1E20ィ⟬ศᏊศගᏛ䠖ᮍ▱ᫍ㛫ศᏊೃ⿵ 㻲㼑㻻㻴 䛾㟁Ꮚᵓ㐀䛸㻌᣺ືᅇ㌿䝇䝨䜽䝖䝹࠾Ⲕ኱⌮ 1, ⏘⥲◊࣭ィ⟬⛉Ꮫ㒊㛛 2㸪NRC (࢝ࢼࢲ) 3, Wuppertal ኱Ꮫ (ࢻ࢖ࢶ) 4

ᖹ㔝 ᜏኵ 1, 2㸪‫ۑ‬㛗ᔱ 㞼ර 2㸪Philip R. Bunker 3㸪Per Jensen 4
FeOH ࡣࠊFeCOࠊFeCN/FeNC ࡞࡝࡜ඹ࡟ Fe ࢆྵࡴᫍ㛫ศᏊೃ⿵࡜ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿࡶࡢࡢࠊᮍࡔ࡟ศගᏛᐇ㦂࡟㛵ࡍࡿሗ࿌ࡀ↓࠸ᮍ▱ศᏊ࡛࠶ࡿࠋࡑࡇ࡛ࠊศගᏛᐇ㦂࡟㈨ࡍࡿࡇ࡜ࢆ㢪ࡗ࡚ࠊศගᏛ⢭ᗘࡢ ab initio ィ⟬ࢆ⾜ࡗ࡚㟁Ꮚᵓ㐀ࢆゎ᫂ࡋࠊ᣺ືᅇ㌿ࢫ࣌ࢡࢺࣝࡢࢩ࣑࣮ࣗࣞࢩ
ࣙࣥࢆ⾜࠺ᚲせࡀ࠶ࡿ࡜⪃࠼ࡓࠋFeOH ࡢ Fe ࡣᚋ㏙ࡢࡼ࠺࡟ࠊFe+࡜ࡋ࡚㓄఩Ꮚ OH!࡜࢖࢜ࣥ⤖ྜ࡛⤖ࡤࢀ࡚࠸ࡿศᏊ࡞ࡢ࡛ࠊFe+ ࡟࠾ࡅࡿ⦰㏥ࡀ FeOH ࡟࡞ࡗ࡚ࡶᗄศ࠿ṧࡗ࡚࠾ࡾࠊᨃ⦰㏥ࢆ
⪃៖ࡋࡘࡘ symmetry adapted ࡞ィ⟬ࢆ⾜࠺ࡼ࠺࡟㓄៖ࡋ࡚ࠊ3 ḟඖ࣏ࢸࣥࢩ࢚ࣕࣝࢿࣝࢠ࣮᭤㠃(PES)ࠊ཮ᴟᏊ⬟⋡ࠊ㑄⛣཮ᴟᏊ⬟⋡㛵ᩘࢆồࡵࠊ᣺ືᅇ㌿ࡢ Schrödinger ᪉⛬ᘧࢆゎ࠸࡚᣺ືᅇ㌿ࢫ࣌ࢡࢺࣝࡢࢩ࣑࣮ࣗࣞࢩࣙࣥࢆ⾜ࡗࡓࠋィ⟬࡟ࡣࠊMOLPRO 2006.1 ࢆ౑࠸ࠊᇶᗏ㛵ᩘ࡜ࡋ࡚ Fe ࡟ࡣ Roos ANOࠊO ࡜ H ࡟ࡣ aug-cc-pVQZ
ࢆ⏝࠸ࡓࠋ3 ḟඖ PES ࡣ Cs ᑐ⛠ࡢୗ࡛ 5 ≧ែ㸦A’ 3 ≧ែࠊA’’ 2 ≧ែ㸧ᖹᆒࡢ CASSCF ࢆ⾜࠸ࠊࡑࡢ⮬↛㌶㐨䠄NO䠅䛻ᇶ䛵䛔䛶 MR-SDCI䠇Q䠄Davidson 䛾⿵ṇ䠅ィ⟬䜢⾜䛳䛯ᚋ䚸Cowan-Griffin 䛾᪉ἲ䛷┦ᑐㄽⓗ䜶䝛䝹䜼䞊䠄Erel䠅䜢⿵ṇ䛧䛶ồ䜑䛯䚹㻌
