ࢪ࣋ࢠࢹࣜ࡞࠽࠷࡙ࡢ㸡N-H ఘ⦨ᣲິࣁࣤࢺ(3291 cm–1)࡛࢓࣐ࢺ I ᣲິࣁࣤࢺ(1653 cm–1)ࡡ㉝አ㞹ሔྺ཭ࢪ࣋
ࢠࢹࣜ࠿ྺ཭ࢪ࣋ࢠࢹࣜࡡ 2 ḗ᚜ฦ࡛ྜྷᵕࡡᙟ≟ࢅ♟ࡊ࡙࠷ࡾࠊᣲິທ㉫࡞ఔ࠹ཫᴗᏄ࣓࣭࣒ࣤࢹࡡን໩࠿㸡ࡆࡿࡼࡡᣲິࣁࣤࢺࡡ㞹ሔን໩࡞ᑊࡊ࡙ᨥ㒼Ⓩ࡚࠵ࡾࡆ࡛࠿ࢂ࠾ࡾࠊୌ᪁㸡ྜྷࡋ୹㙈ࡡᣲິ࡚࠵ࡾ࢓࣐ࢺ II ࣁࣤࢺ࡞ࡗ࠷࡙ࡢ㸡0 ḗ᚜ฦ࡛ 1 ḗ᚜ฦࡡᐞ୙ࡵኬࡀ࠷ࡆ࡛
࠿ࢂ࠾ࡾࠊഁ㙈ࡡᣲິ࡞ࡗ࠷࡙ࡢ㸡࢙ࢪࢷࣜࡡ C=O ఘ⦨ᣲິࣁࣤࢺ(1734 cm–1)ࡡን໩㔖࠿㟸ᖏ࡞ኬࡀ࠷ࡆ࡛࠿ࢂ࠾ࡾ(Fig. 1)ࠊC=O ఘ⦨ᣲິࡡ㉝አ㞹ሔྺ཭ࢪ࣋ࢠࢹࣜࡢୌḗ᚜ฦࡡᙟ≟ࢅ♟ࡊ࡙࠷ࡾࠊᣲິທ㉫࡞ఔ࠹ฦᏄฦᴗ⋙ࡡን໩࠿㸡௙ࡡᣲິ࡞Ẓ࡬࡙㟸ᖏ࡞ኬࡀ࠷ࡆ࡛࠿
♟ြࡈࡿࡾࠊࣆ࢘ࢼࣜᇱࡡ C–C ఘ⦨ᣲິࣁࣤࢺ(1454 cm–1)ࡵྜྷᵕ࡞ୌḗ᚜ฦࡡᙟࢅ♟ࡌࡡ࡞ᑊࡊ㸡࢙ࢪࢷࣜࡡ C–O ఘ⦨ᣲິࣁࣤࢺ(1169 cm–1)ࡢ 0 ḗ᚜ฦ࠿ᨥ㒼Ⓩ࡚࠵ࡖࡒࠊ ᣲິᇱᗇ≟ឺ࡛ᣲິທ㉫≟ឺ࡛ࡡཫᴗᏄ࣓࣭࣒ࣤࢹࡡᕣΔ µ ࡢ㸡ᘟ(2)ࢅ⏕࠷࡙ゝ⟤ࡌࡾࡆ࡛࠿࡚ࡀࡾࠊN-H ఘ⦨㸡࢓࣐ࢺ I㸡࢙ࢪࢷࣜࡡ C=O ఘ⦨ᣲິࣁࣤࢺࡡ|Δµ |ೋࡢ㸡ࡐࡿࡑࡿ 0.11㸡
0.05㸡0.06 D/f ࡚࠵ࡖࡒࠊ௙ࡡᣲິࣁࣤࢺࡡ|Δµ |ೋࡢ㸡0–0.03 D/f ࡡ⠂ᅑහ࡞ྜྷᵕ࡞ぜ✒ࡼࡿࡾࡆ࡛࠾ࡼ㸡N-H ఘ⦨ᣲິࣁࣤࢺࡡ|Δµ |ೋࡢ㸡௙ࡡᣲິࣁࣤࢺ࡞Ẓ࡬࡙࠾࡝ࡽኬࡀ࡝ೋࢅᣚࡔ㸡ᣲິທ㉫࡞ఔ࠹ཫᴗᏄ࣓࣭࣒ࣤࢹࡡን໩࠿㟸ᖏ࡞ኬࡀ࠷ࡆ࡛࠿ࢂ࠾ࡾࠊ࢙ࢪࢷࣜࡡ C=O ఘ⦨ᣲິࣁࣤࢺࡡΔ α ೋࡢ࠽ࡻࡐ 2 Å3/f 2 ࡛ぜ✒ࡾࡆ࡛࠿࡚ࡀࡒࠊࡊ࠾ࡊࡻࡽᏽ㔖Ⓩ࡝ೋࢅᚋࡾࡒࡴ࡞ࡢχ౪Ꮛᛮࡡῼᏽ࠿ᚪさ࡚࠵ࡾࠊ 㸥ḗ᚜ฦࡢአ㒂㞹ሔ࡞ࡻࡾ㧏ฦᏄࡡഷ࠾࡝㒼ྡྷን໩࠿ཋᅄ࡚࠵ࡾ࡛⩻࠻ࡼࡿࡾࠊഁ㙈ࡡᣲິࣁࣤࢺ࠿୹㙈ࡡᣲິࣁࣤࢺ࡞Ẓ࡬࡙ 0 ḗ᚜ฦࡡᐞ୙࠿ኬࡀ࠷ࡆ࡛࠾ࡼ㸡አ㒂㞹ሔ࡞ࡻࡾ㒼ྡྷን໩ࡢഁ㙈ࡡ᪁࠿ኬࡀ࠷ࡆ࡛࠿ࢂ࠾ࡾࠊࡆࡡ㒼ྡྷን໩ࡢ㧏ฦᏄࡡㄇ㞹⋙ࡡ㒼ྡྷฦᴗࡐࡡࡵࡡ࡚࠵ࡾࡆ
࡛࠾ࡼ㸡㉝አ㞹ሔྺ཭ࡡ 0 ḗ᚜ฦࡡ㡧ࢅよᯊࡌࡾࡆ࡛࡞ࡻࡖ࡙㸡㧏ฦᏄࡡㄇ㞹⋙ࡡฦᏄࣝ࣊ࣜࡡ᝗ሒࢅ
ᚋࡾࡆ࡛࠿࡚ࡀࡾࠊ

Fig. 2. Plots of the field-induced change in IR absorption
intensity of PBLG as a function of the square of the field strength.

Fig. 3. IR E-A spectrum (shaded line) and IR
absorption spectrum (solid line) of PBLG around six
prominent band regions.
The simulated IR E-A
spectrum is also shown by a dotted line in every case.

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127 (2005) 7041. 3) T. Nakabayashi, and N. Ohta, Chem. Lett., in press. 4) S. S. Andrews and S. G. Boxer, J. Phys.
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6) H. Hiramatsu and H. Hamaguchi, Appl. Spectrosc. 58 (2004) 355. 7) T. Miyazawa and E. R. Blout, J. Am. Chem. Soc.,
83 (1961) 712. 8) W. Liptay, in "Excited States," ed. by E. C. Lim, Academic Press, New York (1974), Vol. 1, p. 129.