FeOH ࡢᇶᗏ≧ែ !" ࡢᖹ⾮ᵓ㐀ࡣbent ᆺࡢ 6A’࡛ࠊre(Fe-O) = 1.806 Åࠊre (O-H) = 0.952 Åࠊ"e(Fe-O-H㸧 = 134.2°ࠊspin-㌶㐨┦஫స⏝ᐃᩘ ASO = !85 cm-1ࠊ㟁ሙᚤศ࡜ࡋ࡚ồࡵࡓ཮ᴟᏊ⬟⋡ࡣ 1.37 D (ᮇᚅ್ࡣ 1.43 D)࡛࠶ࡿࠋFe-O 㛫ࡢ࢖࢜ࣥ⤖ྜᛶ࠿ࡽᮇᚅࡉࢀࡿࡼ࠺࡟ࠊኚゅ᣺ື࣏ࢸࣥࢩࣕࣝࡣ shallow ࡛኱᣺ᖜኚゅ᣺ືࢆ♧ࡍࡀࠊ┤⥺ᵓ㐀ࡢ࡜ࡇࢁ࡟㞽Ⅼ᣺ື 194 cm-1 ࡼࡾࡸࡸ㧗࠸273 cm-1 ࡢࣂࣜ࢔࣮ࢆᣢࡘࡢ࡛ !" ≧ែࡶ Ã ≧ែࡶ͆quasi-linear”࡛࠶ࡾࠊ!" ≧ែࡣ඲ᇦ࡟΅ࡗ࡚➨㸯ບ㉳≧ែ㸦Renner ຠᯝࡢ∦Წ㸧Ã 6A”࡜࡯ࡰ⦰㏥ࡋ࡚࠸ࡿ㸦ᅗ㸯(a)㸧ࠋࡇࡢ FeOH ࡢᇶᗏ≧ែࡢᖹ⾮ᵓ㐀࡟㛵ࡋ࡚ࡣࠊ
Caoa ࡣࠊ࡯ࡰྠࡌࣞ࣋ࣝࡢ MR-ACPF_DK2 ࡟ࡼࡿィ⟬࡟ࡼࡗ࡚┤⥺ᵓ㐀ࡢ 6#࡛࠶ࡿ࡜୺ᙇࡋ࡚࠸ࡿࡀࠊࡇࢀࡣࠊ㠀┦ᑐㄽࡢࡶ࡜࡛᭱㐺໬ࡋࡓᇶᗏ㛵ᩘࢆ Douglas-Kroll (DK) ┦ᑐㄽࣁ࣑ࣝࢺࢽ࢔࡛ࣥ
౑⏝ࡋ࡚࠸ࡿࡓࡵࡢ artifact ࡛࠶ࡿࠋ ᅗ 1(b) ࡟♧ࡍࡼ࠺࡟ࠊDK ࢆ౑࠺࡞ࡽ DK ࡛᭱㐺໬ࡋࡓᇶᗏ㛵ᩘࢆ౑࠺࡭ࡁ࡛࠶ࡗ࡚ࠊࡑ࠺ࡍࢀࡤࠊᡃࠎࡢ⤖ㄽ࡜ྠࡌࡃ bent ᆺࡢ 6A’ᖹ⾮ᵓ㐀࡟࡞ࡿࠋ
FeOH ࡢ !" ≧ែࡶ Ã ≧ែࡶࠊ࡯ࡰ 1 㓄⨨࡛グ㏙࡛ࡁࡿ㸦ࡋ࠿ࡋࠊsymmetry-broken ࡢゎ࡟࡞ࡽ࡞࠸
ࡼ࠺࡟ࠊᑡ࡞ࡃ࡜ࡶ 2 㓄⨨ࡢィ⟬ࢆ⾜࠺ᚲせࡀ࠶ࡿ㸧ࠋࡇࡢ୺㓄⨨ࡢ 10a’ࡢ NO ࡣ༨᭷ᩘ 2 ࡢ$%OH

ᅗ 1 MR-SDCI+Q+Erel ࡛ࣞ࣋ࣝࡢኚゅ PES

㌶㐨࡞ࡢ࡛ࠊOH ⤖ྜࡣ ඹ ᭷⤖ ྜ࡛ ࠶ ࡿࠋFe ࡢ㛵୚ࡍࡿ NO ࢆࡳࡿ࡜ࠊ3d64s1 ࡢ㟁Ꮚᵓ㐀 ࢆ ࡜ࡗ ࡚࠸ ࡚ ࠊ Feࡢ Mulliken 㟁 Ⲵ ࡣ+083 ࡛࠶ࡿࡇ࡜࡜ྜ
ࢃࡏࡿ࡜ࠊFeOH ࡢ Fe
ࡣ a 6D ࡢ Fe+࡟⏤᮶ࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡿࠋࡲࡓࠊvalence ࡢ NO ࡟ࡣࠊFe-O ࡢඹ᭷⤖ྜᛶ࡟ᐤ୚ࡍࡿ NO ࡣぢᙜࡽ ࡞ ࠸ ࡢ ࡛ ࠊ Fe 㸩 ࡜OH!ࡣ࢖࢜ࣥ⤖ྜ࡛⤖ࡤ ࢀ ࡚࠸ ࡿ࡜ ⤖ ㄽ࡛ࡁࡿࠋ

ᅗ 2 Predicted spectra of the 6A’ (6#) FeOH Renner-degenerate states (at 10 K).

ᚓࡽࢀࡓ 3 ḟඖࡢ PESࠊ཮ᴟᏊ⬟⋡ࠊ㑄⛣཮ᴟᏊ⬟⋡㛵ᩘࢆ⏝࠸࡚ࣉࣟࢢ࣒ࣛ RENNER ࡟ࡼࡗ࡚ண ࡋࡓࠊJ ! 21/2, T = 10 K ࡢࢫ࣌ࢡࢺࣝࢆᅗ 2 ࡟♧ࡍࠋ
FeOH ࡟࠾ࡅࡿ Renner ศ⿣ࡣᴟࡵ࡚ᑠࡉ࠸ࡢ࡛ࠊ!" ≧ែ࡜ Ã ≧ែ࡜ࡢᖹᆒ PES ࡟ᑐࡋ࡚ࠊMORBID ࣉࣟࢢ࣒ࣛ࡟ࡼࡾ᣺ືᅇ㌿ࡢ Schrödinger ᪉⛬ᘧࢆゎ࠸࡚ࠊࡑࡢἼື㛵ᩘࡢᮇᚅ್࡜ࡋ࡚᣺ືᅇ㌿ࢆྲྀࡾ㎸ࢇࡔሙྜࡢศᏊᵓ㐀ࢆồࡵࡓࠋࡇ࠺ࡋ࡚ồࡵࡓ r0 ᵓ㐀ࡣࠊ<r(Fe-O)>0 = 1.806 Åࠊ<r(O-H)>0 = 0.952 Åࠊ<"(Fe-O-H)>0 = 134.2° ࡜࡞ࡾࠊᖹ⾮ᵓ㐀࡟ᴟࡵ࡚㏆࠸ࠋࡇࡢ<r(O-H)>0 ࡢ್ࡣࠊ඾ᆺⓗ࡞ඹ᭷⤖ྜᛶࡢ H2O ศᏊࡢ⤖ྜ㊥㞳࡜࡯ࡰ୍⮴ࡍࡿࠋࡲࡓࠊࡇࡢศᏊࡢ a-㍈࡟ᢞᙳࡋࡓࠊFe-O ࠾ࡼࡧ O-H ࡢ r0 ⤖ྜ㊥㞳ࡣࠊࡑࢀࡒࢀࠊ1.805 Åࠊ0.732 Å ࡜࡞ࡿࠋࡇࢀࡣࠊH ࡀ Fe ࡸO ࡟㍑࡭࡚ᴟࡵ࡚㍍࠸ࡓࡵࠊኚゅ᣺ື࣮ࣔࢻ࡛ࡣࠊFe-O ⤖ྜࡣᖖ࡟ศᏊࡢ a ㍈࡜ࠕ࡯ࡰ୍⮴ࠖࡋ࡚࠸࡚ࠊO-H ⤖ྜࡣࡑࡢ㔜ᚰ㸦O ࡢ఩⨨࡟ᴟࡵ࡚㏆࠸㸧ࢆ୰ᚰ࡟ኚゅ᣺ືࡋ࡚࠸ࡿࡓࡵ࡛࠶ࡿࠋ
ᚑࡗ࡚ࠊᚑ᮶ࠊࡋࡤࡋࡤᐇ㦂ࢧ࢖ࢻ࡛⾜ࢃࢀ࡚࠸ࡁࡓ㢮ࡢ quasi-linear ࡢྲྀࡾᢅ࠸࡛ࡣࠊ࡜࡚ࡘࡶ࡞ࡃ▷࠸ O-H ⤖ྜ㊥㞳㸦0.73 Å㸧࡟࡞ࡗ࡚ࡋࡲ࠺ࠋࡇࡢࡇ࡜ࡣࠊ኱᣺ᖜኚゅ᣺ືࢆ♧ࡍ࢖࢜ࣥᛶ
ࡢ FeNCbࠊFeCNcࠊCoCNdࠊNiCNe, BrCN+ f ࡢ◊✲࡛⧞ࡾ㏉ࡋᣦ᦬ࡋࡓࡇ࡜࡛࠶ࡿࠋ
FeOH ࡣࠊኚゅ࣏ࢸࣥࢩࣕࣝࡀ shallow ࡛࠶ࡗ࡚ࡶࠊ┤⥺ᵓ㐀ࡢሙᡤ࡟㞽Ⅼ᣺ືࡼࡾࡸࡸ㧗࠸barrier ࢆ᭷ࡍࡿࡢ࡛ quasi-linear ࡞ศᏊ࡛࠶ࡿࠋ኱஦࡞ࡇ࡜ࡣࠊquasi-linear ࡜ྡࡀࡘ࠸࡚࠸࡚ࡶࠊ᣺ືᅇ㌿ࢆ⪃៖ࡋࡓᖹᆒᵓ㐀ࡣ bent ᆺ࡛࠶ࡗ࡚ࠊࡑࡢᖹ⾮ᵓ㐀㸦࣏ࢸࣥࢩࣕࣝᴟᑠ㸧ࡢ㏆ഐ࡟᭱኱Ꮡᅾ☜⋡ࢆᣢࡗ࡚࠸ࡿࠊ࡜࠸࠺ࡇ࡜࡛࠶ࡿࠋྠࡌ኱᣺ᖜኚゅ᣺ືࢆ♧ࡍ linear ࡞ศᏊ㸦ᖹ⾮ᵓ㐀ࡀ┤⥺ᆺ㸧࡛࠶ࡿ FeNCࠊCoCNࠊNiCN, BrCN+࡞࡝࡛ࡣࠊࡸࡣࡾ bent ᆺ࡟࡞ࡿࡀࠊ┤⥺࡟㏆࠸ᡤࠊࡘࡲࡾ⤖ྜゅ࡛ 170 ᗘ఩ࡢᡤ࡟᭱኱Ꮡᅾ☜⋡ࢆᣢࡘࡢ࡜ᑐ↷ⓗ࡛࠶ࡿࠋ Linear ࡞ศᏊ࡜ࠊquasi-linear ࡞ศᏊࡣࠊ␗࡞ࡿᣲືࢆࡍࡿ࡜࠸࠺ࡇ࡜࡛࠶ࡿࠋa

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c

T. Hirano, M. Amano, Y. Mitsui, S.S. Itono, R. Okuda, U. Nagashima, and P. Jensen, J. Mol. Spectrosc.,

243, 267 (2007).

dT. Hirano, R. Okuda, U. Nagashima, and P. Jensen, Mol. Phys., 105, 599 (2007).

U. Nagashima, and P. Jensen, J. Mol. Spectrosc., 250, 33, (2008).
Tanaka, P. Jensen, J. Mol. Spctrosc., 243, 202 (2007).

fe

T. Hirano, R. Okuda,

T. Hirano, R. Okuda, U. Nagashima, Y. Nakashima, K.